JP2011246543A - Epoxy resin composition for sealing and electronic part device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an epoxy resin composition for sealing that exhibits good adhesive properties to a noble metal such as Ag and Au and good reflow resistance and exhibits good flame retardancy without deteriorating moldability and reliability such as moisture resistance and a shelf property at a higher temperature, and an electronic part device equipped with an element sealed with the same.SOLUTION: The epoxy resin composition for sealing comprises (A) an epoxy resin represented by general formula (I), (B) a curing agent, (C) an inorganic filler and (D) a specific cyclic phosphazene compound. In the formula, Rand Rare the same or different and are each a hydrogen atom, a 1-6C alkyl group or a 1-2C alkoxy group; and n is an integer of 0-10.

Description

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

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

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

  However, in the case of using an indene / styrene / phenol copolymer oligomer (see, for example, Patent Document 1) or a sulfur atom-containing silane coupling agent (see, for example, Patent Document 4), the effect of improving adhesion to noble metals such as Ag and Au. In addition, even when a sulfur atom-containing compound (see, for example, Patent Documents 2 and 3) is added in an amount disclosed in the literature, the adhesion with noble metals is not sufficiently improved, and none of them satisfies reflow resistance. .

  The present invention has been made in view of such a situation, and has good adhesion to noble metals such as Ag and Au, good reflow resistance, and reduced reliability such as moldability, moisture resistance, and high temperature storage characteristics. Therefore, it is an object of the present invention to provide an epoxy resin composition for sealing having good flame retardancy with non-halogen and non-antimony from the viewpoint of environmental friendliness, and an electronic component device including an element sealed thereby. .

  As a result of intensive studies in order to solve the above problems, the present inventors have found that the above object can be achieved by an epoxy resin composition for sealing containing a specific epoxy resin and a specific phosphorus compound. The present invention has been completed.

The present invention relates to the following.
(1) (A) an epoxy resin represented by the following general formula (I), (B) a curing agent, (C) an inorganic filler, and (D) a cyclic phosphazene compound represented by the following general formula (II) Stopping epoxy resin composition.

（一般式（Ｉ）中、Ｒ^１、Ｒ^２は水素原子、炭素数１〜６のアルキル基及び炭素数１〜２のアルコキシ基から選ばれ、互いに同一であっても異なってもよい。ｎは０〜１０の整数を示す。）

(In the general formula (I), R ¹ and R ² are selected from a hydrogen atom, an alkyl group having 1 to 6 carbon atoms and an alkoxy group having 1 to 2 carbon atoms, and may be the same or different from each other. Represents an integer of 0 to 10.)

（一般式（ＩＩ）中、ｎは３〜５の整数で、Ｒ^１、Ｒ^２は炭素数１〜４のアルキル基またはアリール基から選ばれ、互いに同一であっても異なってもよい。）
（２）（Ｄ）成分の環状ホスファゼン化合物の含有量が無機充填剤（Ｃ）を除く配合成分の合計量に対して燐原子の量が０．２〜３．０質量％となる量である上記（１）に記載の封止用エポキシ樹脂組成物。
（３）（Ｄ）成分の環状ホスファゼン化合物のｎが、３である上記（１）又は（２）に記載の封止用エポキシ樹脂組成物。
（４）（Ｄ）成分の環状ホスファゼン化合物のｎ個のＲ^１及びｎ個のＲ^２が、全てフェニル基である上記（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）成分の環状ホスファゼン化合物のｎ個のＲ^１とｎ個のＲ^２のうち少なくとも１個がヒドロキシフェニル基であり、他の全てがフェニル基である上記（１）〜（３）のいずれかに記載の封止用エポキシ樹脂組成物。
（６）上記（１）〜（５）のいずれかに記載の封止用エポキシ樹脂組成物で封止された素子を備えた電子部品装置。

(In general formula (II), n is an integer of 3 to 5, and R ¹ and R ² are selected from an alkyl group or an aryl group having 1 to 4 carbon atoms, and may be the same or different from each other.)
(2) The content of the cyclic phosphazene compound as the component (D) is such that the amount of phosphorus atoms is 0.2 to 3.0% by mass with respect to the total amount of the blending components excluding the inorganic filler (C). The epoxy resin composition for sealing according to (1) above.
(3) The epoxy resin composition for sealing according to the above (1) or (2), wherein n of the cyclic phosphazene compound as the component (D) is 3.
(4) The epoxy resin composition for sealing according to any one of the above (1) to (3), wherein n R ¹ and n R ² of the cyclic phosphazene compound of component (D) are all phenyl groups. object.
(5) The above (1) to (3), wherein at least one of n R ¹ and n R ² of the cyclic phosphazene compound of component (D) is a hydroxyphenyl group and all the others are phenyl groups. ) The epoxy resin composition for sealing according to any one of the above.
(6) An electronic component device including an element sealed with the sealing epoxy resin composition according to any one of (1) to (5).

