JP2010095709A - Epoxy resin composition for sealing and electronic parts device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an epoxy resin composition for sealing in which adhesion with a noble metal like Ag or Au is good, reflow resistance is good, and flame retardancy is good without reducing dependability such as moldability, moisture resistance, elevated temperature neglect characteristics or the like, and to provide an electronic parts device equipped with an element which is sealed by the same. <P>SOLUTION: The epoxy resin composition for sealing includes: (A) an epoxy resin; and (B) a hardener, wherein the content of (A1) an epoxy resin shown by general formula (I) is 30 mass% or more based on (A) the whole amount of epoxy resin. In the formula, R<SP>1</SP>-R<SP>5</SP>are each selected from a hydrogen atom, a 1-6C alkyl group and a 1-2C alkoxy group and are the same as or different from each other, and n denotes an integer. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

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. As a result, the resin-encapsulated semiconductor devices are mainly in the surface mount type package from the conventional pin insertion type package. Surface-mounted ICs, LSIs, etc. are thin and small packages in order to increase the mounting density and reduce the mounting height. For this reason, the area occupied by the package of the element has increased, and the thickness of the package has become very thin. Furthermore, these packages are different in mounting method from the conventional pin insertion type.

  That is, since the pin insertion type package is soldered from the back side of the wiring board after the pins are inserted into the wiring board, the package is not directly exposed to high temperature. However, surface mount ICs are temporarily attached to the surface of a wiring board and processed by a solder bath, a reflow device, or the like, so that they are 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 hygroscopicity, there is a strong demand for improvement in adhesion and adhesion to different interfaces such as lead frames (Cu, Ag, Au) and chip interfaces. In order to meet these requirements, various studies have been made from the epoxy resin side as a main material, and for example, a method using a biphenyl type epoxy resin has been studied (for example, Patent Document 1).

JP-A 64-65116

However, when the biphenyl type epoxy resin is used, it is difficult to balance physical properties due to molding failure due to a decrease in flame retardancy and a decrease in curability.
The present invention has been made in view of such circumstances, and has good adhesion and reflow resistance to metals such as Cu and PPF (core material: copper alloy, three-layer (Ni / Pd / Au) plated product). An epoxy resin composition for sealing having good flame retardancy without degrading moldability, 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 a sealing epoxy resin composition containing a specific epoxy resin, and the present invention has been completed. It came to do.
The present invention relates to the following.

（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は整数を示す。）
（２）前記（Ａ）エポキシ樹脂が、更に（Ａ２）下記一般式（ＩＩ）で示されるエポキシ樹脂を含有する上記（１）に記載の封止用エポキシ樹脂組成物。

（ここで、Ｒ^１〜Ｒ^８は水素原子、置換基を有する炭素数１〜１０の一価の炭化水素基、及び非置換の炭素数１〜１０の一価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い。ｎは０〜３の整数を示す。） (1) In an epoxy resin composition for sealing containing (A) an epoxy resin and (B) a curing agent, (A1) the content of the epoxy resin represented by the following general formula (I) is the above (A) epoxy The epoxy resin composition for sealing which is 30 mass% or more with respect to the whole resin.

(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 or different. N represents an integer. .)
(2) The sealing epoxy resin composition according to (1), wherein the (A) epoxy resin further contains (A2) an epoxy resin represented by the following general formula (II).

(Here, R ^{1 to} R ⁸ are a group consisting of a hydrogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms having a substituent, and an unsubstituted monovalent hydrocarbon group having 1 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は整数を示す。）

（ここで、Ｒ^１〜Ｒ^８は水素原子、置換基を有する炭素数１〜１０の一価の炭化水素基、及び非置換の炭素数１〜１０の一価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い。ｎは０〜３の整数を示す。） (3) In an epoxy resin composition for sealing containing (A) an epoxy resin and (B) a curing agent, the (A) epoxy resin comprises (A1) an epoxy resin represented by the general formula (I) and (A2 ) An epoxy resin composition for sealing containing an epoxy resin represented by the following general formula (II), wherein the content of (A2) is 5 to 70% by mass with respect to the sum of (A1) + (A2) .

(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 or different. N represents an integer. .)

(Here, R ^{1 to} R ⁸ are a group consisting of a hydrogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms having a substituent, and an unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms. All may be the same or different, and n represents an integer of 0 to 3.)

(4) The epoxy resin composition for sealing according to any one of the above (1) to (3), wherein the (B) curing agent contains at least one of an aralkyl type phenol resin and a novolac type phenol resin. object.

(5) The epoxy resin composition for sealing according to any one of (1) to (4), further comprising (D) a curing accelerator.
(6) The epoxy resin composition for sealing according to the above (5), wherein the (D) curing accelerator is an adduct of a third phosphine compound and a quinone compound.

(7) The epoxy resin composition for sealing according to any one of (1) to (6), further comprising (E) an inorganic filler.
(8) The epoxy resin composition for sealing according to the above (7), wherein the content of the (E) inorganic filler is 60 to 95% by mass.
(9) An electronic component device including an element sealed with the sealing epoxy resin composition according to any one of (1) to (8) above.

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

  The present invention relates to an epoxy resin containing (A) an epoxy resin and (B) a curing agent, and (A) an epoxy resin represented by the following general formula (I) as the epoxy resin.

  The (A) epoxy resin used in the present invention contains (A1) an epoxy resin represented by the following general formula (I).

（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は整数を示す。）
上記（Ｉ）で示されるエポキシ樹脂としては、例えばＲ^１〜Ｒ^５が水素原子であるＮＣ−２０００（商品名、日本化薬株式会社製）等が市販品として入手可能である。
硬化性向上の観点からエポキシ樹脂（Ａ１）は、エポキシ樹脂全体に対して、３０質量％以上含有する。また、好ましくは５０質量％以上である。

(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 or different. N represents an integer. .)
As the epoxy resin represented by (I) above, for example, NC-2000 (trade name, manufactured by Nippon Kayaku Co., Ltd.) in which R ^{1 to} R ⁵ are hydrogen atoms is commercially available.
From the viewpoint of improving curability, the epoxy resin (A1) is contained in an amount of 30% by mass or more based on the entire epoxy resin. Moreover, Preferably it is 50 mass% or more.

  The (A) epoxy resin used in the present invention preferably further contains (A2) a biphenyl type epoxy resin represented by the following general formula (II) from the viewpoint of improving fluidity.

（ここで、Ｒ^１〜Ｒ^８は水素原子、置換基を有する炭素数１〜１０の一価の炭化水素基、及び非置換の炭素数１〜１０の一価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い。ｎは０〜３の整数を示す。）

(Here, R ^{1 to} R ⁸ are a group consisting of a hydrogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms having a substituent, and an unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms. All may be the same or different, and n represents an integer of 0 to 3.)

Examples of the biphenyl type epoxy resin represented by the above (II) include 4,4′-bis (2,3-epoxypropoxy) biphenyl or 4,4′-bis (2,3-epoxypropoxy) -3,3. Reaction of epoxy resin based on ', 5,5'-tetramethylbiphenyl, epichlorohydrin and 4,4'-biphenol or 4,4'-(3,3 ', 5,5'-tetramethyl) biphenol And an epoxy resin obtained by the treatment. Among these, an epoxy resin mainly composed of 4,4′-bis (2,3-epoxypropoxy) -3,3 ′, 5,5′-tetramethylbiphenyl is preferable. As such a compound, in the above formula (II), when the oxygen atom substitution positions are the 4 and 4 'positions, the 3, 3', 5, 5 'positions are methyl groups, and the others are Epicoat YX-4000 (trade name, manufactured by Japan Epoxy Resin Co., Ltd.), which is a hydrogen atom, is commercially available.
In order to improve sufficient fluidity, the epoxy resin (A2) is preferably contained in an amount of 5% by mass or more based on the entire epoxy resin.

