JP2006193618A - Epoxy resin composition for sealing and electronic part device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an epoxy resin composition for sealing, having reliability such as excellent flame resistance, moldability, reflow resistance, moisture resistance and characteristics after being left at high temperature, and suitable for sealing VLSI (Very Large Scale Integration); and to provide an electronic part device having an element sealed with the composition. <P>SOLUTION: The epoxy resin composition for sealing contains (A) an epoxy resin, (B) a curing agent, (C) a cyclic phosphazene compound and (D) a phosphoric ester compound. <P>COPYRIGHT: (C)2006,JPO&NCIPI

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.

  Conventionally, in the field of sealing technology for elements of electronic component devices such as transistors and ICs, sealing using a resin has been the mainstream in terms of productivity, cost, etc., and a sealing resin composition Of these, epoxy resin compositions are widely used. This is because epoxy resins have an excellent balance in various properties such as electrical properties, moisture resistance, heat resistance, mechanical properties, and adhesion to inserts. Generally, a flame retardant is added to the epoxy resin composition for sealing in order to increase the flame retardancy of a molded product. Typically, the epoxy resin composition for sealing is made flame retardant by using a combination of a brominated resin such as diglycidyl ether of tetrabromobisphenol A and antimony oxide as a flame retardant.

  However, in recent years, there is a movement to regulate the use of halogenated resins and antimony compounds from the viewpoint of environmental protection. Accordingly, demands for non-halogenated (non-brominated) and non-antimony-ized epoxy resin compositions for sealing are also increasing. In the first place, it is known that an IC package sealed with a composition containing a brominated resin for flame retardancy has an adverse effect on the high temperature storage characteristics of the package. It is also desirable to reduce the amount of brominated resin used.

  Under such circumstances, various methods have been reported for achieving flame retardancy of epoxy resin compositions without using conventional flame retardants such as brominated resin and antimony oxide. For example, as a non-halogen and non-antimony flame retardant, a method using red phosphorus (for example, see Patent Document 1), a method using a phosphate ester compound (for example, see Patent Document 2), a method using a phosphazene compound (for example, see Patent Document 3) ), A method using a metal hydroxide (for example, see Patent Document 4), and a method for using a metal hydroxide and a metal oxide in combination (for example, see Patent Document 5). Also known are methods using organometallic compounds such as cyclopentadienyl compounds such as ferrocene (see, for example, Patent Document 6) and acetylacetonate copper (see, for example, Non-Patent Document 1). In addition, a method of increasing the proportion of the filler in the composition (for example, see Patent Document 7), a method of using a highly flame-retardant resin (for example, see Patent Document 8), and metal hydroxide having a surface treated A method of using an object (see, for example, Patent Document 9) is known.

JP-A-9-227765 JP 9-235449 A JP-A-8-225714 Japanese Patent Laid-Open No. 9-241383 Japanese Patent Laid-Open No. 9-130037 JP-A-11-269349 JP 7-82343 A JP-A-11-140277 Japanese Patent Laid-Open No. 10-338818 Hiroshi Kato, Functional Materials, 11 (6), 34 (1991)

  However, with the above-described method, even if the flame retardancy of the resin composition is not sufficient or the flame retardancy can be achieved, it is difficult to obtain satisfactory results in other various characteristics. That is, in the method using red phosphorus, the problem of decrease in moisture resistance, in the method using a phosphate ester compound or phosphazene compound, the problem of decrease in moldability and humidity resistance due to plasticization, and in the method using metal hydroxide, it is fluid There is a tendency that a problem of decrease in fluidity and mold releasability, a method of using metal oxides, and a method of increasing the proportion of fillers cause a problem of decrease in fluidity.

  Further, in the method using an organometallic compound such as acetylacetonate copper, the curing reaction is inhibited and the moldability tends to be lowered. Further, in the method using a resin having high flame retardancy, it is difficult to achieve V-0 flame retardance in the UL-94 test required for materials of electronic component devices.

  Furthermore, in the method using a metal hydroxide, it is suggested that magnesium hydroxide can be suitably used among the metal hydroxides. If not used, flame retardancy does not appear. Use of a large amount of magnesium hydroxide tends to lower the moldability of the composition such as fluidity. In addition, since metal oxides are inferior in acid resistance, their surface is corroded in the solder plating process when manufacturing a semiconductor device, and whitening tends to occur. Such a whitening phenomenon cannot be solved even when a surface-treated metal oxide is used.

  As described above, it is difficult to obtain satisfactory results in various properties in any of the above-described methods, and it is equal to or more than the conventional epoxy resin composition for sealing using a combination of brominated resin and antimony oxide. The flame retardancy, moldability and reliability have not been achieved. Therefore, an epoxy resin composition for sealing containing a non-halogen and non-antimony flame retardant that is effective in making the resin composition flame-retardant but does not reduce moldability and package reliability is desired.

  Therefore, in the present invention, in view of such a situation, it is non-halogen and non-antimony, and good flame retardancy can be achieved without reducing the reliability of the package such as moldability, reflow resistance, moisture resistance, and high temperature storage characteristics. It is an object of the present invention to provide an epoxy resin composition for sealing that can be achieved, and an electronic component device including an element that is sealed using such a composition.

  As a result of intensive studies to solve the above problems, the present inventors have achieved the intended purpose by using a specific phosphazene compound and a phosphate ester compound in combination in the epoxy resin composition for sealing. The inventors have found that this is possible and have completed the present invention.

The present application relates to the following inventions.
(1) An epoxy resin composition for sealing comprising (A) an epoxy resin, (B) a curing agent, (C) a cyclic phosphazene compound, and (D) a phosphate ester compound.
(2) The epoxy resin composition for sealing according to the above (1), wherein the (C) cyclic phosphazene compound contains a compound represented by the following general formula (I).

（式中、ｎは３〜５の整数であり、ＲおよびＲ’はそれぞれ独立して同じでも異なってもよく、炭素数１〜４のアルキル基またはアリール基を示し、ヒドロキシ基で置換されてもよい。）
（３）式（I）中、ＲおよびＲ’の一方または両方がヒドロキシフェニル基であり、ヒドロキシフェニル基の数が１〜１０のいずれかであることを特徴とする上記（２）に記載の封止用エポキシ樹脂組成物。
（４）（Ｃ）環状ホスファゼン化合物が、架橋された化合物を含むことを特徴とする上記（１）〜（３）のいずれかに記載の封止用エポキシ樹脂組成物。
（５）（Ｄ）リン酸エステル化合物が、下記一般式（II）で示される化合物を含有することを特徴とする上記（１）〜（４）のいずれかに記載の封止用エポキシ樹脂組成物。

(In the formula, n is an integer of 3 to 5, and R and R ′ may be the same or different and each represents an alkyl or aryl group having 1 to 4 carbon atoms, and is substituted with a hydroxy group. May be.)
(3) In formula (I), one or both of R and R ′ are hydroxyphenyl groups, and the number of hydroxyphenyl groups is any one of 1 to 10, as described in (2) above An epoxy resin composition for sealing.
(4) The epoxy resin composition for sealing according to any one of the above (1) to (3), wherein the (C) cyclic phosphazene compound contains a crosslinked compound.
(5) The epoxy resin composition for sealing according to any one of the above (1) to (4), wherein the phosphate ester compound (D) contains a compound represented by the following general formula (II): object.

（式中、８個のＲは炭素数１〜４のアルキル基を示し、全て同一でも異なっていてもよく、Ａｒは芳香族環を示す。）
（６）（Ａ）エポキシ樹脂が、ビフェニル型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、スチルベン型エポキシ樹脂、硫黄原子含有エポキシ樹脂、ノボラック型エポキシ樹脂、ジシクロペンタジエン型エポキシ樹脂、ナフタレン型エポキシ樹脂、トリフェニルメタン型エポキシ樹脂、ビフェニレン型エポキシ樹脂及びナフトール・アラルキル型フェノール樹脂からなる群より選択される少なくとも１種を含有することを特徴とする上記（１）〜（５）のいずれか記載の封止用エポキシ樹脂組成物。
（７）硫黄原子含有エポキシ樹脂が、下記一般式（III）で示される化合物であることを特徴とする上記（６）に記載の封止用エポキシ樹脂組成物。

(In the formula, 8 Rs represent an alkyl group having 1 to 4 carbon atoms, which may all be the same or different, and Ar represents an aromatic ring.)
(6) (A) The epoxy resin is biphenyl type epoxy resin, bisphenol F type epoxy resin, stilbene type epoxy resin, sulfur atom containing epoxy resin, novolac type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, tri The sealing according to any one of (1) to (5) above, which comprises at least one selected from the group consisting of phenylmethane type epoxy resin, biphenylene type epoxy resin and naphthol / aralkyl type phenolic resin Epoxy resin composition.
(7) The epoxy resin composition for sealing according to the above (6), wherein the sulfur atom-containing epoxy resin is a compound represented by the following general formula (III).

（式中、Ｒ¹〜Ｒ⁸は水素原子、および置換又は非置換の炭素数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く、ｎは０〜３の整数を示す。）
（８）（Ｂ）硬化剤が、ビフェニレン型フェノール樹脂、アラルキル型フェノール樹脂、ジシクロペンタジエン型フェノール樹脂、トリフェニルメタン型フェノール樹脂及びノボラック型フェノール樹脂からなる群より選択される少なくとも１種を含有する上記（１）〜（７）のいずれかに記載の封止用エポキシ樹脂組成物。
（９）（Ｅ）硬化促進剤をさらに含有することを特徴とする上記（１）〜（８）のいずれかに記載の封止用エポキシ樹脂組成物。
（１０）（Ｅ）硬化促進剤が、ホスフィン化合物とキノン化合物との付加物を含むことを特徴とする上記（９）に記載の封止用エポキシ樹脂組成物。
（１１）（Ｅ）硬化促進剤が、リン原子に少なくとも１つのアルキル基が結合したホスフィン化合物とキノン化合物との付加物を含むことを特徴とする上記（１０）に記載の封止用エポキシ樹脂組成物。
（１２）（Ｆ）無機充填剤をさらに含有することを特徴とする上記（１）〜（１１）のいずれかに記載の封止用エポキシ樹脂組成物。
（１３）（Ｇ）シランカップリング剤をさらに含有することを特徴とする上記（１）〜（１２）のいずれかに記載の封止用エポキシ樹脂組成物。
（１４）（Ｇ）シランカップリング剤が、２級アミノ基を有するシランカップリング剤を含有することを特徴とする上記（１３）に記載の封止用エポキシ樹脂組成物。
（１５）（Ｇ）２級アミノ基を有するシランカップリング剤が、下記一般式（IV）で示される化合物を含有することを特徴とする上記（１４）に記載の封止用エポキシ樹脂組成物。

Wherein R ^{1 to} R ⁸ are selected from the group consisting of a hydrogen atom and a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, all of which may be the same or different, and n is Represents an integer of 0 to 3.)
(8) (B) The curing agent contains at least one selected from the group consisting of a biphenylene type phenol resin, an aralkyl type phenol resin, a dicyclopentadiene type phenol resin, a triphenylmethane type phenol resin, and a novolac type phenol resin. The sealing epoxy resin composition according to any one of (1) to (7) above.
(9) The epoxy resin composition for sealing according to any one of the above (1) to (8), further comprising (E) a curing accelerator.
(10) The epoxy resin composition for sealing according to the above (9), wherein the (E) curing accelerator contains an adduct of a phosphine compound and a quinone compound.
(11) (E) The curing accelerator includes an adduct of a phosphine compound and a quinone compound in which at least one alkyl group is bonded to a phosphorus atom, and the epoxy resin for sealing according to the above (10) Composition.
(12) The epoxy resin composition for sealing according to any one of the above (1) to (11), further comprising (F) an inorganic filler.
(13) The sealing epoxy resin composition according to any one of (1) to (12) above, further comprising (G) a silane coupling agent.
(14) The epoxy resin composition for sealing according to the above (13), wherein the (G) silane coupling agent contains a silane coupling agent having a secondary amino group.
(15) (G) The epoxy resin composition for sealing according to the above (14), wherein the silane coupling agent having a secondary amino group contains a compound represented by the following general formula (IV): .