  The epoxy resin composition for sealing according to the present invention has good adhesion to noble metals such as Ag and Au, good reflow resistance, excellent moldability, moisture resistance, high temperature storage characteristics, etc. It has good flame retardancy without using halogen or antimony from the viewpoint of environmental friendliness without reducing reliability, and it can be used to obtain products such as electronic component devices having the above characteristics and characteristics. , Its industrial value is great.

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

（一般式（Ｉ）中、Ｒ^１、Ｒ^２は水素原子、炭素数１〜６のアルキル基及び炭素数１〜２のアルコキシ基から選ばれ、互いに同一であっても異なってもよい。ｎは０〜１０の整数を示す。）

(In the general formula (I), R ¹ and R ² are selected from a hydrogen atom, an alkyl group having 1 to 6 carbon atoms and an alkoxy group having 1 to 2 carbon atoms, and may be the same or different from each other. Represents an integer of 0 to 10.)

Examples of the epoxy resin represented by the general formula (I) include HP-5000 (trade name, manufactured by DIC Corporation) of the following general formula (I-2) in which R ¹ is a methyl group and R ² is a methoxy group. Is commercially available.

  In order to exhibit the performance of the epoxy resin, the blending amount is preferably 30% by mass or more, more preferably 50% by mass or more, and further preferably 60% by mass or more with respect to the total amount of the epoxy resin. .

  In the present invention, a conventionally known epoxy resin can be used in combination. Examples of the epoxy resins that can be used in combination include phenol novolac type epoxy resins, orthocresol novolac type epoxy resins, and epoxy resins having a triphenylmethane skeleton, such as phenol, cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol F. And / or naphthols such as α-naphthol, β-naphthol and dihydroxynaphthalene and compounds having an aldehyde group such as formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde and salicylaldehyde in an acidic catalyst. Epoxidized novolac resin obtained by the process. Diglycidyl ethers such as bisphenol A, bisphenol F, bisphenol S, alkyl-substituted or unsubstituted biphenol. Stilbene epoxy resin, hydroquinone epoxy resin, glycidyl ester epoxy resin obtained by reaction of polybasic acid such as phthalic acid and dimer acid and epichlorohydrin, glycidyl amine obtained by reaction of polyamine such as diaminodiphenylmethane, isocyanuric acid and epichlorohydrin Type epoxy resin, epoxidized product of co-condensation resin of dicyclopentadiene and phenol, epoxy resin having naphthalene ring, phenol / aralkyl resin containing biphenylene skeleton, epoxidized product of aralkyl type phenol resin such as naphthol / aralkyl resin, 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, And the like sulfur atom-containing epoxy resins may be used in combination or in combination of two or more with these alone.

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

  Examples of the biphenyl type epoxy resin include an epoxy resin represented by the following general formula (III). Examples of the bisphenol F type epoxy resin include an epoxy resin represented by the following general formula (IV), and a stilbene type. Examples of the epoxy resin include an epoxy resin represented by the following general formula (V), and examples of the sulfur atom-containing epoxy resin include an epoxy resin represented by the following general formula (VI).

（一般式（ＩＩＩ）中、Ｒ^１〜Ｒ^８は水素原子及び炭素数１〜１０の置換又は非置換の一価の炭化水素基から選ばれ、全てが同一でも異なっていてもよい。ｎは０〜３の整数を示す。）

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

（一般式（ＩＶ）中、Ｒ^１〜Ｒ^８は水素原子、炭素数１〜１０のアルキル基、炭素数１〜１０のアルコキシル基、炭素数６〜１０のアリール基、及び炭素数６〜１０のアラルキル基から選ばれ、全てが同一でも異なっていてもよい。ｎは０〜３の整数を示す。）

(In the general formula ^(IV), R 1 ~R ⁸ are 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 6 to 10 carbon atoms And all may be the same or different. N represents an integer of 0 to 3.)

（一般式（Ｖ）中、Ｒ^１〜Ｒ^８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。）

(In the general formula (V), 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. Represents an integer of 0 to 10.)

（一般式（ＶＩ）中、Ｒ^１〜Ｒ^８は水素原子、置換又は非置換の炭素数１〜１０のアルキル基及び置換又は非置換の炭素数１〜１０のアルコキシ基から選ばれ、全てが同一でも異なっていてもよい。ｎは０〜３の整数を示す。）

(In the general formula (VI), 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 (It may be the same or different. N represents an integer of 0 to 3.)