  For example, when the above epoxy resins (A1) and (A2) are used in combination as an epoxy resin, in order to exhibit the performance of each epoxy resin, the blending amount is the sum of the epoxy resins (A1) + (A2). On the other hand, the content of (A2) is 5 to 70% by mass. Moreover, it is preferable to set it as 10-60 mass%. When it is 5% by mass or more, reflow resistance and fluidity are improved, and when it is 70% by mass or less, flame retardancy is improved. Furthermore, it is particularly preferable to use only the epoxy resin (A1) and the epoxy resin (A2) as the (A) epoxy resin.

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 phenol novolac type epoxy resin, orthocresol novolak type epoxy resin, epoxy resin having triphenylmethane skeleton, phenol, cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol. Condensation of phenols such as F and / or naphthols such as α-naphthol, β-naphthol and dihydroxynaphthalene with compounds having an aldehyde group such as formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde and salicylaldehyde in the presence of an acidic catalyst Or epoxidized novolak resin obtained by co-condensation;
Diglycidyl ethers such as bisphenol A, bisphenol F, bisphenol S, alkyl-substituted or unsubstituted biphenol, and stilbene phenols (bisphenol-type epoxy resin, biphenyl-type epoxy resin, stilbene-type epoxy resin, etc.);
Hydroquinone type epoxy resin;
Glycidyl ester type epoxy resin obtained by reaction of polybasic acids such as phthalic acid and dimer acid with epichlorohydrin;
Glycidylamine type epoxy resin obtained by reaction of polyamine such as diaminodiphenylmethane and isocyanuric acid with epichlorohydrin;
Epoxidized product of co-condensation resin of dicyclopentadiene and phenols;
An epoxy resin having a naphthalene ring;
Epoxidized products of aralkyl-type phenol resins such as phenol-aralkyl resins and naphthol-aralkyl resins containing a biphenylene skeleton;
Trimethylolpropane type epoxy resin; Terpene modified epoxy resin;
A linear aliphatic epoxy resin obtained by oxidizing an olefinic bond with a peracid such as peracetic acid;
Examples thereof include alicyclic epoxy resins; sulfur atom-containing epoxy resins; and the like. These may be used alone or in combination of two or more.

  Among them, bisphenol F type epoxy resin, stilbene type epoxy resin and sulfur atom-containing epoxy resin are preferable from the viewpoint of fluidity and reflow resistance, and novolak type epoxy resin is preferable from the viewpoint of curability, and low hygroscopic viewpoint. Is preferably a dicyclopentadiene type epoxy resin, naphthalene type epoxy resin and triphenylmethane type epoxy resin are preferable from the viewpoint of heat resistance and low warpage, and biphenylene type epoxy resin and naphthol aralkyl are preferable from the viewpoint of flame retardancy. Type epoxy resin is preferred. It is preferable to contain at least one of these epoxy resins. It is preferable to use non-halogen and non-antimony from the above-mentioned resin having good flame retardancy from the viewpoint of improving the high-temperature storage property.

  Examples of the bisphenol F type epoxy resin include an epoxy resin represented by the following general formula (III). Examples of the stilbene type epoxy resin include an epoxy resin represented by the following general formula (IV). As a sulfur atom containing epoxy resin, the epoxy resin etc. which are shown by the following general formula (V) are mentioned, for example.

（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^８は水素原子、置換基を有する炭素数１〜５の一価の炭化水素基、及び非置換の炭素数１〜５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０〜１０の整数を示す。）

(Here, R ^{1 to} R ⁸ are selected from a hydrogen atom, a monovalent hydrocarbon group having 1 to 5 carbon atoms having a substituent, and an unsubstituted monovalent hydrocarbon group having 1 to 5 carbon atoms, All may be the same or different. N represents an integer of 0 to 10.)

（ここで、Ｒ^１〜Ｒ^８は水素原子、置換基を有する炭素数１〜１０のアルキル基、非置換の炭素数１〜１０のアルキル基、置換基を有する炭素数１〜１０のアルコキシ基、及び非置換の炭素数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 a hydrogen atom, an alkyl group having 1 to 10 carbon atoms having a substituent, an unsubstituted alkyl group having 1 to 10 carbon atoms, and an alkoxy group having 1 to 10 carbon atoms having a substituent. And an unsubstituted alkoxy group having 1 to 10 carbon atoms, all of which may be the same or different, and n represents an integer of 0 to 3.)

As the bisphenol F type epoxy resin represented by the general formula (III), 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 Toto Kasei Co., Ltd.) having n = 0 as a main component is commercially available.

  The stilbene type epoxy resin represented by the general formula (IV) can be obtained by reacting a stilbene phenol as a raw material with epichlorohydrin in the presence of a basic substance. Examples of the raw material stilbene phenols include 3-tert-butyl-4,4′-dihydroxy-3 ′, 5,5′-trimethylstilbene, 3-tert-butyl-4,4′-dihydroxy-3. ', 5', 6-trimethylstilbene, 4,4'-dihydroxy-3,3 ', 5,5'-tetramethylstilbene, 4,4'-dihydroxy-3,3'-di-tert-butyl-5 , 5'-dimethylstilbene, 4,4'-dihydroxy-3,3'-di-tert-butyl-6,6'-dimethylstilbene, among others, 3-tert-butyl-4,4'- Dihydroxy-3 ', 5,5'-trimethylstilbene and 4,4'-dihydroxy-3,3', 5,5'-tetramethylstilbene are preferred. These stilbene type phenols may be used alone or in combination of two or more.

Among the sulfur atom-containing epoxy resins represented by the general formula (V), 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. An epoxy resin is preferred, 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 preferred. As such a compound, YSLV-120TE (trade name, manufactured by Toto Kasei Co., Ltd.) and the like are commercially available. These epoxy resins may be used alone or in combination of two or more.

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

（ここで、Ｒは水素原子、置換基を有する炭素数１〜１０の一価の炭化水素基、及び非置換の炭素数１〜１０の一価の炭化水素基から選ばれ、ｎは０〜１０の整数を示す。）

(Where R is selected from a hydrogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms having a substituent, and an unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms; Indicates an integer of 10.)

The novolak type epoxy resin represented by the general formula (VI) can be easily obtained by reacting a novolak type phenol resin with epichlorohydrin. Especially, as R in general formula (VI), it is a C1-C10 alkyl group, such as a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, a methoxy group, an ethoxy group, a 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 (VI), orthocresol novolak type epoxy resins are preferable. As such a compound, EOCN-1020 (trade name, manufactured by Nippon Kayaku Co., Ltd.), in which R in the general formula (VI) is CH ₃ in an ortho position with respect to the epoxy group, is obtained as a commercially available product. Is possible.