（式中、Ｒ¹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なる群より選ばれ、Ｒ²は炭素数１〜６のアルキル基及びフェニル基からなる群より選ばれ、Ｒ³はメチル基又はエチル基を示し、ｎは１〜６の整数を示し、ｍは１〜３の整数を示す。）
（１６）上記（１）〜（１５）いずれかに記載の封止用エポキシ樹脂組成物で封止された素子を備えることを特徴とする電子部品装置。

(In the formula, R ¹ is selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 6 carbon atoms and an alkoxy group having 1 to ² carbon atoms, and R ² is composed of an alkyl group having 1 to 6 carbon atoms and a phenyl group. Selected from the group, R ³ represents a methyl group or an ethyl group, n represents an integer of 1 to 6, and m represents an integer of 1 to 3)
(16) An electronic component device comprising an element sealed with the sealing epoxy resin composition according to any one of (1) to (15).

  According to the present invention, an epoxy resin composition for sealing having good flame retardancy and excellent moldability, reflow resistance, moisture resistance and high temperature storage characteristics, and the use of such a composition are reliable. It is possible to provide products such as highly functional electronic component devices, and its industrial value is high.

Hereinafter, the present invention will be described in detail. The epoxy resin composition for sealing according to the present invention comprises (A) an epoxy resin, (B) a curing agent, (C) a cyclic phosphazene compound, and (D) a phosphate ester compound. In the present invention, the combined use of (C) a cyclic phosphazene compound and (D) a phosphate ester compound achieves flame retardancy of the resin composition without using a conventional flame retardant such as brominated resin or antimony oxide. Is possible. The epoxy resin composition for sealing according to the present invention comprises (E) a curing accelerator, (F) an inorganic filler, and (G) a silane coupling, in addition to the components (A) to (D) described above. You may add the well-known component used for the resin composition for sealing, such as an agent and (H) other various additives. (H) As various additives, a mold release agent, an ion exchanger, and a coloring agent are mentioned, for example. In addition, in the epoxy resin composition for sealing according to the present invention, in addition to the (C) cyclic phosphazene compound and the (D) phosphoric ester compound used in combination as a flame retardant, other known non-halogen and non-antimony flame retardants are added. May be. Hereinafter, the various components which comprise the epoxy resin composition for sealing by this invention are demonstrated in detail.
(A) Epoxy resin
The (A) epoxy resin used in the present invention may be one generally used in an epoxy resin composition for sealing, and is not particularly limited. For example, phenol novolac type epoxy resin, orthocresol novolak type epoxy resin, phenol resin including epoxy resin having triphenylmethane skeleton, phenols such as cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol F and / or α -Epoxy novolak resin obtained by condensation or co-condensation of naphthols such as naphthol, β-naphthol, dihydroxynaphthalene and the like and compounds having aldehyde groups such as formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, salicylaldehyde, etc. under acidic catalyst Diglycidyl ether such as bisphenol A, bisphenol F, bisphenol S, alkyl-substituted or unsubstituted biphenol, stilbene type Epoxy resin, hydroquinone type epoxy resin, glycidyl ester type epoxy resin obtained by reaction of polybasic acid such as phthalic acid and dimer acid and epichlorohydrin, polyamine such as diaminodiphenylmethane, isocyanuric acid and glycidyl amine type obtained by reaction of epichlorohydrin Epoxy resin, epoxidized product of co-condensation resin of cyclopentadiene and phenol, epoxy resin having naphthalene ring, epoxidized product of aralkyl type phenol resin such as phenol / aralkyl resin, naphthol / aralkyl resin, biphenylene type epoxy resin, triphenylene type Methylolpropane type epoxy resin, terpene modified epoxy resin, linear aliphatic epoxy resin obtained by oxidizing olefin bond with peracid such as peracetic acid, alicyclic epoxy resin, sulfur atom containing And epoxy resins. Even with these alone or may be used in combinations of two or more.

  Among the above epoxy resins, biphenyl type epoxy resins, bisphenol F type epoxy resins, stilbene type epoxy resins and sulfur atom-containing epoxy resins are preferable from the viewpoint of reflow resistance. From the viewpoint of curability, a novolac type epoxy resin is preferable. From the viewpoint of low hygroscopicity, a dicyclopentadiene type epoxy resin is preferable. From the viewpoint of heat resistance and low warpage, naphthalene type epoxy resins and triphenylmethane type epoxy resins are preferred. From the viewpoint of flame retardancy, biphenylene type epoxy resins and naphthol / aralkyl type epoxy resins are preferred.

  Hereinafter, the preferable epoxy resin will be described more specifically. The sealing epoxy resin composition according to the present invention preferably contains at least one of the following epoxy resins, but the epoxy resin is not limited to those exemplified below.

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

（式中、Ｒ¹〜Ｒ⁸は水素原子及び炭素数１〜１０の置換又は非置換の一価の炭化水素基から選ばれ、全てが同一でも異なっていてもよい。ｎは０〜３の整数を示す。）
上記一般式（V）で示されるビフェニル型エポキシ樹脂としては、例えば、４，４’−ビス（２，３−エポキシプロポキシ）ビフェニル又は４，４’−ビス（２，３−エポキシプロポキシ）−３，３’，５，５’−テトラメチルビフェニルを主成分とするエポキシ樹脂、エピクロルヒドリンと４，４’−ビフェノール又は４，４’−（３，３’，５，５’−テトラメチル）ビフェノールとを反応させて得られるエポキシ樹脂等が挙げられる。なかでも４，４’−ビス（２，３−エポキシプロポキシ）−３，３’，５，５’−テトラメチルビフェニルを主成分とするエポキシ樹脂が好ましい。ｎ＝０を主成分とするＹＸ−４０００（ジャパンエポキシレジン株式会社製商品名）が市販品として入手可能である。

Wherein R ^{1 to} R ⁸ are selected from a hydrogen atom and a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, all of which may be the same or different. N is 0 to 3 Indicates an integer.)
Examples of the biphenyl type epoxy resin represented by the general formula (V) include 4,4′-bis (2,3-epoxypropoxy) biphenyl or 4,4′-bis (2,3-epoxypropoxy) -3. , 3 ′, 5,5′-tetramethylbiphenyl as the main component, epichlorohydrin and 4,4′-biphenol or 4,4 ′-(3,3 ′, 5,5′-tetramethyl) biphenol An epoxy resin obtained by reacting is used. Among these, an epoxy resin mainly composed of 4,4′-bis (2,3-epoxypropoxy) -3,3 ′, 5,5′-tetramethylbiphenyl is preferable. YX-4000 (trade name, manufactured by Japan Epoxy Resin Co., Ltd.) whose main component is n = 0 is available as a commercial product.

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

（式中、Ｒ¹〜Ｒ⁸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。）
上記一般式（VI）で示されるビスフェノールＦ型エポキシ樹脂としては、例えば、Ｒ¹、Ｒ³、Ｒ⁶及びＲ⁸がメチル基で、Ｒ²、Ｒ⁴、Ｒ⁵及びＲ⁷が水素原子であり、ｎ＝０を主成分とするＹＳＬＶ−８０ＸＹ（新日鉄化学株式会社製商品名）が市販品として入手可能である。

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

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

（式中、Ｒ¹〜Ｒ⁸は水素原子及び炭素数１〜５の置換又は非置換の一価の炭化水素基から選ばれ、全てが同一でも異なっていてもよい。ｎは０〜１０の整数を示す。）
上記一般式（VII）で示されるスチルベン型エポキシ樹脂は、原料であるスチルベン系フェノール類とエピクロルヒドリンとを塩基性物質存在下で反応させて得ることができる。この原料であるスチルベン系フェノール類としては、例えば３−ｔ−ブチル−４，４’−ジヒドロキシ−３’，５，５’−トリメチルスチルベン、３−ｔ−ブチル−４，４’−ジヒドロキシ−３’，５’，６−トリメチルスチルベン、４，４’−ジヒドロキシ−３，３’，５，５’−テトラメチルスチルベン、４，４’−ジヒドロキシ−３，３’−ジ−ｔ−ブチル−５，５’−ジメチルスチルベン、４，４’−ジヒドロキシ−３，３’−ジ−ｔ−ブチル−６，６’−ジメチルスチルベン等が挙げられ、なかでも３−ｔ−ブチル−４，４’−ジヒドロキシ−３’，５，５’−トリメチルスチルベン、及び４，４’−ジヒドロキシ−３，３’，５，５’−テトラメチルスチルベンが好ましい。これらのスチルベン型フェノール類は単独で用いても２種以上を組み合わせて用いてもよい。
硫黄原子含有エポキシ樹脂としては、例えば下記一般式（III）で示されるエポキシ樹脂等が挙げられる。

(Wherein R ^{1 to} R ⁸ are selected from a hydrogen atom and a substituted or unsubstituted monovalent hydrocarbon group having 1 to 5 carbon atoms, and all may be the same or different. N is 0 to 10) Indicates an integer.)
The stilbene type epoxy resin represented by the general formula (VII) 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-t-butyl-4,4′-dihydroxy-3 ′, 5,5′-trimethylstilbene, 3-t-butyl-4,4′-dihydroxy-3. ', 5', 6-trimethylstilbene, 4,4'-dihydroxy-3,3 ', 5,5'-tetramethylstilbene, 4,4'-dihydroxy-3,3'-di-t-butyl-5 , 5'-dimethylstilbene, 4,4'-dihydroxy-3,3'-di-t-butyl-6,6'-dimethylstilbene and the like, among others, 3-t-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.
Examples of the sulfur atom-containing epoxy resin include an epoxy resin represented by the following general formula (III).

（式中、Ｒ¹〜Ｒ⁸は水素原子、置換又は非置換の炭素数１〜１０のアルキル基及び置換又は非置換の炭素数１〜１０のアルコキシ基から選ばれ、全てが同一でも異なっていてもよい。ｎは０〜３の整数を示す。）
上記一般式（III）で示される硫黄原子含有エポキシ樹脂のなかでも、Ｒ²、Ｒ³、Ｒ⁶及びＲ⁷が水素原子で、Ｒ¹、Ｒ⁴、Ｒ⁵及びＲ⁸がアルキル基であるエポキシ樹脂が好ましく、Ｒ²、Ｒ³、Ｒ⁶及びＲ⁷が水素原子で、Ｒ¹及びＲ⁸がｔ−ブチル基で、Ｒ⁴及びＲ⁵がメチル基であるエポキシ樹脂がより好ましい。このような化合物としては、ＹＳＬＶ−１２０ＴＥ(新日鐵化学社製)等が市販品として入手可能である。

(Wherein R ^{1 to} R ⁸ are selected from a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms and a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, all of which are the same or different. (N represents an integer of 0 to 3.)
Among the sulfur atom-containing epoxy resins represented by the general formula (III), 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 preferable, and an epoxy resin in which R ² , R ³ , R ⁶ and R ⁷ are hydrogen atoms, R ¹ and R ⁸ are t-butyl groups, and R ⁴ and R ⁵ are methyl groups is more preferable. As such a compound, YSLV-120TE (manufactured by Nippon Steel Chemical Co., Ltd.) and the like are commercially available.