  Examples of the biphenyl type epoxy resin represented by the general formula (III) 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. As such a compound, YX-4000 (trade name, manufactured by Mitsubishi Chemical Corporation) is commercially available.

Examples of the bisphenol F-type epoxy resin represented by the general formula (IV) include, 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 Kasei Epoxy Manufacturing Co., Ltd.) having n = 0 as a main component is available as a commercial product.

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

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

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

（一般式（ＶＩＩ）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。）

(In General Formula (VII), 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 (VII) can be easily obtained by reacting novolak-type phenol resin with epichlorohydrin. Especially, as R in general formula (VII), it is a C1-C10 alkyl group, such as a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, a methoxy group, an ethoxy group, a propoxy group. C1-C10 alkoxyl groups, such as a butoxy group, are preferable, and a hydrogen atom or a methyl group is more preferable. n is preferably an integer of 0 to 3. Among the novolak type epoxy resins represented by the general formula (VII), orthocresol novolak type epoxy resins are preferable. As such a compound, EOCN-1020 (trade name, manufactured by Nippon Kayaku Co., Ltd.) and the like are commercially available.

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

（一般式（ＶＩＩＩ）中、Ｒ^１及びＲ^２は水素原子及び炭素数１〜１０の置換又は非置換の一価の炭化水素基からそれぞれ独立して選ばれ、ｎは０〜１０の整数を示し、ｍは０〜６の整数を示す。）

(In General Formula (VIII), R ¹ and R ² are each independently selected from a hydrogen atom and a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and n is an integer of 0 to 10. M represents an integer of 0 to 6.)

R ¹ in the above formula (VIII) is, for example, a hydrogen atom, an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, or a tert-butyl group, a vinyl group, an allyl group, or 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 tert-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. As such a compound, HP-7200 (trade name, manufactured by Dainippon Ink and Chemicals, Inc.) is available as a commercial product.

  Examples of the naphthalene type epoxy resin include an epoxy resin represented by the following general formula (IX), and examples of the triphenylmethane type epoxy resin include an epoxy resin represented by the following general formula (X).

（一般式（ＩＸ）中、Ｒ^１〜Ｒ^３は水素原子及び置換又は非置換の炭素数１〜１２の一価の炭化水素基から選ばれ、それぞれ全てが同一でも異なっていてもよい。ｐは１又は０で、ｌ、ｍはそれぞれ０〜１１の整数であって、（ｌ＋ｍ）が１〜１１の整数でかつ（ｌ＋ｐ）が１〜１２の整数となるよう選ばれる。ｉは０〜３の整数、ｊは０〜２の整数、ｋは０〜４の整数を示す。）

(In General Formula (IX), 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 0 to 0. 3 is an integer, j is an integer from 0 to 2, and k is an integer from 0 to 4.)

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

（一般式（Ｘ）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。）

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

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

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

（一般式（ＸＩ）中のＲ^１〜Ｒ^９は全てが同一でも異なっていてもよく、水素原子、メチル基、エチル基、プロピル基、ブチル基、イソプロピル基、イソブチル基等の炭素数１〜１０のアルキル基、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基等の炭素数１〜１０のアルコキシル基、フェニル基、トリル基、キシリル基等の炭素数６〜１０のアリール基、及び、ベンジル基、フェネチル基等の炭素数６〜１０のアラルキル基から選ばれ、なかでも水素原子とメチル基が好ましい。ｎは０〜１０の整数を示す。）

(R ^{1 to} R ⁹ in the general formula (XI) may all be the same or different and have 1 to 1 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. 10 alkyl groups, methoxy groups, ethoxy groups, propoxy groups, butoxy groups, etc., C1-C10 alkoxyl groups, phenyl groups, tolyl groups, xylyl groups, etc. aryl groups, and benzyl groups And a hydrogen atom and a methyl group are preferable, and n represents an integer of 0 to 10.)

（一般式（ＸＩＩ）中、Ｒ^１〜Ｒ^２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。）

(In General Formula (XII), R ^{1 to} R ² 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. Represents an integer of 1 to 10.)

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

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

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

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

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

  Especially, the epoxy resin shown by the said general formula (XIV) is preferable from a viewpoint of a flame retardance and a moldability. As such a compound, YX-8800 (trade name, manufactured by Mitsubishi Chemical Corporation) and the like are available.

  Moreover, the compound shown by the following general formula (XXXIII) can also be used.