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

（ここで、Ｒ^１及びＲ^２は水素原子、置換基を有する炭素数１〜１０の一価の炭化水素基、及び非置換の炭素数１〜１０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。）

(Here, R ¹ and R ² are each independently a hydrogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms having a substituent, and an unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms. And n represents an integer of 0 to 10, and m represents an integer of 0 to 6.)

R ¹ in the above formula (VII) is, for example, a hydrogen atom, methyl group, ethyl group, propyl group, butyl group, isopropyl group, tert-butyl group or other alkyl group, vinyl group, allyl group, butenyl group, etc. A monovalent hydrocarbon group having 1 to 5 carbon atoms having a substituent such as an alkenyl group, a halogenated alkyl group, an amino group-substituted alkyl group, or a mercapto group-substituted alkyl group, or an unsubstituted monovalent carbon group having 1 to 5 carbon atoms. These hydrocarbon groups are mentioned. Of these, an alkyl group such as a methyl group or an ethyl 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. And a monovalent hydrocarbon group having 1 to 5 carbon atoms or an unsubstituted monovalent hydrocarbon group having 1 to 5 carbon atoms having a substituent such as a group, an amino group-substituted alkyl group, a mercapto group-substituted alkyl group. Of these, a hydrogen atom is preferable. As such a compound, HP-7200 (trade name, manufactured by Dainippon Ink & Chemicals, Inc.) in which R ¹ is H, R ² is H, and m = 0 is commercially available. .

  Examples of the naphthalene type epoxy resin include an epoxy resin represented by the following general formula (VIII). Examples of the triphenylmethane type epoxy resin include an epoxy resin represented by the following general formula (IX). It is done.

（ここで、Ｒ^１〜Ｒ^３は水素原子、置換基を有する炭素数１〜１２の一価の炭化水素基及び非置換の炭素数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の整数で且つ（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, a monovalent hydrocarbon group having 1 to 12 carbon atoms and a monovalent hydrocarbon group having 1 to 12 carbon atoms having a substituent, All may be the same or different, p is 1 or 0, l and m are each an integer of 0 to 11, (l + m) is an integer of 1 to 11, and (l + p) is 1 to 12. (I is an integer from 0 to 3, j is an integer from 0 to 2, and k is an integer from 0 to 4.)

The naphthalene type epoxy resin represented by the general formula (VIII) includes a random copolymer containing 1 constituent unit and m constituent units at random, an alternating copolymer containing alternating units, and 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. In R ^{1, R 2} is a hydrogen atom, ^{R 3} is a methyl group, examples of the compounds of i = 1, j = 0, k = 0, NC-7000 ( trade name, manufactured by Nippon Kayaku Co., Ltd.) Is 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.)

  As said compound whose R is a hydrogen atom, E-1032 (a brand name, Japan Epoxy Resin Co., Ltd. product) etc. can be obtained as a commercial item.

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

（上記式中の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、なか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 above formula may all be the same or different and have 1 to 10 carbon atoms such as hydrogen atom, methyl group, ethyl group, propyl group, butyl group, isopropyl group, isobutyl group, etc. Alkyl groups having 1 to 10 carbon atoms such as alkyl groups, methoxy groups, ethoxy groups, propoxy groups and butoxy groups, aryl groups having 6 to 10 carbon atoms such as phenyl groups, tolyl groups and xylyl groups, and benzyl groups and phenethyl groups. Selected from aralkyl groups having 6 to 10 carbon atoms such as a group, among which a hydrogen atom and a methyl group are preferred, and n represents an integer of 0 to 10.)

（ここで、Ｒ^１〜Ｒ^２は水素原子、置換基を有する炭素数１〜１２の一価の炭化水素基及び非置換の炭素数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 ² are selected from a hydrogen atom, a monovalent hydrocarbon group having 1 to 12 carbon atoms having a substituent, and an unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, All may be the same or different, and n represents an integer of 1 to 10.)

As the biphenylene type epoxy resin, NC-3000 (trade name, manufactured by Nippon Kayaku Co., Ltd.) in which R ^{1 to} R ⁹ are H is commercially available. As naphthol / aralkyl type epoxy resins, ESN-175 (trade name, manufactured by Toto Kasei Co., Ltd.) having R ¹ and R ² of H are commercially available. These epoxy resins may be used alone or in combination.

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

（一般式（ＸＩＩ）中のＲ^１は、置換基を有する炭素数１〜１２の炭化水素基、非置換の炭素数１〜１２の炭化水素基、置換基を有する炭素数１〜１２のアルコキシ基、及び非置換の炭素数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、置換基を有する炭素数１〜１２の炭化水素基、非置換の炭素数１〜１２の炭化水素基、置換基を有する炭素数１〜１２のアルコキシ基、及び非置換の炭素数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 (XII) is a hydrocarbon group having 1 to 12 carbon atoms having a substituent, an unsubstituted hydrocarbon group having 1 to 12 carbon atoms, or an alkoxy having 1 to 12 carbon atoms having a substituent. Selected from a group and an unsubstituted alkoxy group having 1 to 12 carbon atoms, all of which may be the same or different, n represents an integer of 0 to 4. R ² has 1 carbon atom having a substituent. -12 hydrocarbon groups, unsubstituted C1-C12 hydrocarbon groups, substituted C1-C12 alkoxy groups, and unsubstituted C1-C12 alkoxy groups, all May be the same or different, and m represents an integer of 0 to 2.)

  Examples of the epoxy resin represented by the general formula (XII) include epoxy resins represented by the following general formulas (XIII) to (XXXI).

  Especially, the epoxy resin shown by the said general formula (XV) is preferable from a viewpoint of a flame retardance and a moldability. As such a compound, YX-8800 (trade name, manufactured by Japan Epoxy Resin Co., Ltd.) and the like are available.

  Moreover, the compound shown by the following general formula (XXXII) can also be used as an epoxy resin used together with said (A1) or (A1) and (A2).

（一般式（ＸＸＸＩＩ）中のＲ^１は水素原子、水酸基、炭素数１〜８のアルキル基、炭素数１〜６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。Ｒ^２、Ｒ^３は水素原子、炭素数１〜６のア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１〜２０の整数を示し、ｍは１〜３の整数を示す。）

(R ¹ in the general formula (XXXII) is selected from a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 8 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms, all of which may be the same or different. R ² , R ³ is selected from a hydrogen atom and an alkyl group having 1 to 6 carbon atoms, all of which may be the same or different, n represents an integer of 1 to 20, and m represents an integer of 1 to ^3. )

M in the general formula (XXXII) is preferably 1 or 2 from the viewpoints of flame retardancy and curability. The compound represented by the general formula (XXXII) is obtained by reacting an indole with a crosslinking agent in the presence of an acid catalyst and then reacting with an epihalohydrin compound. The indole substituent R ¹ includes a hydrogen atom, a methoxy group, an ethoxy group, a vinyl ether group, an isopropoxy group, an allyloxy group, a propargyl ether group, a butoxy group, a phenoxy group, a methyl group, an ethyl group, a vinyl group, an ethyne group, Examples include n-propyl group, isopropyl group, allyl group, propargyl group, butyl group, n-amyl group, sec-amyl group, tert-amyl group, cyclohexyl group, phenyl group, benzyl group and the like. Preferably they are a hydrogen atom and a C1-C3 alkyl group, More preferably, it is a hydrogen atom.