  The above-mentioned epoxy resin may be used alone or in combination of two or more, but the blending amount thereof is 20% in total with respect to the total amount of the epoxy resin in order to exhibit its performance. % Or more, preferably 30% by weight or more, and more preferably 50% by weight or more.

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

（式中、Ｒは水素原子及び炭素数１〜１０の置換又は非置換の一価の炭化水素基から選ばれ、ｎは０〜１０の整数を示す。）
上記一般式（VIII）で示されるノボラック型エポキシ樹脂は、ノボラック型フェノール樹脂にエピクロルヒドリンを反応させることによって容易に得られる。なかでも、一般式（X）中のＲとしては、メチル基、エチル基、プロピル基、ブチル基、イソプロピル基、イソブチル基等の炭素数１〜１０のアルキル基、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基等の炭素数１〜１０のアルコキシル基が好ましく、水素原子又はメチル基がより好ましい。ｎは０〜３の整数が好ましい。上記一般式（VIII）で示されるノボラック型エポキシ樹脂のなかでも、オルトクレゾールノボラック型エポキシ樹脂が好ましい。Ｎ−６００シリーズ（大日本インキ化学工業株式会社製商品名）が市販品として入手可能である。

(In the formula, R is selected from a hydrogen atom and a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and n represents an integer of 0 to 10)
The novolak type epoxy resin represented by the general formula (VIII) can be easily obtained by reacting a novolak type phenol resin with epichlorohydrin. Especially, as R in general formula (X), 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 epoxy resins represented by the general formula (VIII), orthocresol novolac epoxy resins are preferable. N-600 series (Dainippon Ink Chemical Co., Ltd. trade name) is available as a commercial product.

  In the case of using a novolac type epoxy resin, its blending amount is preferably 20% by weight or more, more preferably 30% by weight or more, based on the total amount of the epoxy resin in order to exhibit its performance.

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

（式中、Ｒ¹及びＲ²は水素原子及び炭素数１〜１０の置換又は非置換の一価の炭化水素基からそれぞれ独立して選ばれ、ｎは０〜１０の整数を示し、ｍは０〜６の整数を示す。）
上記式（IX）中のＲ¹としては、例えば、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、ｔ−ブチル基等のアルキル基、ビニル基、アリル基、ブテニル基等のアルケニル基、ハロゲン化アルキル基、アミノ基置換アルキル基、メルカプト基置換アルキル基などの炭素数１〜５の置換又は非置換の一価の炭化水素基が挙げられ、なかでもメチル基、エチル基等のアルキル基及び水素原子が好ましく、メチル基及び水素原子がより好ましい。Ｒ²としては、例えば、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、ｔ−ブチル基等のアルキル基、ビニル基、アリル基、ブテニル基等のアルケニル基、ハロゲン化アルキル基、アミノ基置換アルキル基、メルカプト基置換アルキル基などの炭素数１〜５の置換又は非置換の一価の炭化水素基が挙げられ、なかでも水素原子が好ましい。ＨＰ−７２００（大日本インキ化学工業株式会社製商品名）が市販品として入手可能である。

Wherein R ¹ and R ² are each independently selected from a hydrogen atom and a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, n is an integer of 0 to 10, and m is Represents an integer of 0 to 6.)
Examples of R ¹ in the above formula (IX) 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 t-butyl group, a vinyl group, an allyl group, and a butenyl group. C1-C5 substituted or unsubstituted monovalent hydrocarbon groups such as alkenyl groups, halogenated alkyl groups, amino group-substituted alkyl groups, mercapto group-substituted alkyl groups, and the like. Among them, methyl groups, ethyl groups Alkyl groups and hydrogen atoms such as methyl groups and hydrogen atoms 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 t-butyl group, an alkenyl group such as a vinyl group, an allyl group, and a butenyl group, and an alkyl halide. Examples thereof include substituted or unsubstituted monovalent hydrocarbon groups having 1 to 5 carbon atoms such as a group, an amino group-substituted alkyl group, and a mercapto group-substituted alkyl group, and among them, a hydrogen atom is preferable. HP-7200 (Dainippon Ink Chemical Co., Ltd. product name) is available as a commercial product.

  When a dicyclopentadiene type epoxy resin is used, its blending amount is preferably 20% by weight or more, more preferably 30% by weight or more, based on the total amount of the epoxy resin in order to exhibit its performance.

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

（式中、Ｒ¹〜Ｒ³は水素原子及び置換又は非置換の炭素数１〜１２の一価の炭化水素基から選ばれ、それぞれ全てが同一でも異なっていてもよい。ｐは１又は０で、ｌ、ｍはそれぞれ０〜１１の整数であって、（ｌ＋ｍ）が１〜１１の整数でかつ（ｌ＋ｐ）が１〜１２の整数となるよう選ばれる。ｉは０〜３の整数、ｊは０〜２の整数、ｋは０〜４の整数を示す。）
上記一般式（X）で示されるナフタレン型エポキシ樹脂としては、ｌ個の構成単位及びｍ個の構成単位をランダムに含むランダム共重合体、交互に含む交互共重合体、規則的に含む共重合体、ブロック状に含むブロック共重合体が挙げられ、これらのいずれか１種を単独で用いても、２種以上を組み合わせて用いてもよい。

Wherein R ^{1 to} R ³ are selected from a hydrogen atom and a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, and each may be the same or different. P is 1 or 0 And l and m are each an integer of 0 to 11, wherein (l + m) is an integer of 1 to 11 and (l + p) is an integer of 1 to 12. i is an integer of 0 to 3, j represents an integer of 0 to 2, and k represents an integer of 0 to 4.)
As the naphthalene type epoxy resin represented by the general formula (X), a random copolymer containing 1 constituent unit and m constituent units at random, an alternating copolymer containing alternately, a copolymer containing regularly Examples thereof include block copolymers which are included in a combined or block form, and any one of these may be used alone, or two or more may be used in combination.

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

（式中、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。）
ＥＰＰＮ−５００シリーズ（日本化薬株式会社製商品名）が市販品として入手可能である。

(In the formula, 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.)
EPPN-500 series (trade name, manufactured by Nippon Kayaku Co., Ltd.) is available as a commercial product.

  The above-mentioned epoxy resin may be used alone or in combination, but the blending amount is 20% by weight or more in total with respect to the total amount of the epoxy resin in order to exhibit its performance. Preferably, it is 30% by weight or more, more preferably 50% by weight or more.

  The biphenyl type epoxy resin, the stilbene type epoxy resin, the sulfur atom-containing epoxy resin, the novolac type epoxy resin, the dicyclopentadiene type epoxy resin, the naphthalene type epoxy resin, and the triphenylmethane type epoxy resin are any one kind. Although it may be used alone or in combination of two or more, the blending amount is preferably 50% by weight or more, more preferably 60% by weight or more, more preferably 80% by weight based on the total amount of the epoxy resin. More preferably, the above is used.

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

（式中、Ｒ¹〜Ｒ⁹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。）
ビフェニレン型エポキシ樹脂としては、ＮＣ−３０００（日本化薬株式会社製商品名）が市販品として入手可能である。

(In the formula, all of R ^{1 to} R ⁹ may be the same or different, and an alkyl group having 1 to 10 carbon atoms such as a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, and an isobutyl group) C1-C10 alkoxyl group such as methoxy group, ethoxy group, propoxy group, butoxy group, aryl group having 6-10 carbon atoms such as phenyl group, tolyl group, xylyl group, benzyl group, phenethyl group, etc. A hydrogen atom and a methyl group are preferable, and n represents an integer of 0 to 10.)
As a biphenylene type epoxy resin, NC-3000 (trade name, manufactured by Nippon Kayaku Co., Ltd.) is commercially available.

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

（式中、Ｒ¹〜Ｒ³は水素原子及び置換又は非置換の炭素数１〜１２の一価の炭化水素基から選ばれ、それぞれ全てが同一でも異なっていてもよい。ｎは１〜１０の整数を示す。）
ナフトール・アラルキル型エポキシ樹脂としてはＥＳＮ−１７５等（東都化成株式会社製商品名）が市販品として入手可能である。

(In the formula, R ^{1 to} R ³ are selected from a hydrogen atom and a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, and each may be the same or different. N is 1 to 10) Indicates an integer.)
As the naphthol / aralkyl type epoxy resin, ESN-175 (trade name, manufactured by Tohto Kasei Co., Ltd.) is available as a commercial product.

  From the viewpoint of flame retardancy, any one of the epoxy resins represented by the formulas (XII) and (XIII) may be used alone or in combination, but the blending amount is determined by the performance. In order to exhibit it, it is preferable to set it as 20 weight% or more in total with respect to the epoxy resin whole quantity, More preferably, it is 30 weight% or more, It is further more preferable to set it as 50 weight% or more.

  Among the epoxy resins, a sulfur atom-containing epoxy resin having the structure represented by the general formula (I) is most preferable, particularly from the viewpoint of reliability such as reflow resistance, moldability, and flame retardancy.

The melt viscosity at 150 ° C. of the (A) epoxy resin used in the present invention is preferably 2 poise or less, more preferably 1 poise or less, and even more preferably 0.5 poise or less from the viewpoint of fluidity. Here, the melt viscosity is a viscosity measured with an ICI cone plate viscometer.
(B) Curing agent
The (B) curing agent used in the present invention may be one generally used in an epoxy resin composition for sealing, and is not particularly limited. For example, phenol, cresol, resorcin, catechol, bisphenol A, bisphenol F, phenylphenol, aminophenol and other phenols and / or naphthols such as α-naphthol, β-naphthol, dihydroxynaphthalene and formaldehyde, benzaldehyde, salicylaldehyde, etc. Phenol aralkyl synthesized from novolak-type phenol resins, phenols and / or naphthols and dimethoxyparaxylene or bis (methoxymethyl) biphenyl obtained by condensation or cocondensation of a compound having an aldehyde group with an acidic catalyst Resin, biphenylene type phenol resin, aralkyl type phenol resin such as naphthol / aralkyl resin, phenol and / or naphthols and cyclopentadiene And dicyclopentadiene type phenolic resins such as dichloropentadiene type phenol novolak resin and naphthol novolak resin, terpene modified phenolic resins, etc., which may be used alone or in combination of two or more. .

  Among these, from the viewpoint of flame retardancy, a biphenylene type phenol resin is preferable. From the viewpoint of reflow resistance and curability, aralkyl type phenol resins are preferred. From the viewpoint of low hygroscopicity, a dicyclopentadiene type phenol resin is preferable. From the viewpoints of heat resistance, low expansion rate and low warpage, a triphenylmethane type phenol resin is preferable. From the viewpoint of curability, a novolac type phenol resin is preferable. It is preferable that the epoxy resin composition for sealing according to the present invention contains at least one of these phenol resins.

  Hereinafter, the preferable curing agent in the present invention will be described more specifically, but the curing agent is not limited to the following.

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

上記式(XIV)中のＲ¹〜Ｒ⁹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 (XIV) may all be the same or different and have 1 to 10 carbon atoms such as a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, and 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.

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

  When a biphenylene type phenol resin is used, its blending amount is preferably 30% by weight or more, more preferably 50% by weight or more, more preferably 60% by weight or more based on the total amount of the curing agent in order to exhibit its performance. Further preferred.

  Examples of the aralkyl type phenol resin include phenol aralkyl resin and naphthol aralkyl resin. When such an aralkyl type phenol resin is used, its blending amount is preferably 30% by weight or more, more preferably 50% by weight or more, based on the total amount of the curing agent in order to exhibit its performance.