（一般式（ＸＸＸＩＩＩ）中のＲ¹は水素原子、水酸基、炭素数１〜８のアルキル基、炭素数１〜６のアルコキシ基から選ばれ、全てが同一でも異なっていてもよい。Ｒ²、Ｒ³は水素原子、炭素数１〜６のアルキル基から選ばれ、全てが同一でも異なっていてもよい。
ｎは１〜２０の整数を示し、ｍは１〜３の整数を示す。）

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

M in the general formula (XXXIII) is preferably 1 or 2 from the viewpoint of flame retardancy and curability. The compound represented by the general formula (XXXIII) is obtained by reacting an indole with a crosslinking agent in the presence of an acid catalyst and then reacting with an epihalohydrin compound. The indole substituent R ¹ includes a hydrogen atom, a methoxy group, an ethoxy group, a vinyl ether group, an isopropoxy group, an allyloxy group, a propargyl ether group, a butoxy group, a phenoxy group, a methyl group, an ethyl group, a vinyl group, an ethyne group, Examples include n-propyl group, isopropyl group, allyl group, propargyl group, butyl group, n-amyl group, sec-amyl group, tert-amyl group, cyclohexyl group, phenyl group, benzyl group and the like. Preferably they are a hydrogen atom and a C1-C3 alkyl group, More preferably, it is a hydrogen atom. As a crosslinking group of the following general formula (a) obtained by reacting with a crosslinking agent, p-xylylene group, m-xylylene group, 1,4-bisethylidenephenyl group, 1,3-bisethylidenephenylene group, 1,4 -Bisisopropylidenephenylene group, 1,3-isopropylidenephenylene group, 4,4'-bismethylenebiphenyl group, 3,4'-bismethylenebiphenyl group, 3,3'-bismethylenebiphenyl group, 4,4 ' -Bisethylidenebiphenyl group, 3,4'-bisethylidenebiphenyl group, 3,3'-bisethylidenebiphenyl group, 4,4'-bisisopropylidenebiphenyl group, 3,4'-bisisopropylidenebiphenyl group, 3, A 3′-bisisopropylidenebiphenyl group may be mentioned. Moreover, you may use together aldehydes and ketones, such as formaldehyde, acetaldehyde, propyl aldehyde, butyraldehyde, amyl aldehyde, benzaldehyde, acetone, as a crosslinking agent. n represents an integer of 1 to 20, preferably 1 to 5. Acid catalysts include hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, oxalic acid, trifluoroacetic acid, p-toluenesulfonic acid, dimethyl sulfate, diethyl sulfate, zinc chloride, aluminum chloride, iron chloride, boron trifluoride, ion exchange resin, Examples include activated clay, silica alumina, and zeolite.

（一般式（ａ）中のＲ²、Ｒ³は水素原子、炭素数１〜６のアルキル基から選ばれ、全てが同一でも異なっていてもよい。ｍは１〜３の整数を示す。）

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

  As the compound represented by the general formula (XXXIII), ENP-80 (manufactured by Nippon Kasei Epoxy Manufacturing Co., Ltd.) and the like are available. The softening point of the compound represented by the general formula (XXXIII) is preferably 40 to 200 ° C, more preferably 50 to 160 ° C, and further preferably 60 to 120 ° C. When the temperature is lower than 40 ° C, the curability is lowered, and when it exceeds 200 ° C, the fluidity tends to be lowered. Here, the softening point indicates a softening point measured based on the ring and ball method of JIS-K-6911.

  In order to exhibit the performance of the epoxy resin from each viewpoint, the blending amount is preferably 30% by mass or more, more preferably 50% by mass or more, and more preferably 60% by mass or more with respect to the total amount of the epoxy resin. More preferably.

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

  Of these, phenol / aralkyl resins are preferred from the viewpoints of flame retardancy and moldability. As a phenol aralkyl resin, the phenol resin shown by the following general formula (XXXIV) is mentioned.

（一般式（ＸＸＸＩＶ）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。）

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

  A phenol / aralkyl resin in which R in the general formula (XXXIV) is a hydrogen atom and the average value of n is 0 to 8 is more preferable. Specific examples include p-xylylene type phenol / aralkyl resins, m-xylylene type phenol / aralkyl resins, and the like. As such a compound, XLC (trade name, manufactured by Mitsui Chemicals, Inc.) is available as a commercial product. When using these aralkyl type phenol resins, the blending amount is preferably 30% by mass or more, more preferably 50% by mass or more, based on the total amount of the curing agent in order to exhibit the performance.

  From the viewpoint of flame retardancy and moldability, naphthol / aralkyl resins are preferred. Examples of the naphthol / aralkyl resin include a phenol resin represented by the following general formula (XXXV).

(In General Formula (XXXV), R ^{1 to} R ² are selected from a hydrogen atom and a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and each may be the same or different. Represents an integer of 0 to 10.)
Examples of the naphthol-aralkyl resin represented by the general formula (XXXV) include compounds in which R ¹ and R ² are all hydrogen atoms, and examples of such compounds include SN-170 (Nippon Steel Chemical Co., Ltd.). Company name) is available as a commercial product.