Examples of the crosslinking group represented by the following general formula (1) obtained by reacting with a crosslinking agent include p-xylylene group, m-xylylene group, 1,4-bisethylidenephenylene group, 1,3-bisethylidenephenylene group, 1, 4-bisisopropylidenephenylene group, 1,3-isopropylidenephenylene group, 4,4′-bismethylenebiphenylene group, 3,4′-bismethylenebiphenylene group, 3,3′-bismethylenebiphenylene group, 4,4 '-Bisethylidenebiphenylene group, 3,4'-bisethylidenebiphenylene group, 3,3'-bisethylidenebiphenylene group, 4,4'-bisisopropylidenebiphenylene group, 3,4'-bisisopropylidenebiphenylene group, 3 , 3'-bisisopropylidenebiphenylene group.
Moreover, you may use together aldehydes and ketones, such as formaldehyde, acetaldehyde, propyl aldehyde, butyraldehyde, amyl aldehyde, benzaldehyde, acetone, as a crosslinking agent.
In general formula (XXXII), n represents an integer of 1 to 20, preferably 1 to 5. Acid catalysts include hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, oxalic acid, trifluoroacetic acid, p-toluenesulfonic acid, dimethyl sulfate, diethyl sulfate, zinc chloride, aluminum chloride, iron chloride, boron trifluoride, ion exchange resin, Examples include activated clay, silica alumina, and zeolite.

（一般式（１）中のＲ^２、Ｒ^３は水素原子、炭素数１〜６のア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。ｍは１〜３の整数を示す。）

(R ² and R ³ in the general formula (1) are selected from a hydrogen atom and an alkyl group having 1 to 6 carbon atoms, all of which may be the same or different. M represents an integer of 1 to 3)

As the compound represented by the general formula (XXXII), R ¹ , R ² , R ³ are H, and m = 2 ENP-80 (trade name, manufactured by Toto Kasei Co., Ltd.) is available. The softening point of the compound represented by the general formula (XXXII) is preferably 40 to 200 ° C, more preferably 50 to 160 ° C, and further preferably 60 to 120 ° C. When the temperature is lower than 40 ° C, the curability is lowered, and when it exceeds 200 ° C, the fluidity tends to be lowered. Here, the softening point indicates a softening point measured based on the ring and ball method of JIS-K-6911.

  In order to demonstrate the performance of the above epoxy resin from each viewpoint, the amount of the epoxy resin (A1) and the other epoxy resin used in combination with the epoxy resin (A2) is 30% by mass or more based on the total amount of the epoxy resin. Preferably, it is 50 mass% or more, and more preferably 60 mass% or more.

In the present invention, a conventionally known curing agent can be used as the (B) curing agent. 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 Obtained by condensation or co-condensation of 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. Novolak-type phenolic resin;
Aralkyl-type phenol resins, such as phenol-aralkyl resins, biphenylene-type phenol-aralkyl resins, naphthol-aralkyl resins, synthesized from phenols and / or naphthols and dimethoxyparaxylene or bis (methoxymethyl) biphenyl;
Dicyclopentadiene-type phenol resins such as dicyclopentadiene-type phenol novolak resins and dicyclopentadiene-type naphthol novolak resins synthesized by copolymerization from phenols and / or naphthols and dicyclopentadiene;
Triphenylmethane type phenolic resin; Terpene modified phenolic resin;
Paraxylylene and / or metaxylylene-modified phenolic resin;
Melamine-modified phenolic resin;
Cyclopentadiene modified phenolic resin;
And phenol resins obtained by copolymerizing two or more of these. These may be used alone or in combination of two or more.
Among these, an aralkyl type phenol resin such as a biphenylene type phenol aralkyl resin is more preferable from the viewpoint of flame retardancy, and a novolak type phenol resin is more preferable from the viewpoint of curability.

  Of the aralkyl-type phenol resins, a phenol-aralkyl resin represented by the following general formula (XXXIII) is preferable from the viewpoint of flame retardancy and moldability.

（ここで、Ｒは水素原子、置換基を有する炭素数１〜１０の一価の炭化水素基、及び非置換の炭素数１〜１０の一価の炭化水素基から選ばれ、ｎは０〜１０の整数を示す。）

(Where R is selected from a hydrogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms having a substituent, and an unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms; Indicates an integer of 10.)

  A phenol / aralkyl resin in which R in the general formula (XXXIII) 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, Milex XLC (trade name, manufactured by Mitsui Chemicals, Inc.) and the like are commercially available. 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.

  Examples of the naphthol-aralkyl resin in the aralkyl type phenol resin include a phenol resin represented by the following general formula (XXXIV).

The naphthol-aralkyl resin represented by the general formula (XXXIV), for example ^R 1, ^{R 2} are all hydrogen atom compounds and the like, as such compounds, SN-170 (trade name, Nippon (Available from Sakai Chemical Co., Ltd.) is commercially available.

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

（ここで、Ｒ^１及びＲ^２は水素原子、置換基を有する炭素数１〜１０の一価の炭化水素基、及び非置換の炭素数１〜１０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。）

(Here, R ¹ and R ² are each independently a hydrogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms having a substituent, and an unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms. And n represents an integer of 0 to 10, and m represents an integer of 0 to 6.)

As said compound whose R < ¹ > and R < ² > is a hydrogen atom, DPP (brand name, the Nippon Petrochemical Co., Ltd. product) etc. are available as a commercial item.

  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 (XXXVI).

（ここで、Ｒは水素原子、置換基を有する炭素数１〜１０の一価の炭化水素基、及び非置換の炭素数１〜１０の一価の炭化水素基から選ばれ、ｎは１〜１０の整数を示す。）

(Where R is selected from a hydrogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms having a substituent, and an unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms; Indicates an integer of 10.)

  As the compound in which R is a hydrogen atom, MEH-7500 (trade name, manufactured by Meiwa Kasei Co., Ltd.) and the like are commercially available.

  The blending 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.

  Examples of the novolak type phenol resin include a phenol novolak resin, a cresol novolak resin, a naphthol novolak resin, and the like. Among these, a phenol novolak resin is preferable.

  Examples of the biphenylene type phenol-aralkyl resin include a phenol resin represented by the following general formula (XXXVII).

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

Examples of the biphenylene type phenol / aralkyl resin represented by the general formula (XXXVII) include compounds in which R ^{1 to} R ⁹ are all hydrogen atoms, and in particular, from the viewpoint of melt viscosity, n is a condensation having 1 or more. A mixture of condensates containing 50% by mass or more of the product 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 a seed | species or more.

  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 present invention, a compound represented by the following general formula (XXXVIII) can also be included as an epoxy resin used in combination.

（前記式中のＲ^１は水素原子、置換基を有する炭素数１〜１０の一価の炭化水素基、及び非置換の単価数１〜１０の一価の炭化水素基から選ばれ、Ｒ^２は水素原子置換基を有する炭素数１〜１０の一価の炭化水素基、及び非置換の単価数１〜１０の一価の炭化水素基から選ばれ、ｎは０〜１０の整数を示し、ｍは０〜１０の整数を示す。）

(Wherein R ¹ in formula is selected from a hydrocarbon group, and unsubstituted bid number 1-10 monovalent hydrocarbon group of monovalent to 10 carbon atoms and having a hydrogen atom, a substituted group, R ² Is selected from a monovalent hydrocarbon group having 1 to 10 carbon atoms having a hydrogen atom substituent and an unsubstituted monovalent hydrocarbon group having a unit price of 1 to 10, n represents an integer of 0 to 10, m represents an integer of 0 to 10.)