  As the phenol / aralkyl resin, those represented by the following general formula (XV) are preferable.

（式中、Ｒは水素原子及び炭素数１〜１０の置換又は非置換の一価の炭化水素基から選ばれ、ｎは０〜１０の整数を示す。）
上記一般式(XV)で示されるフェノール・アラルキル樹脂において、Ｒが水素原子で、ｎの平均値が０〜８であるものがより好ましい。具体例としては、ｐ−キシリレン型フェノール・アラルキル樹脂、ｍ−キシリレン型フェノール・アラルキル樹脂等が挙げられる。

(In the formula, R is selected from a hydrogen atom and a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and n represents an integer of 0 to 10)
In the phenol / aralkyl resin represented by the general formula (XV), it is more preferable that R is a hydrogen atom and the average value of n is 0 to 8. Specific examples include p-xylylene type phenol / aralkyl resins, m-xylylene type phenol / aralkyl resins, and the like.

  As the naphthol / aralkyl resin, those represented by the following general formula (XVI) are preferable.

（式中、Ｒは水素原子及び炭素数１〜１０の置換又は非置換の一価の炭化水素基から選ばれ、ｎは０〜１０の整数を示す。）
ジシクロペンタジエン型フェノール樹脂としては、例えば下記一般式(XVII)で示されるフェノール樹脂等が挙げられる。

(In the formula, R is selected from a hydrogen atom and a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and n represents an integer of 0 to 10)
Examples of the dicyclopentadiene type phenol resin include a phenol resin represented by the following general formula (XVII).

（式中、Ｒ¹及びＲ²は水素原子及び炭素数１〜１０の置換又は非置換の一価の炭化水素基からそれぞれ独立して選ばれ、ｎは０〜１０の整数を示し、ｍは０〜６の整数を示す。）
ジシクロペンタジエン型フェノール樹脂を用いる場合、その配合量は、その性能を発揮するために硬化剤全量に対して３０重量％以上とすることが好ましく、５０重量％以上がより好ましい。

Wherein R ¹ and R ² are each independently selected from a hydrogen atom and a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, n is an integer of 0 to 10, and m is Represents an integer of 0 to 6.)
When a dicyclopentadiene type phenol resin is used, the blending amount is preferably 30% by weight or more, more preferably 50% by weight or more, based on the total amount of the curing agent in order to exhibit its performance.

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

（式中、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。）
トリフェニルメタン型フェノール樹脂を用いる場合、その配合量は、その性能を発揮するために硬化剤全量に対して３０重量％以上とすることが好ましく、５０重量％以上がより好ましい。

(In the formula, 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.)
When using a triphenylmethane type phenol resin, the blending amount is preferably 30% by weight or more, more preferably 50% by weight or more, based on the total amount of the curing agent in order to exhibit its performance.

  Examples of the novolak type phenol resin include a phenol novolak resin, a cresol novolak resin, a naphthol novolak resin, and the like. Among these, a phenol novolak resin is preferable. In the case of using a novolac type phenol resin, the blending amount is preferably 30% by weight or more, more preferably 50% by weight or more based on the total amount of the curing agent in order to exhibit its performance.

  The biphenylene type phenol resin, aralkyl type phenol resin, dicyclopentadiene type phenol resin, triphenylmethane type phenol resin and novolac type phenol resin mentioned above may be used alone or in combination of two or more of them. Although they may be used in combination, the blending amount is preferably 60% by weight or more, more preferably 80% by weight or more, based on the total amount of the curing agent.

  The melt viscosity at 150 ° C. of the (B) curing agent used in the present invention is preferably 2 poises or less, more preferably 1 poise or less from the viewpoint of fluidity. Here, the melt viscosity indicates the ICI viscosity.

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: There is no particular limitation. However, in order to keep each unreacted component small, the equivalent ratio is preferably set in the range of 0.5 to 2, more preferably in the range of 0.6 to 1.3. In order to obtain a sealing epoxy resin composition excellent in moldability and reflow resistance, the equivalent ratio is more preferably set in the range of 0.8 to 1.2.
(C) Cyclic phosphazene compound
The cyclic phosphazene compound (C) used in the present invention may be a cyclic phosphazene compound generally used in the art, and is not particularly limited. However, from the viewpoints of stability and hydrolysis resistance, a cyclic phosphazene compound represented by the following general formula (I) is preferable.

（式中、ｎは３〜５の整数であり、ＲおよびＲ’はそれぞれ独立して同じでも異なってもよく、炭素数１〜４のアルキル基またはアリール基を示し、ヒドロキシ基で置換されてもよい。）
上記一般式（I）で示される環状ホスファゼン化合物としては、３量体（ｎ＝３）の６員環、４量体（ｎ＝４）の８員環、及び５量体（ｎ＝５）の１０員環の化合物を単独あるいは混合して用いることができる。なかでも流動性の観点からは、３量体の化合物を主成分として用いることが好ましい。

(In the formula, n is an integer of 3 to 5, and R and R ′ may be the same or different and each represents an alkyl or aryl group having 1 to 4 carbon atoms, and is substituted with a hydroxy group. May be.)
The cyclic phosphazene compound represented by the general formula (I) includes a trimer (n = 3) 6-membered ring, a tetramer (n = 4) 8-membered ring, and a pentamer (n = 5). These 10-membered ring compounds can be used alone or in combination. Among these, from the viewpoint of fluidity, it is preferable to use a trimer compound as a main component.

  In the above general formula (I), there are n R and R 'each independently, and they may be the same or different. For example, in the case of a 6-membered ring of a trimer (n = 3), R and R ′ are 6 substituents, which may all be the same or different. R and R 'are selected from an alkyl group having 1 to 4 carbon atoms or an aryl group, and may be substituted with a hydroxy group. From the viewpoints of heat resistance, moisture resistance and moldability, an aryl group is preferred. Among the aryl groups, a phenyl group is preferable, and a phenyl group (hydroxyphenyl group) substituted with a hydroxy group is more preferable.

  In the cyclic phosphazene compound represented by the above general formula (I), when a hydroxyphenyl group is introduced into one or both of R and R ′, the number of hydroxyphenyl groups can be selected from 1 to 10 It is. Especially, it is preferable that the number of hydroxyphenyl groups is 1-4, and it is more preferable that it is 1-3. In the case of less than one, components that are not taken into the crosslinked structure of the cured epoxy resin come out, so that the moldability and heat resistance are likely to deteriorate. On the other hand, when it exceeds four, hardened | cured material tends to become weak.

  A preferable structure of the cyclic phosphazene compound used in the present invention includes, for example, the following general formula (XIX).

（式中、Ｒ¹〜Ｒ⁶は、それぞれ独立し、同じでも異なってもよく、水酸基または水素原子を示し、化合物中の水酸基は０〜６個で、水素原子は６〜０個である）
また本発明に用いられる環状ホスファゼン化合物は、化合物の少なくとも一部が架橋されていてもよい。架橋されてなる（架橋構造を有する）環状ホスファゼンとしては、主鎖骨格中に次式（XX）及び／又は次式（XXI）を繰り返し単位として含む環状ホスファゼン化合物、あるいはホスファゼン環中の燐原子に対する置換位置が異なる次式（XXII）及び／又は次式（XXIII）を繰り返し単位として含む化合物等が挙げられる。

(Wherein, R ¹ to R ⁶ are each independently, it may be the same or different, represents a hydroxyl group or a hydrogen atom, a hydroxyl group in the compound 0-6, hydrogen atom is 6-0 pieces)
In the cyclic phosphazene compound used in the present invention, at least a part of the compound may be crosslinked. As the cyclic phosphazene having a crosslinked structure (having a crosslinked structure), a cyclic phosphazene compound containing the following formula (XX) and / or the following formula (XXI) as a repeating unit in the main chain skeleton, or a phosphorus atom in the phosphazene ring Examples thereof include compounds containing the following formula (XXII) and / or the following formula (XXIII) having different substitution positions as repeating units.

ここで、式（XX）及び式（XXII）中のｍは１〜１０の整数で、Ｒ^１〜Ｒ^４は置換基を有しても良い炭素数１〜１２のアルキル基、アリール基から選ばれ、全て同一でも異なっていても良い。Ａは炭素数１〜４のアルキレン基又はアリレン基を示す。式（XXI）及び式（XXIII）中のｎは１〜１０の整数で、Ｒ^５〜Ｒ^８は置換基を有しても良い炭素数１〜１２のアルキル基又はアリール基から選ばれ、全て同一でも異なっていても良く、Ａは炭素数１〜４のアルキレン基又はアリレン基を示す。また、式中ｍ個のＲ^１、Ｒ^２、Ｒ^３、Ｒ^４はｍ個全てが同一でも異なっていても良く、ｎ個のＲ^５、Ｒ^６、Ｒ^７、Ｒ^８はｎ個全てが同一でも異なっていても良い。

Here, m in the formula (XX) and the formula (XXII) is an integer of 1 to 10, and R ^{1 to} R ⁴ are selected from an alkyl group having 1 to 12 carbon atoms and an aryl group which may have a substituent. 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 (XXI) and Formula (XXIII) is an integer of 1 to 10, and R ^{5 to} R ⁸ are selected from an alkyl group having 1 to 12 carbon atoms or an aryl group which 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.

In the above formula (XX) to formula (XXIII), the alkyl group or aryl group having 1 to 12 carbon atoms which may have a substituent represented by R ^{1 to} R ⁸ is not particularly limited. For example, methyl groups, ethyl groups, propyl groups, isopropyl groups, butyl groups, isobutyl groups, sec-butyl groups, tert-butyl groups and other alkyl groups, phenyl groups, 1-naphthyl groups, 2-naphthyl groups and other aryl groups Alkyl such as 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. Examples thereof include aryl-substituted alkyl groups such as group-substituted aryl groups, benzyl groups, and phenethyl groups. Further, examples of substituents that can be substituted for these include alkyl groups, alkoxyl groups, aryl groups, hydroxyl groups, amino groups, epoxy groups, vinyls Group, hydroxyalkyl group, 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 (XX) to (XXIII) 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, biphenylene group and the like. From the viewpoint of heat resistance and moisture resistance of the epoxy resin composition, an arylene group is preferable, among which a phenylene group, A biphenylene group is more preferred.

  The cyclic phosphazene compound is a polymer of any one of the above formulas (XX) to (XXIII), a copolymer of the above formula (XX) and the above formula (XXI), or the above formula (XXII) and the above formula (XXIII). 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 cyclic phosphazene compound include a polymer of the following formula (XXIV) and a copolymer of the following formula (XXV).

（式中、ｎは、０〜９の整数であり、Ｒ^１〜Ｒ⁶はそれぞれ独立に水素又は水酸基を示す。）

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

上記式中、ｍ、ｎは、０〜９の整数であり、Ｒ^１〜Ｒ⁶はそれぞれ独立に水素または水酸基から選ばれる。また、上記式で示される環状ホスファゼン化合物は、次に示すｍ個の繰り返し単位（ａ）とｎ個の繰り返し単位（ｂ）を交互に含むもの、ブロック状に含むもの、ランダムに含むもののいずれであってもかまわないが、ランダムに含むものが好ましい。

In the above formula, m and n are integers of 0 to 9, and R ^{1 to} R ⁶ are each independently selected from hydrogen or a hydroxyl group. In addition, the cyclic phosphazene compound represented by the above formula includes any of the following m repeating units (a) and n repeating units (b) alternately included, those included in a block form, and those included randomly. Although it does not matter, it is preferable to include it at random.