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

（一般式（ＸＸＸＶＩ）中、Ｒ^１及びＲ^２は水素原子及び炭素数１〜１０の置換又は非置換の一価の炭化水素基からそれぞれ独立して選ばれ、ｎは０〜１０の整数を示し、ｍは０〜６の整数を示す。）

(In General Formula (XXXVI), R ¹ and R ² are each independently selected from a hydrogen atom and a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and n is an integer of 0 to 10). M represents an integer of 0 to 6.)

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

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

（一般式（ＸＸＸＶＩＩ）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。）

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

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

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

  From the viewpoint of curability, a novolac type phenol resin is preferable. 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.

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

R ^{1 to} R ⁹ in the general formula (XXXVIII) may all be the same or different and have 1 to 1 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. 10 alkyl groups, methoxy groups, ethoxy groups, propoxy groups, butoxy groups, etc., C1-C10 alkoxyl groups, phenyl groups, tolyl groups, xylyl groups, etc. aryl groups, and benzyl groups , An aralkyl group having 6 to 10 carbon atoms such as a phenethyl group, among which a hydrogen atom and a methyl group are preferable. n represents an integer of 0 to 10.

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

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

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

  In this invention, the compound shown by the following general formula (XXXIX) can also be included.

（一般式（ＸＸＸＩＸ）中のＲ¹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、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選ばれ、ｎは０〜１０の整数を示し、ｍは０〜１０の整数を示す。）

(R ¹ in the general formula (XXXIX) is selected from a hydrogen atom and a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and R ² is a hydrogen atom and a substituted or unsubstituted group having 1 to 10 carbon atoms. (Selected from a substituted monovalent hydrocarbon group, n represents an integer of 0 to 10, and m represents an integer of 0 to 10.)

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

  As the compound represented by the general formula (XXXIX), HE-610C, 620C (manufactured by Air Water Co., Ltd.) and the like are available.

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

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

  The sealing epoxy resin composition of the present invention must contain (D) a cyclic phosphazene compound represented by the following general formula (II).

（一般式（ＩＩ）中、ｎは３〜５の整数で、Ｒ^１、Ｒ^２は炭素数１〜４のアルキル基またはアリール基から選ばれ、互いに同一であっても異なってもよい。）
上記一般式（ＩＩ）で示される化合物としては、３量体（ｎ＝３）の６員環、４量体（ｎ＝４）の８員環、５量体（ｎ＝５）の１０員環を単独あるいは混合して用いることができるが、エポキシ樹脂組成物の流動性向上という観点からはｎ＝３の３量体を主成分として用いることが好ましい。

(In general formula (II), n is an integer of 3 to 5, and R ¹ and R ² are selected from an alkyl group or an aryl group having 1 to 4 carbon atoms, and may be the same or different from each other.)
The compound represented by the general formula (II) includes a trimer (n = 3) 6-membered ring, a tetramer (n = 4) 8-membered ring, and a pentamer (n = 5) 10-membered. Rings can be used alone or in combination, but from the viewpoint of improving the fluidity of the epoxy resin composition, it is preferable to use a trimer of n = 3 as a main component.

In the general formula (II), n R ¹ and R ² may be the same or different and may be the same or different, and may be a C 1-4 alkyl group or aryl group, for example, n is a trimeric 6-membered ring R ¹ and R ² are 6 substituents, which may all be the same or different. R ¹ and R ² are preferably aryl groups from the viewpoint of heat resistance and moisture resistance of the epoxy resin composition, and more preferably phenyl groups and / or hydroxyphenyl groups. In the case of introducing a hydroxyphenyl group, all of n R ¹ and n R ² may be a hydroxyphenyl group, but at least one is preferable from the viewpoint of improving heat resistance and flame retardancy. More preferably, it is -4.

  Preferred structures of the cyclic phosphazene compound of component (D) used in the present invention include, for example, the following general formulas (XXXX) to (XXXXII).

（一般式（ＸＸＸＸＩＩ）中、Ｒ^１〜Ｒ^６のうち少なくとも１個は水酸基で、他は水素を示す。）

(In General Formula (XXXXII), at least one of R ^{1 to} R ⁶ is a hydroxyl group, and the other represents hydrogen.)

  The amount of these cyclic phosphazene compounds added is preferably such that the amount of phosphorus atoms is in the range of 0.2 to 3.0% by mass with respect to all other components except (C) inorganic filler. More preferably, it is 0.5-1.5 mass%. When it is 0.2% by mass or more, reflow resistance and flame retardancy are improved, and when it is 3.0% by mass or less, moisture resistance is improved.