The compound represented by the general formula (XXXVIII) can be obtained by reacting a phenol compound, an aromatic aldehyde and a biphenylene compound in the presence of an acid catalyst. As the phenol compound, substituted phenols such as phenol, cresol, ethylphenol and butylphenol are used. An aromatic aldehyde is an aromatic compound having one aldehyde group bonded to the aromatic. Aromatic aldehydes include benzaldehyde, methylbenzaldehyde, ethylbenzaldehyde, tert-butylbenzaldehyde and the like. Examples of the biphenylene compound include biphenylene glycol, biphenylene glycol dimethyl ether, biphenylene glycol diethyl ether, biphenylene glycol diacetoxy ester, biphenylene glycol dipropoxy ester, biphenylene glycol monomethyl ether, and biphenylene glycol monoacetoxy ester. In particular, biphenylene glycol and biphenylene glycol dimethyl ether are preferable.
Biphenylene compounds represented by the following general formula (2) can also be used.

As the compound represented by the general formula (XXXVIII), HE-610C, 620C (manufactured by Air Water Co., Ltd.) and the like in which R ¹ and R ² are H are available.

  The compounding quantity of the compound shown by general formula (XXXVIII) is 50-90 mass% with respect to (B) hardening | curing agent whole quantity, and 70-85 mass% is preferable. When it is 50% by mass or more, the flame retardancy is good, and when it is 90% by mass or less, the warp reduction effect is good.

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

In the sealing epoxy resin composition of the present invention, it is preferable to use (D) a curing accelerator as necessary in order to promote the reaction between (A) the epoxy resin and (B) the 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 , 5-diaza-bicyclo (4,3,0) nonene, cycloamidine compounds such as 5,6-dibutylamino-1,8-diaza-bicyclo (5,4,0) undecene-7; and these compounds Maleic anhydride, 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4 -Compounds having a π bond such as quinone compounds such as benzoquinone, 2,3-dimethoxy-1,4-benzoquinone and phenyl-1,4-benzoquinone, diazophenylmethane and phenol resin. Compounds having a pressurized intramolecular polarization comprising;
Tertiary amines such as benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol; and derivatives thereof;
Imidazoles such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole; and derivatives thereof;
Phosphine compounds such as tributylphosphine, methyldiphenylphosphine, triphenylphosphine, tris (4-methylphenyl) phosphine, diphenylphosphine, phenylphosphine; and maleic anhydride, quinone compounds, diazophenylmethane, phenol A phosphorus compound having intramolecular polarization formed by adding a compound having a π bond such as a resin;
Tetraphenylphosphonium tetraphenylborate, triphenylphosphine tetraphenylborate, 2-ethyl-4-methylimidazole tetraphenylborate, tetraphenylboron salts such as N-methylmorpholine tetraphenylborate; and their derivatives; These may be used alone or in combination of two or more.

Of these, an adduct of a tertiary phosphine compound and a quinone compound is preferable from the viewpoints 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, it is preferable to mix | blend (E) inorganic filler 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 (manufactured by US Borax), FRZ-500C (manufactured by Mizusawa Chemical Co., Ltd.), etc., and as zinc molybdate, KEGGARD 911B, 911C, 1100 ( Sherwin-Williams) etc. are each commercially available.

  These inorganic fillers may be used alone or in combination of two or more. Of these, 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 preferably spherical from the viewpoint of filling property and mold wear.

  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 using an inorganic filler, it is preferable to further mix a coupling agent in the sealing epoxy resin composition of the present invention in order to enhance the adhesion between the resin component and the filler. The coupling agent is generally used in the epoxy resin composition for sealing and is not particularly limited. For example, a silane compound having primary and / or secondary and / or tertiary amino groups, epoxy silane , Various silane compounds such as mercaptosilane, alkylsilane, ureidosilane, vinylsilane, 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 (ditridecyl phosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, bis (dioctyl pyrophosphate) oxyacetate titanate, bis (dioctyl pyrophosphate) 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.

  Of these, a silane coupling agent having a secondary amino group is preferred 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 blending amount of the coupling agent is preferably 0.037 to 4.75% by mass, more preferably 0.05 to 5% by mass with respect to the epoxy resin composition for sealing. More preferably, it is 1-2.5 mass%. If it is less than 0.037% by mass, the adhesion to the frame tends to be lowered, and if it exceeds 4.75% by mass, the moldability of the package tends to be lowered.

In the epoxy resin composition for sealing of the present invention, a conventionally known flame retardant for the purpose of further improving the flame retardancy, especially a halogen-free and non-antimony flame retardant, as required from the viewpoint of environmental friendliness and reliability, is required. Can be blended.
Examples of the flame retardant include inorganic compounds such as red phosphorus and zinc oxide; red phosphorus coated with a thermosetting resin such as phenol resin, and phosphorus compounds such as phosphate ester and phosphine oxide; melamine, melamine derivatives, and melamine modified Compounds having a triazine ring such as phenol resin; nitrogen-containing compounds such as cyanuric acid derivatives and isocyanuric acid derivatives; phosphorus and nitrogen-containing compounds such as cyclophosphazene; aluminum hydroxide, magnesium hydroxide, composite metal hydroxide, zinc oxide, A compound containing a metal element such as zinc stannate, zinc borate, iron oxide, molybdenum oxide, zinc molybdate, dicyclopentadienyl iron, etc., and two or more of these may be used alone. You may use it combining.

Of these, phosphate ester, phosphine oxide and cyclophosphazene are preferable from the viewpoint of fluidity.
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 Examples thereof include 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 (XXXIX) is preferable.

（上記式中のＲは、水素原子、置換基を有する炭素数１〜１０の一価の炭化水素基、及び非置換の単価数１〜１０の一価の炭化水素基から選ばれる。）

(R in the above formula is selected from a hydrogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms having a substituent, and an unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms.)

  When the phosphoric acid ester of the said formula (XXXIX) is illustrated, the phosphoric acid ester shown by the following structural formula (XXXX)-(XXXXIV) etc. will be mentioned.

  It is preferable that the addition amount of these phosphate ester exists in the range of 0.2-3.0 mass% in the quantity of a phosphorus atom with respect to all the other compounding components except a filler. When it is less than 0.2% by mass, the flame retardant effect 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 (XXXXV).

（ここで、Ｒ^１、Ｒ^２及びＲ^３は、置換基を有する炭素数１〜１０のアルキル基、及び非置換の単価数１〜１０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 alkyl group having 1 to 10 carbon atoms and an unsubstituted alkyl group, aryl group, aralkyl group and hydrogen atom having a unit price of 1 to 10). , All may be the same or different, except when all are hydrogen atoms.)

Among the phosphorus compounds represented by the above general formula (XXXXV), from the viewpoint of hydrolysis resistance, R ^{1 to} R ³ are preferably an aryl group having a substituent or an unsubstituted aryl group, and particularly preferably phenyl. It is a 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 all the other compounding components except a filler. 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 tends to decrease, and if it exceeds 0.2% by mass, the moldability and moisture resistance tend to decrease.