なかでも、上記式（XXIV）でｎが３〜６の重合体を主成分とするものや、上記式（XXV）でＲ¹〜Ｒ⁶が全て水素又は１つが水酸基であり、ｎ／ｍが１／２〜１／３で、ｎ＋ｍが３〜６の共重合体を主成分とするものが好ましい。また、市販のホスファゼン化合物としては、ＳＰＥ−１００（大塚化学製商品名）、ＳＰＨ−１００（大塚化学製商品名）が入手可能である。
（Ｄ）リン酸エステル化合物
本発明において用いられる（Ｄ）リン酸エステル化合物は、リン酸とアルコール化合物又はフェノール化合物とのエステル化合物であれば特に制限はない。例えば、トリメチルホスフェート、トリエチルホスフェート、トリフェニルホスフェート、トリクレジルホスフェート、トリキシレニルホスフェート、クレジルジフェニルホスフェート、キシレニルジフェニルホスフェート、トリス（２，６ジメチルフェニル）ホスフェート及び芳香族縮合リン酸エステル等が挙げられる。なかでも耐加水分解性の観点からは、下記一般式（II）で示される芳香族縮合リン酸エステルが好ましい。

Among them, the main component is a polymer in which n is 3 to 6 in the above formula (XXIV), or R ^{1 to} R ⁶ are all hydrogen or one is a hydroxyl group in the above formula (XXV), and n / m is The main component is a copolymer of 1/2 to 1/3 and n + m of 3 to 6. Moreover, as a commercially available phosphazene compound, SPE-100 (trade name made by Otsuka Chemical) and SPH-100 (trade name made by Otsuka Chemical) are available.
(D) Phosphate ester compound The (D) phosphate ester compound used in the present invention is not particularly limited as long as it is an ester compound of phosphoric acid and an alcohol compound or a phenol compound. For example, trimethyl phosphate, triethyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, tris (2,6 dimethylphenyl) phosphate and aromatic condensed phosphate ester, etc. Is mentioned. Among these, from the viewpoint of hydrolysis resistance, an aromatic condensed phosphate represented by the following general formula (II) is preferable.

（式中、８個のＲは炭素数１〜４のアルキル基を示し、全て同一でも異なっていてもよく、Ａｒは芳香族環を示す。）
上記式（II）のリン酸エステルを例示すると、下記構造式（XXVI）〜（XXX）で示されるリン酸エステル等が挙げられる。

(In the formula, 8 Rs represent an alkyl group having 1 to 4 carbon atoms, which may all be the same or different, and Ar represents an aromatic ring.)
Examples of the phosphoric acid ester of the above formula (II) include phosphoric acid esters represented by the following structural formulas (XXVI) to (XXX).

本発明では、難燃剤として（Ｃ）環状ホスファゼン化合物と（Ｄ）リン酸エステル化合物とを併用することによって、それぞれの成分を単独で用いるよりも、樹脂組成物の優れた難燃性と成形性とを両立することが可能である。（Ｃ）環状ホスファゼン化合物は化学的に安定であり、またヒドロキシフェニル基を有する環状ホスファゼン化合物を用いた場合はエポキシ樹脂と反応し、硬化性が向上する。一方、（Ｄ）リン酸エステル化合物の化学的安定性は（Ｃ）環状ホスファゼン化合物よりも劣るものの、それ自体が優れた難燃性を示すため、（Ｃ）環状ホスファゼン化合物単独では成し得ない難燃性を発現させることが可能である。

In the present invention, by using together (C) a cyclic phosphazene compound and (D) a phosphate ester compound as a flame retardant, the flame retardancy and moldability of the resin composition are superior to using each component alone. It is possible to achieve both. (C) The cyclic phosphazene compound is chemically stable, and when a cyclic phosphazene compound having a hydroxyphenyl group is used, it reacts with the epoxy resin and the curability is improved. On the other hand, although the chemical stability of the (D) phosphate ester compound is inferior to that of the (C) cyclic phosphazene compound, it exhibits excellent flame retardancy per se and cannot be achieved with the (C) cyclic phosphazene compound alone. It is possible to develop flame retardancy.

The total addition amount of (C) cyclic phosphazene compound and (D) phosphate ester compound used in combination in the epoxy resin composition for sealing according to the present invention is a phosphorus atom relative to all the other ingredients except the filler. It is preferable to be within the range of 0.1 to 5.0% by weight. More preferably, it is 0.2 to 3.0% by weight. When the amount is less than 0.1% by weight, the flame retardant effect tends to be low. If it exceeds 5.0% by weight, the moldability and moisture resistance are lowered and the oozing out during molding may occur, which may impair the appearance.
(E) Curing accelerator
In the epoxy resin composition for sealing according to the present invention, (E) a curing accelerator can be used as necessary in order to promote the reaction between (A) the epoxy resin and (B) the curing agent. (E) A hardening accelerator may be what is generally used for the epoxy resin composition for sealing, and there is no restriction | limiting in particular. For example, 1,8-diaza-bicyclo (5,4,0) undecene-7, 1,5-diaza-bicyclo (4,3,0) nonene, 5,6-dibutylamino-1,8-diaza-bicyclo Cycloamidine compounds such as (5,4,0) undecene-7 and these compounds include maleic anhydride, 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2 , 6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, quinone compounds such as phenyl-1,4-benzoquinone, diazophenylmethane, Compounds with intramolecular polarization formed by adding compounds with π bonds such as phenol resin, benzyldimethylamine, triethanolamine, dimethylamine Tertiary amines such as noethanol and tris (dimethylaminomethyl) phenol and their derivatives, imidazoles such as 2-methylimidazole, 2-phenylimidazole and 2-phenyl-4-methylimidazole and their derivatives, tributylphosphine Phosphine compounds such as methyldiphenylphosphine, triphenylphosphine, tris (4-methylphenyl) phosphine, diphenylphosphine and phenylphosphine, and π such as maleic anhydride, the above quinone compound, diazophenylmethane, phenol resin, etc. Phosphorus compounds having intramolecular polarization formed by adding a compound having a bond, tetraphenylphosphonium tetraphenylborate, triphenylphosphine tetraphenylborate, 2-ethyl-4- Chill imidazole tetraphenyl borate, N- such methylmorpholine tetraphenyl borate tetraphenyl boron salts and derivatives thereof, and the like, may be used in combination of two or more even with these alone.

  Of these, triphenylphosphine is preferable from the viewpoint of flame retardancy and curability. From the viewpoint of flame retardancy, curability, fluidity, and releasability, an adduct of a tertiary phosphine compound and a quinone compound is preferable. 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, alkyl groups such as tris (4-ethoxyphenyl) phosphine, 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. Furthermore, an adduct of a phosphine compound and a quinone compound in which at least one alkyl group is bonded to a phosphorus atom is preferable from the viewpoints of curability, fluidity and flame retardancy.

The blending amount of the curing accelerator is not particularly limited as long as the curing acceleration effect is achieved. For example, 0.005 to 2 weight% is preferable with respect to the epoxy resin composition for sealing, and 0.01 to 0.5 weight% is more preferable. If it is less than 0.005% by weight, the curability in a short time tends to be inferior, and if it exceeds 2% by weight, the curing rate tends to be too high and it tends to be difficult to obtain a good molded product.
(F) Inorganic filler (F) Inorganic filler can be mix | blended with the epoxy resin composition for sealing of this invention as needed. By blending an inorganic filler with the epoxy resin composition, effects such as reduction of the linear expansion coefficient, improvement of other wettability, improvement of thermal conductivity, and improvement of strength can be obtained. The inorganic filler is not particularly limited, and may be a well-known inorganic filler used in the art. Typical inorganic fillers include, for example, fused silica, crystalline silica, alumina, zircon, calcium silicate, calcium carbonate, potassium titanate, silicon carbide, silicon nitride, aluminum nitride, boron nitride, beryllia, zirconia, zircon, phosphor. Examples thereof include powders such as stellite, steatite, spinel, mullite, and titania, beads formed by spheroidizing these, and glass fibers. 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.) and the like are available as commercial products. As zinc molybdate, KEMGARD911B, 911C, 1100 (manufactured by Sherwin-Williams) and the like are commercially available.

These inorganic fillers may be used alone or in combination of two or more. Among them, fused silica is preferable from the viewpoint of filling property and reduction of linear expansion coefficient, 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 preferably 50% by weight or more based on the epoxy resin composition for sealing, from the viewpoint of flame retardancy, moldability, hygroscopicity, linear expansion coefficient reduction, strength improvement and reflow resistance, 60 to 95% by weight is more preferable, and 70 to 90% by weight is more preferable. If the amount is less than 60% by weight, the flame retardancy and reflow resistance tend to decrease, and if it exceeds 95% by weight, the fluidity tends to be insufficient, and the flame retardancy also tends to decrease (G) coupling agent In the present invention, when (F) an inorganic filler is used, it is preferable to further blend (G) a coupling agent in the resin composition in order to enhance the adhesion between the resin component and the inorganic filler. (G) As a coupling agent, it may be generally used for the epoxy resin composition for sealing, and there is no restriction | limiting in particular. For example, various silane compounds such as silane compounds having primary and / or secondary and / or tertiary amino groups, epoxy silane, mercapto silane, alkyl silane, ureido silane, vinyl silane, titanium compounds, aluminum chelates, aluminum / Zirconium compounds and the like. Examples of these are vinyltrichlorosilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycol. Sidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, vinyltriacetoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropyl Triethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-anilinopropyltrimethoxysilane, γ-anilinopropyltriethoxysilane, γ- (N, N-dimethyl) aminopropyltrimethoxy Silane, γ- (N, N-diethyl) aminopropyltrimethoxysilane, γ- (N, N-dibutyl) aminopropyltrimethoxysilane, γ- (N-methyl) anilinopropyltrimethoxysilane, γ- (N -Ethyl) anilinopropyltrimethoxysilane, γ- (N, N-dimethyl) aminopropyltriethoxysilane, γ- (N, N-diethyl) aminopropyltriethoxysilane, γ- (N, N-dibutyl) amino Propyltriethoxysilane, γ- (N-methyl) anilinopropyltriethoxysilane, γ- (N-ethyl) anilinopropyltriethoxysilane, γ- (N, N-dimethyl) aminopropylmethyldimethoxysilane, γ- (N, N-diethyl) aminopropylmethyldimethoxysilane, γ- (N, N-dibutyl) aminopropy Rumethyldimethoxysilane, γ- (N-methyl) anilinopropylmethyldimethoxysilane, γ- (N-ethyl) anilinopropylmethyldimethoxysilane, N- (trimethoxysilylpropyl) ethylenediamine, N- (dimethoxymethylsilylisopropyl) ) Silane coupling agents such as ethylenediamine, methyltrimethoxysilane, dimethyldimethoxysilane, methyltriethoxysilane, γ-chloropropyltrimethoxysilane, hexamethyldisilane, vinyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, isopropyl Triisostearoyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, isopropyl tri (N-aminoethyl-aminoethyl) titanate, tetraoctane Rubis (ditridecylphosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, bis (dioctylpyrophosphate) oxyacetate titanate, bis (dioctylpyrophosphate) ethylene titanate, Isopropyltrioctanoyl titanate, isopropyldimethacrylisostearoyl titanate, isopropyltridodecylbenzenesulfonyl titanate, isopropylisostearoyl diacryl titanate, isopropyltri (dioctylphosphate) titanate, isopropyltricumylphenyl titanate, tetraisopropylbis (dioctylphosphite) titanate And titanate coupling agents such as A seed may be used independently or may be used in combination of 2 or more types.