  Further, as the cyclic phosphazene compound, a cyclic phosphazene compound containing the following formula (XXXXIII) and / or the following formula (XXXXIV) as a repeating unit in the main chain skeleton, or the following formula (XXXXV) having a different substitution position with respect to the phosphorus atom in the phosphazene ring And / or a compound containing the following formula (XXXXVI) as a repeating unit may be used.

Here, m in the formula (XXXXIII) and the formula (XXXXV) is an integer of 1 to 10, and R ^{1 to} R ⁴ are alkyl groups, aryl groups, and hydroxyl groups having 1 to 12 carbon atoms that may have a substituent. And all may be the same or different. A represents an alkylene group having 1 to 4 carbon atoms or an arylene group. N in Formula (XXXXIV) and Formula (XXXXVI) is an integer of 1 to 10, and R ^{5 to} R ⁸ are selected from an alkyl group or aryl group having 1 to 12 carbon atoms that may have a substituent, and all They may be the same or different, and A represents an alkylene group having 1 to 4 carbon atoms or an arylene group. In the formula, m R ¹ , R ² , R ³ and R ⁴ may all be the same or different, and n R ⁵ , R ⁶ , R ⁷ and R ⁸ are all n. It may be the same or different.

In the formulas (XXXXIII) to (XXXXVI), the alkyl group or aryl group having 1 to 12 carbon atoms which may have a substituent represented by R ^{1 to} R ⁸ is not particularly limited. Alkyl groups such as ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group and tert-butyl group, aryl groups such as phenyl group, 1-naphthyl group and 2-naphthyl group, o-tolyl Group, m-tolyl group, p-tolyl group, 2,3-xylyl group, 2,4-xylyl group, o-cumenyl group, m-cumenyl group, p-cumenyl group, mesityl group, etc. , Aryl group-substituted alkyl groups such as benzyl group and phenethyl group, and the like. Further, substituents substituted on these include alkyl groups, alkoxyl groups, aryl groups, Group, an amino group, an epoxy group, a vinyl group, a hydroxyalkyl group, an alkylamino group, and the like.

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

  Further, the alkylene group or arylene group having 1 to 4 carbon atoms represented by A in the above formulas (XXXXIII) to (XXXXVI) is not particularly limited, but for example, a methylene group, an ethylene group, a propylene group, an isopropylene group. , Butylene group, isobutylene group, phenylene group, tolylene group, xylylene group, naphthylene group, and the like. From the viewpoint of heat resistance and moisture resistance of the epoxy resin composition, an arylene group is preferable, and a phenylene group is more preferable.

  The cyclic phosphazene compound is a polymer of any one of the above formulas (XXXXIII) to (XXXXVI), a copolymer of the above formula (XXXXIII) and the above formula (XXXXVI), or the above formula (XXXXV) and the above formula (XXXXVI). 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 (XXXXVII) and a copolymer of the following formula (XXXXVIII).

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

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

Here, m and n in the above formula (XXXXVIII) are integers of 0 to 9, R ^{1 to} R ⁴ are each independently selected from hydrogen or a hydroxyl group, and R ^{5 to} R ⁶ are each independently hydrogen or a hydroxyl group. Chosen from. In addition, the cyclic phosphazene compound represented by the above formula (XXXXVIII) includes the following m repeating units (x) and n repeating units (y) alternately, including in block form, or including randomly Any of these may be used, but those randomly included are preferred.

Among them, the main component is a polymer in which n is 3 to 6 in the above formula (XXXXVII), or R ^{5 to} R ⁶ are all hydrogen or one is a hydroxyl group in the above formula (XXXXVIII), and m / n is 1 The main component is a copolymer of / 2 to 1/3 and m + n of 3 to 6. Moreover, as a commercially available phosphazene compound, SPE-100 whose all substituents are phenyl groups, and SPH-100 which is a mixture of phenyl groups and hydroxyphenyl groups (both are trade names manufactured by Otsuka Chemical Co., Ltd.) are available. .