  Cyclophosphazenes include cyclophosphazene compounds containing the following formula (XXXXVI) and / or the following formula (XXXXVII) as a repeating unit in the main chain skeleton, or the following formulas (XXXXVIII) and different substitution positions with respect to phosphorus atoms in the phosphazene ring. And / or a compound containing the following formula (XXXIX) as a repeating unit.

Here, the formula (XXXXVI) and wherein m in (XXXXVIII) in an integer from 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 And all may be the same or different. A represents an alkylene group having 1 to 4 carbon atoms or an arylene group. N in Formula (XXXXVII) and Formula (XXXXIX) is an integer of 1 to 10, and R ^{5 to} R ⁸ are selected from an alkyl group or aryl group having 1 to 12 carbon atoms that may have a substituent, and all They may be the same or different, and A represents an alkylene group having 1 to 4 carbon atoms or an arylene group. 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 all n. It may be the same or different.

The formula (XXXXVI) ~ formula ^(XXXXIX), is not particularly limited, but an optionally substituted alkyl group or aryl group having 1 to 12 carbon atoms represented by R 1 to R ^8, for example a methyl group Alkyl groups such as 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-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, etc. , Aryl group-substituted alkyl groups such as benzyl group and phenethyl group, and the like. Further, substituents substituted therewith include alkyl groups, alkoxyl groups, aryl groups, hydroxyl groups , An amino group, 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.

  Further, the alkylene group or arylene group having 1 to 4 carbon atoms represented by A in the above formulas (XXXXVI) to (XXXXIX) is not particularly limited, but for example, a methylene group, an 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 cyclophosphazene compound is a polymer of any one of the above formulas (XXXXVI) to (XXXXIX), a copolymer of the above formula (XXXXVI) and the above formula (XXXIX), or the above formula (XXXXVIII) and the above formula (XXXIX). In the case of a copolymer, it may be a random copolymer, a block copolymer or an alternating copolymer. The copolymerization molar ratio m / n is not particularly limited, but is preferably 1/0 to 1/4 from the viewpoint of heat resistance and strength improvement of the cured epoxy resin, and 1/0 to 1 / 1.5. More preferred. Moreover, polymerization degree m + n is 1-20, Preferably it is 2-8, More preferably, it is 3-6.

  Preferred examples of the cyclophosphazene compound include a polymer of the following formula (XXXX), a copolymer of the following formula (XXXXXX), and the like.

（ここで、式（ＸＸＸＸＸ）中のｎは、０〜９の整数で、Ｒ^１〜Ｒ^６はそれぞれ独立に水素又は水酸基を示す。）

(Here, n in the formula (XXXX) is an integer of 0 to 9, and R ^{1 to} R ⁶ each independently represent hydrogen or a hydroxyl group.)

Here, m and n in the above formula (XXXXXXI) 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 a hydroxyl group. Chosen from. In addition, the cyclophosphazene compound represented by the above formula (XXXXXXI) includes the following m repeating units (a) and n repeating units (b) alternately, in a block form, or randomly. Any of these may be used, but those randomly included are preferred.

Among them, the main component is a polymer in which n is 3 to 6 in the above formula (XXXX), or R ^{5 to} R ⁶ are all hydrogen or one is a hydroxyl group in the above formula (XXXXI), and m / n is 1 The main component is a copolymer of / 2 to 1/3 and m + n of 3 to 6. Further, as a commercially available phosphazene compound, SPE-100 (trade name, manufactured by Otsuka Chemical Co., Ltd.) in which R ^{1 to} R ⁶ of the above formula (XXXX) are H and n = 0 is available.
It is preferable that the compounding quantity of a phosphazene compound is 0.2-3 mass% with respect to all the other compounding components except a filler. More preferably, it is 1-2.5 mass%. When the content is 0.2% by mass or more, a flame-retardant effect is easily obtained.

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

（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 a positive number. Show.)

  Among these, a compound in which r in the composition formula (XXXXII) is 0, that is, a compound represented by the following composition formula (XXXXIII) 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, and l represent positive numbers.)

M ¹ , M ² and M ³ in the above composition formulas (XXXXII) and (XXXXIII) 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 Preferably, the transition metal element is selected from Group IIIB to IIB, M ¹ is selected from magnesium, calcium, aluminum, tin, titanium, iron, cobalt, nickel, copper and zinc, and M ² is iron, cobalt, nickel, More preferably, it is selected from 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 (XXXXII) is not particularly limited as long as the effects of the present invention can be obtained. However, when r = 0, the molar ratio p / q of p and q is 99/1 to Preferably it is 50/50. That is, the molar ratio m / n between m and n in the composition formula (XXXXIII) is preferably 99/1 to 50/50.

Examples of commercially available products include water in which M ¹ in the above composition formula (XXXXIII) 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. In addition, what is called a metalloid element also includes what is called a metal element, and refers to all elements except a nonmetallic element.

  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”, February 15, 1987) (Reduced plate 30th printing).

  The shape of the composite metal hydroxide is not particularly limited, but from the viewpoint of fluidity and filling properties, a polyhedral shape having an appropriate thickness is preferable to a flat plate shape. 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- 12 mass% is more preferable. 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 be lowered.

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 and octylphenol; polyphenols such as resorcin, catechol, bisphenol A, bisphenol F and bisphenol S; phenylphenol, Aminophenol or naphthols such as α-naphthol, β-naphthol and dihydroxynaphthalene; or obtained by condensing or cocondensing a compound having a phenolic hydroxyl group and a compound having an aldehyde group such as formaldehyde under an acidic catalyst. Resin; Of these, phenol, cresol, or a copolycondensation product of these with formaldehyde is preferable from the viewpoint of moldability.

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; 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 hardly occurs, 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. 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 likely to gel 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 nitrogen content of the produced resin tends to be low. There is.

  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, 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 copolycondensation product obtained as a compound which has a triazine ring 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 (XXXXIV) to (XXXXXXIX) (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 500 to 1,000, and more preferably 550 to 800. If it is less than 500, moldability and reflow crack resistance are lowered, and if it exceeds 1000, fluidity tends to be lowered.

The weight average molecular weight is preferably 1500 to 10,000, and more preferably 1700 to 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. 0 is more preferable. When it is less than 2.0, the reflow crack resistance is lowered, and when it exceeds 10.0, the fluidity tends to be lowered.

  The phenol resin used for the compound having a triazine ring is not particularly limited as long as it is as listed above, but when it is synthesized by the method shown below, its molecular weight, molecular weight The distribution is preferable in that it can be synthesized within the preferred range described in the present invention. 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 1 to 30 hours.

  In addition, in the synthesis of a phenol resin as a raw material for a compound having a triazine ring, an amine catalyst such as trimethylamine and triethylamine, an acid catalyst such as p-toluenesulfonic acid and oxalic acid, and an alkali catalyst such as sodium hydroxide and ammonia, as necessary. Etc. may be used in an amount of 0.00001 to 0.01 mol per mol of the phenol derivative. The pH of the reaction system is preferably 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 ratio of the triazine derivative and the compound having an aldehyde group when the compound having a triazine derivative and an aldehyde group is added to the phenol resin obtained as described above is reacted with the compound having a phenol derivative and an aldehyde group. Polycondensate (phenol resin) (unreacted phenol derivative, compound having an aldehyde group, water or the like removed under reduced pressure by heating, or those not removed (in this case, unreacted phenol is The triazine derivative is preferably 3 to 50 g, more preferably 4 to 30 g based on 100 g of the condensate. 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 of the compound having a triazine ring 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. Tend to be disadvantageous. The reaction time is preferably 1 to 30 hours.