  Of these, a silane coupling agent having a secondary amino group is preferred from the viewpoint of fluidity 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-anilinomethyl Ethyldiethoxysilane, γ-anilinomethylethyldimethoxysilane, N- (p-methoxyphenyl) -γ-aminopropyltrimethoxysilane, N- (p-methoxyphenyl) -γ-aminopropyltriethoxysilane, N- (P-methoxyphenyl) -γ Aminopropylmethyldimethoxysilane, N- (p-methoxyphenyl) -γ-aminopropylmethyldiethoxysilane, N- (p-methoxyphenyl) -γ-aminopropylethyldiethoxysilane, N- (p-methoxyphenyl) -Γ-aminopropylethyldimethoxysilane, γ- (N-methyl) aminopropyltrimethoxysilane, γ- (N-ethyl) aminopropyltrimethoxysilane, γ- (N-butyl) aminopropyltrimethoxysilane, γ- (N-benzyl) aminopropyltrimethoxysilane, γ- (N-methyl) aminopropyltriethoxysilane, γ- (N-ethyl) aminopropyltriethoxysilane, γ- (N-butyl) aminopropyltriethoxysilane, γ- (N-benzyl) aminopropyltriethoxysilane γ- (N-methyl) aminopropylmethyldimethoxysilane, γ- (N-ethyl) aminopropylmethyldimethoxysilane, γ- (N-butyl) aminopropylmethyldimethoxysilane, γ- (N-benzyl) aminopropylmethyldimethoxysilane Silane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, γ- (β-aminoethyl) aminopropyltrimethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyl Examples include trimethoxysilane. Of these, aminosilane coupling agents represented by the following general formula (IV) are particularly preferred.

（式中、Ｒ^１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なる群より選ばれ、Ｒ^２は炭素数１〜６のアルキル基及びフェニル基からなる群より選ばれ、Ｒ^３はメチル基又はエチル基を示し、ｎは１〜６の整数を示し、ｍは１〜３の整数を示す。）
（Ｇ）カップリング剤の全配合量は、封止用エポキシ樹脂組成物に対して０．０３７〜４．７５重量％であることが好ましく、０．０５〜５重量％であることがより好ましく、０．１〜２．５重量％であることがさらに好ましい。０．０３７重量％未満ではフレームとの接着性が低下する傾向があり、４．７５重量％を超えるとパッケージの成形性が低下する傾向がある。
（Ｈ）その他添加剤
本発明による封止用エポキシ樹脂組成物では、必要に応じて、（Ｃ）環状ホスファゼン化合物と（Ｄ）リン酸エステル化合物との併用に加えて、その他ノンハロゲンおよびノンアンチモンの周知の難燃剤を配合してもよい。また、必要に応じて離型剤、イオン交換体、着色剤といった、当技術分野において周知の各種添加剤を添加してもよい。以下に本発明において使用可能な各種添加剤の一例を示す。
（その他の難燃剤）
本発明による封止用エポキシ樹脂組成物において使用可能な成分（Ｃ）および（Ｄ）以外の難燃剤の例としては、リン化合物、メラミン、メラミン誘導体、メラミン変性フェノール樹脂、トリアジン環を有する化合物、シアヌル酸誘導体、イソシアヌル酸誘導体等の窒素含有化合物、水酸化アルミニウム、水酸化マグネシウム、複合金属水酸化物、錫酸亜鉛、硼酸亜鉛、モリブデン酸亜鉛、ジシクロペンタジエニル鉄等の金属元素を含む化合物などが挙げられ、これらの１種を単独で用いても２種以上を組み合わせて用いてもよい。但し、樹脂組成物中に使用される難燃剤の合計量を基準として、（Ｃ）環状ホスファゼン化合物および（Ｄ）リン酸エステル化合物の合計量を、好ましくは５０重量％以上、より好ましくは６０重量％以上、さらに好ましくは７０重量％以上とすることが望ましい。成分（Ｃ）および（Ｄ）の合計量が５０重量％を下回ると、難燃性に加えて、優れた成形性および耐湿性等のその他の特性を達成することが困難となる。

(In the formula, R ¹ is selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 6 carbon atoms and an alkoxy group having 1 to ² carbon atoms, and R ² consists of an alkyl group having 1 to 6 carbon atoms and a phenyl group. Selected from the group, R ³ represents a methyl group or an ethyl group, n represents an integer of 1 to 6, and m represents an integer of 1 to 3)
(G) The total amount of coupling agent is preferably 0.037 to 4.75% by weight, more preferably 0.05 to 5% by weight, based on the epoxy resin composition for sealing. More preferably, the content is 0.1 to 2.5% by weight. If it is less than 0.037% by weight, the adhesion to the frame tends to be lowered, and if it exceeds 4.75% by weight, the moldability of the package tends to be lowered.
(H) Other additives In the epoxy resin composition for sealing according to the present invention, if necessary, in addition to the combined use of (C) cyclic phosphazene compound and (D) phosphate ester compound, other non-halogen and non-antimony You may mix | blend a known flame retardant. Moreover, you may add various additives well-known in this technical field, such as a mold release agent, an ion exchanger, and a coloring agent as needed. Examples of various additives that can be used in the present invention are shown below.
(Other flame retardants)
Examples of flame retardants other than components (C) and (D) that can be used in the epoxy resin composition for sealing according to the present invention include phosphorus compounds, melamine, melamine derivatives, melamine-modified phenol resins, compounds having a triazine ring, Contains nitrogen-containing compounds such as cyanuric acid derivatives and isocyanuric acid derivatives, aluminum hydroxide, magnesium hydroxide, composite metal hydroxides, zinc stannate, zinc borate, zinc molybdate, dicyclopentadienyl iron and other metal elements A compound etc. are mentioned, These 1 type may be used independently or may be used in combination of 2 or more type. However, based on the total amount of the flame retardant used in the resin composition, the total amount of (C) cyclic phosphazene compound and (D) phosphate ester compound is preferably 50% by weight or more, more preferably 60% by weight. % Or more, more preferably 70% by weight or more. When the total amount of components (C) and (D) is less than 50% by weight, it becomes difficult to achieve other properties such as excellent moldability and moisture resistance in addition to flame retardancy.

  Examples of phosphorus compounds that can be used as flame retardants in addition to components (C) and (D) include coated or uncoated red phosphorus, nitrilotrismethylenephosphonic acid tricalcium salt, methane-1-hydroxy-1,1- Phosphonates such as diphosphonic acid dicalcium salt, triphenylphosphine oxide, 2- (diphenylphosphinyl) hydroquinone, 2,2-[(2- (diphenylphosphinyl) -1,4-phenylene) bis (oxy Methylene)] bis-oxirane, phosphine such as tri-n-octylphosphine oxide, and phosphine oxide compounds.

  The red phosphorus is preferably coated red phosphorus such as red phosphorus coated with a thermosetting resin, red phosphorus coated with an inorganic compound, and an organic compound.

  Examples of thermosetting resins used for red phosphorus coated with thermosetting resins include epoxy resins, phenol resins, melamine resins, urethane resins, cyanate resins, urea-formalin resins, aniline-formalin resins, furan resins, Polyamide resin, polyamideimide resin, polyimide resin and the like can be mentioned, and one of these may be used alone or two or more of them may be used in combination. Moreover, it is possible to coat and polymerize simultaneously using monomers or oligomers of these resins and to coat the thermosetting resin produced by the polymerization, and the thermosetting resin may be cured after coating. Especially, an epoxy resin, a phenol resin, and a melamine resin are preferable from a compatible viewpoint with the base resin mix | blended with the epoxy resin composition for sealing.

  Examples of inorganic compounds used for red phosphorus coated with inorganic compounds and organic compounds include aluminum hydroxide, magnesium hydroxide, calcium hydroxide, titanium hydroxide, zirconium hydroxide, hydrous zirconium oxide, bismuth hydroxide, and carbonic acid. Examples include barium, calcium carbonate, zinc oxide, titanium oxide, nickel oxide, iron oxide, and the like. These may be used alone or in combination of two or more. Of these, zirconium hydroxide, hydrous zirconium oxide, aluminum hydroxide and zinc oxide, which are excellent in the phosphate ion capturing effect, are preferable.

  Moreover, as an organic compound used for red phosphorus coated with an inorganic compound and an organic compound, for example, a low molecular weight compound used for surface treatment such as a coupling agent or a chelating agent, a thermoplastic resin, a thermosetting resin, etc. Examples thereof include relatively high molecular weight compounds, and these may be used alone or in combination of two or more. Among these, a thermosetting resin is preferable from the viewpoint of the coating effect, and an epoxy resin, a phenol resin, and a melamine resin are more preferable from the viewpoint of compatibility with the base resin blended in the sealing epoxy resin composition.

  When red phosphorus is coated with an inorganic compound and an organic compound, the order of the coating process may be either the coating with the inorganic compound followed by the coating with the organic compound, or the coating with the organic compound followed by the coating with the inorganic compound. You may coat | cover both simultaneously using a mixture. Further, the coating form may be physically adsorbed, chemically bonded, or other forms. Further, the inorganic compound and the organic compound may exist separately after coating, or a part or all of them may be bonded.

  The amount of the inorganic compound and the organic compound is such that the weight ratio of the inorganic compound to the organic compound (inorganic compound / organic compound) is preferably 1/99 to 99/1, more preferably 10/90 to 95/5, and 30/70. ~ 90/10 is more preferable, and it is preferable to adjust the amount of the inorganic compound and the organic compound or the monomers and oligomers used as the raw materials so as to achieve such a weight ratio.

  Methods for producing coated red phosphorus such as red phosphorus coated with a thermosetting resin, red phosphorus coated with an inorganic compound and an organic compound are disclosed in, for example, Japanese Patent Laid-Open Nos. 62-217044 and 52-131695. A known coating method described in a gazette or the like can be used. The thickness of the coating film is not particularly limited as long as the effects of the present invention can be obtained, and the coating may be uniformly coated on the surface of red phosphorus or non-uniform.

  The particle size of red phosphorus is preferably 1 to 100 μm, and more preferably 5 to 50 μm, in terms of average particle size (particle size with a cumulative particle size distribution of 50% by weight). If the average particle size is less than 1 μm, the phosphate ion concentration of the molded product tends to be high and the moisture resistance tends to be inferior. If it exceeds 100 μm, when a highly integrated and high-density semiconductor device with a narrow pad pitch is used, the wire There is a tendency that defects due to deformation, short circuit, cutting, etc. are likely to occur.

  As the phosphine oxide, a compound represented by the following general formula (XXXI) is preferable.

（式中、Ｒ^１、Ｒ^２及びＲ^３は炭素数１〜１０の置換又は非置換のアルキル基、アリール基、アラルキル基及び水素原子を示し、すべて同一でも異なってもよい。但し、すべてが水素原子である場合を除く。）
上記一般式（XXXI）で示されるリン化合物のなかでも、耐加水分解性の観点からはＲ^１〜Ｒ^３が置換又は非置換のアリール基であることが好ましく、特に好ましくはフェニル基である。

(Wherein R ¹ , R ² and R ³ represent a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, an aryl group, an aralkyl group and a hydrogen atom, which may all be the same or different. Except for the case of hydrogen atoms.)
Among the phosphorus compounds represented by the general formula (XXXI), R ^{1 to} R ³ are preferably a substituted or unsubstituted aryl group, particularly preferably a phenyl group, from the viewpoint of hydrolysis resistance.

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

Magnesium hydroxide has a [101] / [001] peak intensity ratio by X-ray diffraction of 0.9 or more, a BET specific surface area of 1 to 4 m ² / g, and an average particle diameter of 5 μm or less. The inclusion is preferred. The method for synthesizing magnesium hydroxide as described above is not particularly limited, but lithium hydroxide or sodium hydroxide is added to an aqueous suspension of magnesium hydroxide or magnesium oxide, and the solid content in terms of magnesium hydroxide is 100 weight. 100% by weight or more based on%, wet pulverized, and hydrothermally treated at 180 to 230 ° C. are preferred.