  In the sealing epoxy resin composition of the present invention, (E) a curing accelerator can be used as necessary to promote the reaction between (A) the epoxy resin and (B) the curing agent. (E) The curing accelerator is generally used in the epoxy resin composition for sealing and is not particularly limited. For example, 1,8-diaza-bicyclo (5,4,0) undecene-7, 1 Cycloamidine compounds such as 1,5-diaza-bicyclo (4,3,0) nonene, 5,6-dibutylamino-1,8-diaza-bicyclo (5,4,0) undecene-7 and these compounds Maleic acid, 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone , Quinone compounds such as 2,3-dimethoxy-1,4-benzoquinone and phenyl-1,4-benzoquinone, and compounds having a π bond such as diazophenylmethane and phenol resin. A compound having intramolecular polarization, tertiary amines such as benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol, and derivatives thereof, 2-methylimidazole, 2-phenylimidazole, Imidazoles such as 2-phenyl-4-methylimidazole and derivatives thereof, phosphine compounds such as tributylphosphine, methyldiphenylphosphine, triphenylphosphine, tris (4-methylphenyl) phosphine, diphenylphosphine, and phenylphosphine, and these phosphines Phosphorus compound having intramolecular polarization, tetraphenylphosphoric acid, which is obtained by adding a compound having a π bond such as maleic anhydride, the above quinone compound, diazophenylmethane, or phenol resin to the compound. And tetraphenyl boron salts such as um tetraphenyl borate, triphenylphosphine tetraphenyl borate, 2-ethyl-4-methylimidazole tetraphenyl borate, N-methylmorpholine tetraphenyl borate, and derivatives thereof. It may be used or two or more types may be used in combination.

  Among these, an adduct of a tertiary phosphine compound and a quinone compound is preferable from the viewpoint of flame retardancy, curability, fluidity, and releasability. Although it does not specifically limit as a tertiary phosphine compound, Tricyclohexyl phosphine, tributyl phosphine, dibutyl phenyl phosphine, butyl diphenyl phosphine, ethyl diphenyl phosphine, triphenyl phosphine, tris (4-methylphenyl) phosphine, tris (4 -Ethylphenyl) phosphine, tris (4-propylphenyl) phosphine, tris (4-butylphenyl) phosphine, tris (isopropylphenyl) phosphine, tris (t-butylphenyl) phosphine, tris (2,4-dimethylphenyl) phosphine , Tris (2,6-dimethylphenyl) phosphine, tris (2,4,6-trimethylphenyl) phosphine, tris (2,6-dimethyl-4-ethoxyphenyl) phosphine, Squirrel (4-methoxyphenyl) phosphine, 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.

  (E) Although the compounding quantity of a hardening accelerator will not be restrict | limited especially if the hardening acceleration effect is achieved, 0.005-2 mass% is preferable with respect to the epoxy resin composition for sealing. 0.01 to 0.5 mass% is more preferable. If it is 0.005% by mass or more, the curability in a short time tends to be improved, and if it is 2% by mass or less, the fluidity is improved and a good molded product can be obtained.

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

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

The blending amount of the inorganic filler is 60 to 95 mass with respect to the epoxy resin composition for sealing from the viewpoints of fluidity, flame retardancy, moldability, hygroscopicity, linear expansion coefficient reduction, strength improvement and reflow resistance. % Is preferable, and 70 to 90% by mass is more preferable.
If it is 60% by mass or more, flame retardancy and reflow resistance tend to be improved, and if it is 95% by mass or less, fluidity tends to be improved.