Moreover, in this invention, you may contain a silicon-containing polymer in an epoxy resin composition from a viewpoint of the further curvature reduction. The silicon-containing polymer has the following bonds (c) and (d), the terminal is a functional group selected from R ¹ , a hydroxyl group and an alkoxy group, and the epoxy equivalent is 500 to 4000. There is no such polymer, but examples include branched polysiloxane.

（ここで、Ｒ^１は置換基を有する炭素数１〜１２の一価の炭化水素基、及び非置換の炭素数１〜１２の一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一価の有機基を示す。）

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

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

  X in the general formula (d) is 2,3-epoxypropyl group, 3,4-epoxybutyl group, 4,5-epoxypentyl group, 2-glycidoxyethyl group, 3-glycidoxy Propyl group, 4-glycidoxybutyl group, 2- (3,4-epoxycyclohexyl) ethyl group, 3- (3,4-epoxycyclohexyl) propyl group and the like, among which 3-glycidoxypropyl group is mentioned. preferable.

Further, 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 is more than 4000, it tends to ooze out on the surface of the cured product and tends to cause molding defects. The silicon-containing polymer is further preferable from the viewpoint of coexistence of fluidity and low warpage of the sealing epoxy resin composition obtained to have the following bond (e).

（ここで、Ｒ^１、Ｒ^２は置換基を有する炭素数１〜１２の一価の炭化水素基、及び非置換の炭素数１〜１２の一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、Ｒ^２はすべてが同一でも異なっていてもよい。）

(Wherein R ¹ and R ² are selected from a monovalent hydrocarbon group having 1 to 12 carbon atoms having a substituent and an unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms; All of R ¹ and R ² in the product may be the same or different.)

R ¹ and R ² in the general formula (e) are methyl group, ethyl group, propyl group, butyl group, isopropyl group, isobutyl group, t-butyl group, pentyl group, hexyl group, heptyl group, octyl group, Alkyl groups such as 2-ethylhexyl group; alkenyl groups such as vinyl group, allyl group, butenyl group, pentenyl group, hexenyl group; aryl groups 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.

The softening point of such a silicon-containing polymer is preferably set to 40 ° C to 120 ° C, and more preferably set to 50 ° C to 100 ° C. When the temperature is lower than 40 ° C., the mechanical strength of the cured epoxy resin composition obtained tends to decrease. When the temperature is higher than 120 ° C., the dispersibility of the silicon-containing polymer in the epoxy resin composition for sealing is low. It 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 the 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. 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. By setting the content of the phenyl group in the monovalent organic group bonded to the silicon atom in the silicon-containing polymer, preferably 60 mol% to 99 mol%, more preferably 70 mol% to 85 mol%. A silicon-containing polymer having a desired softening point 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 trade name: AY42-119 manufactured by Toray Dow Corning Silicone 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 a partially hydrolyzed condensate thereof that can form the above units (c) to (e) by hydrolysis condensation reaction, an organic solvent capable of dissolving raw materials and reaction products And all the hydrolyzable groups of the raw material can be obtained by mixing them in a hydrolyzable amount of water and subjecting them to a hydrolytic condensation reaction. At this time, in order to reduce the amount of chlorine contained as an impurity in the sealing epoxy resin composition, it is preferable to use organoalkoxysilane and / or siloxane 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, phenyltriethoxysilane, 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 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 content is less than 0.2% by mass, the effect of adding the silicon-containing polymer is not observed, and when the content 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 (XXXXXXX) and / or the compound represented by the following composition formula (XXXXXXI) can be improved as needed to improve moisture resistance and high-temperature storage characteristics of semiconductor elements such as ICs. Therefore, it can be contained in the epoxy resin composition.

（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 formula (XXXXXXX) is available as a brand name: DHT-4A by Kyowa Chemical Industry Co., Ltd. as a commercial item. In addition, the compound of the above formula (XXXXXXI) is commercially available as trade name: IXE500 manufactured by Toa Gosei Co., Ltd.
Further, other anion exchangers can be added as necessary. The anion exchanger is not particularly limited and conventionally known anion exchangers can be used, and examples thereof include hydrated oxides of elements selected from magnesium, aluminum, titanium, zirconium, antimony, and the like. Alternatively, two or more kinds can be used in combination.

  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.

  The electronic component device of the present invention having an element sealed with the sealing epoxy resin composition of the present invention includes a lead frame, a wired tape carrier, a wiring board, glass, a support member such as a silicon wafer, and a mounting substrate. In addition, active elements such as semiconductor chips, transistors, diodes, and thyristors, and passive elements such as capacitors, resistors, and coils are mounted, and necessary portions are sealed with the sealing epoxy resin composition of the present invention. And electronic component devices.

  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 liquid crystal glass substrate, a MCM (Multi Chip Module) substrate, and a hybrid IC substrate. Etc.

As an electronic component device provided with such an element, for example, a semiconductor device can be cited. Specifically, an element such as a semiconductor chip is fixed on a lead frame (island, tab), and a terminal of an element such as a bonding pad. The lead part and the lead part are connected by wire bonding or bump, and then sealed by transfer molding or the like 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), TQFP (Thin A resin-sealed IC such as Quad Flat Package);
TCP (Tape Carrier Package) in which a semiconductor chip lead-bonded to a tape carrier is sealed with the sealing epoxy resin composition of the present invention;
COB (Chip On Board), COG (semiconductor chip connected with wiring formed on a wiring board or glass by wire bonding, flip chip bonding, solder or the like, and sealed with the sealing epoxy resin composition of the present invention. Chip-on-glass and other semiconductor devices mounted with bare chips;
For wiring formed on a wiring board or glass, active elements such as semiconductor chips, transistors, diodes, thyristors and / or passive elements such as capacitors, resistors, coils, etc. connected by wire bonding, flip chip bonding, solder, etc. Hybrid IC sealed with the epoxy resin composition for sealing of the present invention;
A semiconductor chip is mounted on an interposer substrate on which terminals for connecting an MCM (Multi Chip Module) motherboard are formed, and the semiconductor chip and wiring formed on the interposer substrate are connected by bumps or wire bonding, and then the epoxy for sealing of the present invention is used. Examples thereof include BGA (Ball Grid Array), CSP (Chip Size Package), MCP (Multi Chip Package); and the like in which the semiconductor chip mounting side is sealed with a resin composition.
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 1-5, Comparative Examples 1-4)
As the epoxy resin of (A1), an epoxy resin of the above general formula (I) having an epoxy equivalent of 238 and a softening point of 52 ° C. (trade name NC-2000L manufactured by Nippon Kayaku Co., Ltd.) (epoxy resin 1) was used. As the epoxy resin (A2), a biphenyl type epoxy resin (trade name: Epicoat YX-4000H manufactured by Japan Epoxy Resin Co., Ltd.) (epoxy resin 2) having an epoxy equivalent of 196 and a melting point of 106 ° C. was used. (B) Phenol aralkyl resin having a softening point of 70 ° C. and a hydroxyl group equivalent of 175 (trade name: Mirex XLC-3L manufactured by Mitsui Chemicals, Inc.) (curing agent 1), (D) triphenyl as a curing accelerator 1. Adduct of phosphine and 1,4-benzoquinone (curing accelerator 1), γ-glycidoxypropyltrimethoxysilane (epoxysilane) as coupling agent, average particle size of 14.5 μm as inorganic filler, specific surface area In parts by mass shown in Tables 1 and 2, 8 m ² / g of spherical fused silica, carnauba wax (manufactured by Clariant) and carbon black (trade name: MA-100, manufactured by Mitsubishi Chemical Corporation) as other additives are shown. Mixing was performed, and roll kneading was performed under the conditions of a kneading temperature of 80 ° C. and a kneading time of 10 minutes to prepare Examples 1 to 5 and Comparative Examples 1 to 4.