The magnesium hydroxide preferably covers the surface from the viewpoint of acid resistance, and the coating is preferably a mixed coating layer of Si compound and Al compound. The mixed coating layer is preferably formed in a ratio of 0.2 to 10% by weight with respect to 100% by weight of magnesium hydroxide as a total amount in terms of SiO ₂ and Al ₂ O ₃ from the viewpoint of acid resistance. This mixed coating layer is composed of at least one compound selected from the group consisting of Si silicate, colloidal silica, and precursors thereof, and Al compound is aluminum chloride, aluminum sulfate, aluminum nitrate, sodium aluminate, alumina sol, and precursors thereof. From the viewpoint of production, it is preferable that each of the compounds comprises at least one compound of the group consisting of bodies.

  The method of coating magnesium hydroxide with a Si compound is not particularly limited, but a slurry of magnesium hydroxide dispersed in water is neutralized with water-soluble sodium silicate with an acid and deposited on the surface of magnesium hydroxide. The method is preferred. The temperature of the aqueous solution is preferably 5 to 100 ° C. from the viewpoint of coatability, more preferably 50 to 95 ° C., and neutralization is preferably made to have a pH of the slurry of 6 to 10 from the viewpoint of coatability. Furthermore, it is more preferable to set it as 6-9.5.

  The method for coating magnesium hydroxide with an Al compound is not particularly limited, but there is a method in which sodium aluminate and acid are added to the magnesium hydroxide slurry and precipitated.

  From the viewpoint of further improving acid resistance, the magnesium hydroxide formed with the mixed coating layer of the Si compound and the Al compound of the present invention may be further surface-treated with at least one of an aliphatic metal salt and a silane coupling agent. preferable. The surface treatment amount is preferably a ratio of 0.1 to 10% by weight of the silane coupling agent with respect to 100% by weight of magnesium hydroxide.

  As the aliphatic metal salt, sodium salts and potassium salts of higher fatty acids such as oleic acid and stearic acid are preferable. The silane coupling agent used for the surface treatment is not particularly limited. For example, vinylethoxysilane, vinyltris (2-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane. , Β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, and the like. Examples of the aluminum coupling agent include acetylalkoxyaluminum diisopropylate, and examples of the titanate coupling agent include isopropyl triisostearoyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, and isopropyl tri ( N-aminoethylaminoethyl) titanate, isopropyl tridecylbenzenesulfonyl titanate and the like can be exemplified.

From the viewpoint of fluidity, magnesium hydroxide preferably has a [101] / [001] peak intensity ratio of 0.9 or more in X-ray diffraction. If it is less than 0.9, the crystal thickness tends to decrease and the fluidity tends to decrease. Further, the BET specific surface area is preferably ¹ to 4 m ² / g from the viewpoint of flame retardancy and fluidity. When it is less than 1 m ² / g, the flame retardancy is lowered, and when it exceeds 4 m ² / g, the fluidity tends to be lowered. Furthermore, it is preferable that an average particle diameter is 5 micrometers or less. More preferably, it is 1-4 micrometers. When it exceeds 5 μm, the flame retardancy tends to decrease. Moreover, when it is less than 1 μm, the fluidity tends to decrease.

  The magnesium hydroxide used for synthesizing the magnesium hydroxide is not particularly limited. For example, it is obtained by neutralizing a natural product obtained by pulverizing natural ore or an aqueous magnesium salt solution with an alkali. Composites. Moreover, what processed these magnesium hydroxide with borate, a phosphate, zinc salt, etc. may be used. Furthermore, a composite metal hydroxide represented by the following composition formula (XXXII) may be used. Moreover, the following composite metal hydroxide can be used as it is as a combined flame retardant without further treatment.

(Chemical 30)
p (M ¹ aOb) · q (M ² cOd) · r (M ³ cOd) · mH ₂ O (XXXII)
(In the formula, at least one of M ¹ , M ² and M ³ is a magnesium element and represents a metal element different from each other, a, b, c, d, p, q and m are positive numbers, and r is 0 or Indicates a positive number.)
Among these, a compound in which r in the composition formula (XXXII) is 0, that is, a compound represented by the following composition formula (XXXIIa) is more preferable.

(Chemical Formula 31)
m (M ¹ aOb) · n (M ² cOd) · l (H ₂ O) (XXXIIa)
(In the formula, at least one of M ¹ and M ² is a magnesium element and represents a metal element different from each other, and a, b, c, d, m, n, and l represent positive numbers.)
In the composition formulas (XXXII) and (XXXIIa), at least one of M ¹ and M ² is a magnesium element, and there is no particular limitation as long as it is a metal element different from each other.

For example, from the viewpoint of flame retardancy, elements other than magnesium are the third period metal elements, group IIA alkaline earth metal elements, groups IVB, IIB, and VIII so that M ¹ and M ² are not the same. , IB, IIIA and IVA, M ² is preferably selected from IIIB to IIB transition metal elements, M ¹ is magnesium, M ² is calcium, aluminum, tin, titanium More preferably, iron, cobalt, nickel, copper and zinc are selected. 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 (XXXII) is not particularly limited as long as the effects of the present invention can be obtained, but r = 0, and 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 (XXXIIa) is preferably 99/1 to 50/50. 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).
(Release agent)
In the present invention, it is preferable to add a release agent to the resin composition from the viewpoint of releasability. Typical release agents include linear oxidized polyethylene having a weight average molecular weight of 4,000 or more, and a copolymer of an α-olefin having 5 to 30 carbon atoms and maleic anhydride having 5 to 25 carbon atoms. The compound esterified with monohydric alcohol is mentioned.

  A linear oxidized polyethylene having a weight average molecular weight of 4,000 or more is a good release agent. Here, the linear polyethylene refers to polyethylene having a carbon number of the side chain alkyl chain of about 10% or less of the main chain alkyl chain carbon number, and is generally classified as a polyethylene having a penetration of 2 or less. The The oxidized polyethylene means polyethylene having an acid value.

  The weight average molecular weight of the linear oxidized polyethylene having a weight average molecular weight of 4,000 or more is required to be 4,000 or more from the viewpoint of releasability, and from the viewpoint of adhesiveness and prevention of mold / package contamination. Is preferably 30,000 or less, more preferably 5,000 to 20,000, and even more preferably 7,000 to 15,000. Here, the weight average molecular weight refers to a value measured by high temperature GPC (gel permeation chromatography). The acid value of the above component is not particularly limited, but is preferably 2 to 50 mg / KOH, more preferably 10 to 35 mg / KOH from the viewpoint of releasability.

  The amount of the linear oxidized polyethylene having a weight average molecular weight of 4,000 or more is not particularly limited, but is preferably 0.5 to 10% by weight, preferably 1 to 5% by weight, based on the epoxy resin (A). Is more preferable. If the blending amount is less than 0.5% by weight, the releasability tends to decrease, and if it exceeds 10% by weight, the effect of improving the adhesion and mold / package stains may be insufficient.

  A compound obtained by esterifying a copolymer of an α-olefin having 5 to 30 carbon atoms and maleic anhydride with a monohydric alcohol having 5 to 25 carbon atoms is also a suitable release agent. Both the linear polyethylene oxide having a weight average molecular weight of 4,000 or more and the epoxy resin of the component (A) are highly compatible, and have an effect of preventing a decrease in adhesiveness and mold / package contamination.

  The α-olefin having 5 to 30 carbon atoms is not particularly limited. For example, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, Linear α-olefins such as 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 1-docosene, 1-tricosene, 1-tetracocene, 1-pentacocene, 1-hexacosene, 1-heptacene, 3- Methyl-1-butene, 3,4-dimethyl-pentene, 3-methyl-1-nonene, 3,4-dimethyl-octene, 3-ethyl-1-dodecene, 4-methyl-5-ethyl-1-octadecene, Examples include branched α-olefins such as 3,4,5-triethyl-1-eicosene, and these may be used alone or in combination of two or more. Of these, linear α-olefins having 10 to 25 carbon atoms are preferable, and linear α-olefins having 15 to 25 carbon atoms such as 1-eicosene, 1-docosene, and 1-tricosene are more preferable.

  The monohydric alcohol having 5 to 25 carbon atoms is not particularly limited. For example, amyl alcohol, isoamyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, capryl alcohol, nonyl alcohol, decyl alcohol, undecyl alcohol, lauryl alcohol, tridecyl alcohol, myristyl alcohol, pentadecyl alcohol, cetyl alcohol, heptadecyl alcohol Straight chain or branched aliphatic saturated alcohols such as stearyl alcohol, nonadecyl alcohol, eicosyl alcohol, hexenol, 2-hexen-1-ol, 1-hexen-3-ol, pentenol, 2-methyl- Linear or branched aliphatic unsaturated alcohols such as 1-pentenol, cycloaliphatic alcohols such as cyclopentanol and cyclohexanol, benzyl alcohol, syn Aromatic alcohols such as mill alcohols include heterocyclic alcohols such as furfuryl alcohol may be used in combination of two or more even with these alone. Of these, a linear alcohol having 10 to 20 carbon atoms is preferable, and a linear aliphatic saturated alcohol having 15 to 20 carbon atoms is more preferable.

In the epoxy resin composition according to the present invention, components that can be used as a release agent for higher fatty acids, higher fatty acid metal salts, ester waxes, polyolefin waxes, polyethylene, polyethylene oxide, and the like, without being limited to the above-described components. Can also be used.
(Anion exchanger)
An anion exchanger can be added to the sealing epoxy resin composition of the present invention from the viewpoint of improving the moisture resistance and high-temperature storage properties of a semiconductor element such as an IC. The anion exchanger is not particularly limited, and conventionally known anion exchangers can be used. Examples thereof include hydrotalcites and hydrated oxides of elements selected from magnesium, aluminum, titanium, zirconium, bismuth, and the like. These may be used alone or in combination of two or more. Of these, hydrotalcite represented by the following composition formula (XXXIII) is preferable.

(Chemical Formula 32)
Mg _1-x Al _x (OH) ₂ (CO ₃ ) _{x / 2} · mH ₂ O (XXXIII)
(0 <X ≦ 0.5, m is a positive number)
In the epoxy resin composition according to the present invention, in addition to the release agent and the ion exchanger, in the technical field such as a colorant such as carbon black and a stress relaxation agent such as silicone oil or silicone rubber powder, if necessary. Various known additives can be blended.

  The epoxy resin composition for sealing according to the present invention can be prepared by any method as long as the above-mentioned various raw materials can be uniformly dispersed and mixed. As a general method, after mixing raw materials of a predetermined blending amount with a mixer, etc., perform mixing or melt-kneading with a mixing roll, an extruder, a raking machine, a planetary mixer, etc., then cool, and if necessary, Examples of the method include defoaming and pulverization. In addition, if necessary, the composition may be tableted with a size and weight that meet the molding conditions.

  In the present invention, it is possible to provide a highly reliable electronic component device by sealing an element using the above-described sealing epoxy resin composition. As a method for sealing an element of an electronic component device such as a semiconductor device using the sealing epoxy resin composition of the present invention as a sealing material, a low-pressure transfer molding method is the most common, but an injection molding method A compression molding method or the like can also be applied. Further, a dispensing method, a casting method, a printing method, or the like may be applied.

  As an electronic component device according to the present invention, a lead frame, a wired tape carrier, a wiring board, glass, a support member such as a silicon wafer, a mounting substrate, an active element such as a semiconductor chip, a transistor, a diode, a thyristor, a capacitor, a resistor Examples thereof include an electronic component device in which elements such as passive elements such as bodies and coils are mounted and necessary portions are sealed with the sealing epoxy resin composition according to the present invention.

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

EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, the scope of the present invention is not limited to these Examples.
(Examples 1-17, Comparative Examples 1-12)
Hereinafter, various raw materials used in each example and comparative example are shown.
(A) Epoxy resin Epoxy resin 1: Biphenyl type epoxy resin having an epoxy equivalent of 196 and a melting point of 106 ° C. (trade name Epicoat YX-4000H manufactured by Japan Epoxy Resin Co., Ltd.)
Epoxy resin 2: Sulfur atom-containing epoxy resin having an epoxy equivalent of 245 and melting point of 110 ° C.
Epoxy resin 3: β-naphthol-aralkyl type epoxy resin having an epoxy equivalent of 266 and a softening point of 67 ° C. (trade name ESN-175 manufactured by Tohto Kasei Co., Ltd.)
Epoxy resin 4: o-cresol novolak type epoxy resin having an epoxy equivalent of 195 and a softening point of 65 ° C. (trade name ESCN-190 manufactured by Sumitomo Chemical Co., Ltd.)
(B) Curing agent Curing agent 1: Phenol aralkyl resin having a softening point of 70 ° C. and a hydroxyl group equivalent of 175 (trade name: Millex XLC-3L, manufactured by Mitsui Chemicals, Inc.)
Curing agent 2: Biphenylene type phenol resin having a softening point of 80 ° C. and a hydroxyl group equivalent of 199 (trade name MEH-7851 manufactured by Meiwa Kasei Co., Ltd.)
Curing agent 3: Phenol novolac resin having a softening point of 80 ° C. and a hydroxyl group equivalent of 106 (trade name H-1 manufactured by Meiwa Kasei Co., Ltd.)
(C) Cyclic phosphazene Cyclic phosphazene 1: Phenoxy-type cyclic phosphazene compound containing no hydroxyphenyl group having a melting point of 105 ° C. (trade name SPE-100, manufactured by Otsuka Chemical Co., Ltd.)
Cyclic phosphazene 2: Hydroxyphenyl group-containing phenoxy-type cyclic phosphazene compound having a hydroxyl equivalent weight of 242 (trade name SPH-100, manufactured by Otsuka Chemical Co., Ltd.)
(D) Phosphate ester Aromatic condensed phosphate ester (trade name PX-200, manufactured by Daihachi Chemical),
(E) Curing accelerator Curing accelerator 1: Triphenylphosphine Curing accelerator 2: Adduct of triphenylphosphine and 1,4-benzoquinone Curing accelerator 3: Adduct of tributylphosphine and 1,4-benzoquinone (F) Inorganic filler Spherical fused silica: average particle size 14.5 μm, specific surface area 2.8 m ² / g
(G) Coupling agent Epoxysilane: γ-glycidoxypropyltrimethoxysilane Anilinosilane: Silane coupling agent containing secondary amino group (γ-anilinopropyltrimethoxysilane)
(Other additives)
Flame retardant: Triphenylphosphine oxide: Composite metal hydroxide (Echo Mug Z-10 (manufactured by Tateho Chemical Co., Ltd.))
: Antimony trioxide: Brominated epoxy resin (epoxy equivalent 397, softening point 69 ° C, bromine content 49 wt.
% Bisphenol A brominated epoxy resin (trade name Y, manufactured by Toto Kasei Co., Ltd.)
DB-400))
Mold release agent: Carnauba wax Colorant: Carbon black (trade name MA-100 manufactured by Mitsubishi Chemical Corporation)

The above-mentioned various raw materials are blended in parts by weight shown in Tables 1 to 4, and roll kneading is performed under conditions of a kneading temperature of 80 ° C. and a kneading time of 10 minutes, which correspond to Examples 1 to 17 and Comparative Examples 1 to 12. An epoxy resin composition was prepared.

The characteristics of the respective epoxy resin compositions for sealing prepared in Examples 1 to 17 and Comparative Examples 1 to 12 were evaluated by the following tests. The results are shown in Tables 5 to 8.
(1) Spiral flow Using a spiral flow measurement mold according to EMMI-1-66, a transfer molding machine was used to seal the epoxy resin composition for sealing at a mold temperature of 180 ° C., a molding pressure of 6.9 MPa, and a curing time of 90. Molding was performed under the condition of seconds, and the flow distance (cm) was determined.
(2) Hardness upon heating The sealing epoxy resin composition was molded into a disc having a diameter of 50 mm and a thickness of 3 mm under the molding conditions of (1), and measured immediately after molding using a Shore D hardness meter.
(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. After curing, the flame retardancy was evaluated according to the UL-94 test method.
(4) Reflow resistance An 80-pin flat package (QFP) having a silicon chip of 8 mm × 10 mm × 0.4 mm mounted and having an outer dimension of 20 mm × 14 mm × 2 mm is sealed with an epoxy resin composition for sealing (3 ) And after-curing. The manufactured QFP is humidified under conditions of 85 ° C. and 85% RH, reflowed at 240 ° C. for 10 seconds every predetermined time, observed for cracks, and cracks for the number of test packages (5) The number of packages generated was evaluated.
(5) Moisture resistance A test silicon chip of 6 mm x 6 mm x 0.4 mm with 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, and the outer dimensions are 20 mm x 14 mm x 2.7 mm. The 80-pin flat package (QFP) was formed by molding and post-curing using the sealing epoxy resin composition under the condition (3) above. The prepared QFP was pretreated, then humidified, and examined for disconnection failure due to aluminum wiring corrosion every predetermined time, and evaluated by the number of defective packages with respect to the number of test packages (10). 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 A 16-pin DIP (Dual Inline Package) was produced by molding and post-curing using the sealing epoxy resin composition under the conditions of (3) above. This DIP is a 5 mm x 9 mm x 0.4 mm test silicon chip with a 10 μm line width and 1 μm thick aluminum wiring on a 5 μm thick oxide film on a 42 alloy lead frame with partial silver plating. Are mounted using silver paste, and the bonding pads of the chip and the inner leads are connected by Au wires at 200 ° C. with a thermonic wire bonder. The obtained DIP was stored in a high-temperature bath at 200 ° C., taken out every predetermined time and subjected to a continuity test, and the high-temperature standing characteristics were evaluated by the number of defective continuity packages with respect to the number of test packages (10).

  As is clear from Tables 5 to 8 shown above, the epoxy resin compositions for sealing (Examples 1 to 17) according to the present invention all exhibit good flame retardancy (V-0 in the UL-94 test). Are also good in terms of moldability, moisture resistance and high temperature storage properties. Furthermore, the compositions of Examples 1 to 11, 13, and 15 to 17 have good reflow resistance. In addition, the compositions of Examples 4 to 6, particularly the compositions of Examples 5 and 6 using a cyclic phosphazene compound having a hydroxyphenyl group have the most excellent balance in flame retardancy, moldability and reliability. Yes.

On the other hand, the comparative composition (Comparative Examples 1 to 12) in which (C) the cyclic phosphazene compound and (D) the phosphate ester compound are not used together improves the flame retardancy and other characteristics required for the package in a well-balanced manner. I couldn't. More specifically, the compositions of Comparative Examples 1 to 6 blended without the combined use of the components (C) and (D) are inferior in flame retardancy (V-0 achieved in the UL-94 test). Not) This is in contrast to the compositions according to the invention (Examples 1 to 4) in which the amount of flame retardant is approximately equal. Moreover, although the composition (Comparative Examples 7-9) containing only any one of the said (C) and (D), V-0 is achieved by UL-94 test by raising those compounding quantities. In addition, the moisture resistance is poor, the hot hardness is low, and the moldability tends to be poor (particularly, Comparative Example 9). Further, Comparative Example 10 that does not include any of the above (C) and (D) has low heat hardness, Comparative Example 11 has low fluidity, and each has poor moldability. Furthermore, Comparative Example 12 using a brominated flame retardant / antimony flame retardant is inferior in high-temperature storage characteristics.

Claims (16)

  An epoxy resin composition for sealing comprising (A) an epoxy resin, (B) a curing agent, (C) a cyclic phosphazene compound, and (D) a phosphate ester compound. (C) Cyclic phosphazene compound contains the compound shown by the following general formula (I), The epoxy resin composition for sealing of Claim 1 characterized by the above-mentioned.

(In the formula, n is an integer of 3 to 5, and R and R ′ may be the same or different and each represents an alkyl or aryl group having 1 to 4 carbon atoms, and is substituted with a hydroxy group. May be.)   In the formula (I), one or both of R and R 'are hydroxyphenyl groups, and the number of hydroxyphenyl groups is any one of 1 to 10, The sealing epoxy according to claim 2, Resin composition.   (C) Cyclic phosphazene compound contains the bridge | crosslinked compound, The epoxy resin composition for sealing in any one of Claims 1-3 characterized by the above-mentioned. (D) The epoxy resin composition for sealing according to any one of claims 1 to 4, wherein the phosphate ester compound contains a compound represented by the following general formula (II).

(In the formula, 8 Rs represent an alkyl group having 1 to 4 carbon atoms, which may all be the same or different, and Ar represents an aromatic ring.)   (A) Epoxy resin is biphenyl type epoxy resin, bisphenol F type epoxy resin, stilbene type epoxy resin, sulfur atom-containing epoxy resin, novolac type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, triphenylmethane type 6. The epoxy resin composition for sealing according to claim 1, comprising at least one selected from the group consisting of an epoxy resin, a biphenylene type epoxy resin, and a naphthol / aralkyl type epoxy resin. . The epoxy resin composition for sealing according to claim 6, wherein the sulfur atom-containing epoxy resin is a compound represented by the following general formula (III).

Wherein R ^{1 to} R ⁸ are selected from the group consisting of a hydrogen atom and a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, all of which may be the same or different, and n is Represents an integer of 0 to 3.)   (B) The curing agent contains at least one selected from the group consisting of a biphenylene type phenol resin, an aralkyl type phenol resin, a dicyclopentadiene type phenol resin, a triphenylmethane type phenol resin and a novolac type phenol resin. The epoxy resin composition for sealing according to any one of claims 1 to 7.   (E) The epoxy resin composition for sealing according to any one of claims 1 to 8, further comprising a curing accelerator.   (E) The hardening accelerator contains the adduct of a phosphine compound and a quinone compound, The epoxy resin composition for sealing of Claim 9 characterized by the above-mentioned.   The epoxy resin composition for sealing according to claim 10, wherein the curing accelerator (E) contains an adduct of a phosphine compound and a quinone compound in which at least one alkyl group is bonded to a phosphorus atom.   (F) The epoxy resin composition for sealing according to any one of claims 1 to 11, further comprising an inorganic filler.   (G) The epoxy resin composition for sealing according to any one of claims 1 to 12, further comprising a silane coupling agent.   (G) The epoxy resin composition for sealing according to claim 13, wherein the silane coupling agent contains a silane coupling agent having a secondary amino group. (G) The epoxy resin composition for sealing according to claim 14, wherein the silane coupling agent having a secondary amino group contains a compound represented by the following general formula (IV).

(In the formula, R ¹ is selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 6 carbon atoms and an alkoxy group having 1 to ² carbon atoms, and R ² is composed of an alkyl group having 1 to 6 carbon atoms and a phenyl group. Selected from the group, R ³ represents a methyl group or an ethyl group, n represents an integer of 1 to 6, and m represents an integer of 1 to 3)   An electronic component device comprising an element sealed with the sealing epoxy resin composition according to claim 1.