The characteristics of the produced epoxy resin compositions for sealing of Examples 1 to 5 and Comparative Examples 1 to 4 were determined by the following tests. The results are shown in Tables 3-4.
(1) Spiral flow Using a spiral flow measurement mold in accordance with EMMI-1-66, a sealing epoxy resin composition was molded by a transfer molding machine at a mold temperature of 180 ° C., a molding pressure of 6.9 MPa, and a curing time. Molding was performed for 90 seconds, and the flow distance (cm) was determined.

(2) Hardness during heating The sealing epoxy resin composition was molded into a disk having a diameter of 50 mm and a thickness of 3 mm under the molding conditions described in (1) above, and immediately after molding, a Shore D hardness meter (trade name, Shimadzu Corporation) Measured using a manufacturing plant).

(3) Flame retardancy Using a mold for molding a test piece having a thickness of 1/16 inch, the epoxy resin composition for sealing was molded under the molding conditions of (1) above, and further at 180 ° C. for 5 hours. Post-curing was performed and flame retardancy was evaluated according to the UL-94 test method.

(4) Reflow resistance (4.1) Cu lead frame 8mm x 10mm x 0.4mm silicon chip mounted 80mm flat package (QFP) with external dimensions of 20mm x 14mm x 2mm (Lead frame material: copper alloy, Die pad top surface and lead tip silver-plated product) are molded and post-cured using the epoxy resin composition for sealing under the condition (3) above, and humidified at 85 ° C. and 85% RH. Then, reflow treatment was performed at a predetermined time of 240 ° C. for 10 seconds, the presence or absence of cracks was observed, and the number of crack generation packages with respect to the number of test packages (5) was evaluated.
(4.2) PPF lead frame Evaluation was performed in the same manner as in (4.1) except that PPF (core material: copper alloy, three-layer (Ni / Pd / Au) plated product) was used for the lead frame.

(5) Moisture resistance External dimensions of 20 mm x 14 mm x 2.7 mm mounted with a 6 mm x 6 mm x 0.4 mm test silicon chip on which an aluminum wiring with a line width of 10 µm and a thickness of 1 µm is mounted on a 5 µm thick oxide film An 80-pin flat package (QFP) is molded and post-cured using the epoxy resin composition for sealing under the above conditions (3), pre-treated, humidified, and aluminum is added every predetermined time. The disconnection failure due to wiring corrosion was examined, and the number of defective packages relative to the number of test packages (10) was evaluated.

  In addition, after pre-humidifying the flat package on conditions of 85 degreeC and 85% RH for 72 hours, the vapor phase reflow process for 215 degreeC and 90 second was performed. Subsequent humidification was performed under conditions of 0.2 MPa and 121 ° C.

(6) High-temperature storage characteristics 42 mm lead made of 5 mm x 9 mm x 0.4 mm test silicon chip with aluminum wiring with line width of 10 μm and thickness of 1 μm on 5 μm thick oxide film, with partial silver plating A 16-pin DIP (Dual Inline Package), which is mounted on the frame using silver paste and connected to the chip's bonding pads and inner leads with Au wire at 200 ° C by a thermonic wire bonder, is used as an epoxy resin for sealing Molded and post-cured using the composition under the condition (3) above, stored in a high-temperature bath at 200 ° C., taken out every predetermined time, conducted a continuity test, and the number of test packages (10) The high temperature storage characteristics were evaluated based on the number of poorly conductive packages.

  Comparative Examples 1 to 3 in which the epoxy resin of component (A) is not blended within the scope of the present invention are inferior in curability, and Comparative Example 3 achieves UL-94 V-0 in flame retardancy. Not done.

  On the other hand, the Example in which the epoxy resin of the component (A) contains 30% by mass or more of the epoxy resin (A1) is excellent in flame retardancy and curability while maintaining reflow resistance. In particular, Examples 2 to 5 containing the epoxy resin (A2) are excellent from the viewpoint of reflow resistance and fluidity, and from the viewpoint of flame retardancy, the epoxy resin (A1) is 50% by weight or more of the entire epoxy resin. Certain examples 1-4 are excellent. As an overall balance, Examples 3 and 4 in which the epoxy resin (A1) is 50 to 60% by mass and the epoxy resin (A2) is 40 to 50% by mass are preferable. Furthermore, all the examples are excellent in reliability such as moisture resistance and high temperature storage characteristics.

  According to the present invention, the adhesiveness with noble metals such as Ag and Au is good, the reflow resistance is good, and the flame retardancy is not reduced without reducing the reliability such as moldability, moisture resistance, and high temperature storage characteristics. The epoxy resin composition for sealing which is favorable can be provided.

Claims (9)

In the sealing epoxy resin composition containing (A) an epoxy resin and (B) a curing agent, (A1) the content of the epoxy resin represented by the following general formula (I) is in the whole (A) epoxy resin. On the other hand, the epoxy resin composition for sealing which is 30 mass% or more.

(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 or different. N represents an integer. .) The epoxy resin composition for sealing according to claim 1, wherein the (A) epoxy resin further contains (A2) an epoxy resin represented by the following general formula (II).

(Here, R ^{1 to} R ⁸ are a group consisting of a hydrogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms having a substituent, and an unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms. All may be the same or different, and n represents an integer of 0 to 3.) In the sealing epoxy resin composition containing (A) an epoxy resin and (B) a curing agent, the (A) epoxy resin is (A1) an epoxy resin represented by the general formula (I) and (A2) the following general The epoxy resin composition for sealing which contains the epoxy resin shown by Formula (II), and whose content of (A2) is 5-70 mass% with respect to the sum total of (A1) + (A2).

(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 or different. N represents an integer. .)

(Here, R ^{1 to} R ⁸ are a group consisting of a hydrogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms having a substituent, and an unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms. All may be the same or different, and n represents an integer of 0 to 3.)   The epoxy resin composition for sealing according to any one of claims 1 to 3, wherein the (B) curing agent contains at least one of an aralkyl type phenol resin and a novolac type phenol resin.   Furthermore, the epoxy resin composition for sealing as described in any one of Claims 1-4 containing (D) hardening accelerator.   The epoxy resin composition for sealing according to claim 5, wherein the (D) curing accelerator is an adduct of a third phosphine compound and a quinone compound.   Furthermore, the epoxy resin composition for sealing as described in any one of Claims 1-6 containing (E) inorganic filler.   The sealing epoxy resin composition according to claim 7, wherein the content of the (E) inorganic filler is 60 to 95% by mass.   The electronic component apparatus provided with the element sealed with the epoxy resin composition for sealing as described in any one of Claims 1-8.