  In the case of using (C) an inorganic filler, the sealing epoxy resin composition of the present invention may further contain (F) a coupling agent in order to improve the adhesion between the resin component and the filler. preferable. (F) The coupling agent is generally used in an epoxy resin composition for sealing and is not particularly limited. For example, a silane compound having a primary and / or secondary and / or tertiary amino group And various silane compounds such as epoxy silane, mercapto silane, alkyl silane, ureido silane, and vinyl silane, titanium compounds, aluminum chelates, and aluminum / zirconium compounds. Examples of these are vinyltrichlorosilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycol. Sidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, vinyltriacetoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropyl Triethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-anilinopropyltrimethoxysilane, γ-anilinopropyltriethoxysilane, γ- (N, N-dimethyl) aminopropyltrimethoxy Silane, γ- (N, N-diethyl) aminopropyltrimethoxysilane, γ- (N, N-dibutyl) aminopropyltrimethoxysilane, γ- (N-methyl) anilinopropyltrimethoxysilane, γ- (N -Ethyl) anilinopropyltrimethoxysilane, γ- (N, N-dimethyl) aminopropyltriethoxysilane, γ- (N, N-diethyl) aminopropyltriethoxysilane, γ- (N, N-dibutyl) amino Propyltriethoxysilane, γ- (N-methyl) anilinopropyltriethoxysilane, γ- (N-ethyl) anilinopropyltriethoxysilane, γ- (N, N-dimethyl) aminopropylmethyldimethoxysilane, γ- (N, N-diethyl) aminopropylmethyldimethoxysilane, γ- (N, N-dibutyl) aminopropy Rumethyldimethoxysilane, γ- (N-methyl) anilinopropylmethyldimethoxysilane, γ- (N-ethyl) anilinopropylmethyldimethoxysilane, N- (trimethoxysilylpropyl) ethylenediamine, N- (dimethoxymethylsilylisopropyl) ) Silane coupling agents such as ethylenediamine, methyltrimethoxysilane, dimethyldimethoxysilane, methyltriethoxysilane, γ-chloropropyltrimethoxysilane, hexamethyldisilane, vinyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, isopropyl Triisostearoyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, isopropyl tri (N-aminoethyl-aminoethyl) titanate, tetraoctane Rubis (ditridecyl phosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, bis (dioctyl pyrophosphate) oxyacetate titanate, bis (dioctyl pyrophosphate) ethylene titanate, Isopropyltrioctanoyl titanate, isopropyldimethacrylisostearoyl titanate, isopropyltridodecylbenzenesulfonyl titanate, isopropylisostearoyl diacryl titanate, isopropyltri (dioctylphosphate) titanate, isopropyltricumylphenyl titanate, tetraisopropylbis (dioctylphosphite) titanate And titanate coupling agents such as 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 viewpoints of fluidity, gold wire deformation reduction, and flame retardancy. The silane coupling agent having a secondary amino group is not particularly limited as long as it is a silane compound having a secondary amino group in the molecule. For example, γ-anilinopropyltrimethoxysilane, γ-anilinopropyltriethoxysilane Γ-anilinopropylmethyldimethoxysilane, γ-anilinopropylmethyldiethoxysilane, γ-anilinopropylethyldiethoxysilane, γ-anilinopropylethyldimethoxysilane, γ-anilinomethyltrimethoxysilane, γ- Anilinomethyltriethoxysilane, γ-anilinomethylmethyldimethoxysilane, γ-anilinomethylmethyldiethoxysilane, γ-anilinomethylethyldiethoxysilane, γ-anilinomethylethyldimethoxysilane, N- (p- Methoxyphenyl) -γ-aminopropyltrimeth Sisilane, N- (p-methoxyphenyl) -γ-aminopropyltriethoxysilane, N- (p-methoxyphenyl) -γ-aminopropylmethyldimethoxysilane, N- (p-methoxyphenyl) -γ-aminopropylmethyl Diethoxysilane, N- (p-methoxyphenyl) -γ-aminopropylethyldiethoxysilane, N- (p-methoxyphenyl) -γ-aminopropylethyldimethoxysilane, γ- (N-methyl) aminopropyltrimethoxy Silane, γ- (N-ethyl) aminopropyltrimethoxysilane, γ- (N-butyl) aminopropyltrimethoxysilane, γ- (N-benzyl) aminopropyltrimethoxysilane, γ- (N-methyl) aminopropyl Triethoxysilane, γ- (N-ethyl) aminopropyltriethoxy Lan, γ- (N-butyl) aminopropyltriethoxysilane, γ- (N-benzyl) aminopropyltriethoxysilane, γ- (N-methyl) aminopropylmethyldimethoxysilane, γ- (N-ethyl) aminopropyl Methyldimethoxysilane, γ- (N-butyl) aminopropylmethyldimethoxysilane, γ- (N-benzyl) aminopropylmethyldimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, γ- ( β-aminoethyl) aminopropyltrimethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane and the like.

  The total blending amount of the coupling agent is preferably 0.037 to 5% by mass, more preferably 0.05 to 4.75% by mass with respect to the sealing epoxy resin composition. More preferably, it is 1-2.5 mass%. If it is 0.037% by mass or more, the adhesion to the frame tends to be improved, and if it is 5% by mass or less, the moldability of the package tends to be improved.

  In the epoxy resin composition for sealing of the present invention, a conventionally known flame retardant for the purpose of further improving the flame retardancy, especially a halogen-free and non-antimony flame retardant, as required from the viewpoint of environmental friendliness and reliability, is required. Can be blended. For example, red phosphorus coated with inorganic compounds such as red phosphorus and zinc oxide and thermosetting resins such as phenolic resins, phosphorus compounds such as phosphate esters and phosphine oxides, melamine, melamine derivatives, melamine-modified phenolic resins, triazine rings , Nitrogen-containing compounds such as cyanuric acid derivatives and isocyanuric acid derivatives, aluminum hydroxide, magnesium hydroxide, composite metal hydroxides, zinc oxide, zinc stannate, zinc borate, iron oxide, molybdenum oxide, zinc molybdate And compounds containing metal elements such as dicyclopentadienyl iron, etc., and one of these may be used alone or two or more of them may be used in combination.

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

  Examples of the phosphoric acid ester represented by the general formula (XXXIX) include the phosphoric acid esters represented by the following structural formulas (XXXX) to (XXXXIV).

  The addition amount of these phosphate esters is preferably in the range of 0.2 to 3.0 mass% in terms of the amount of phosphorus atoms with respect to all the other compounding ingredients except the filler. If the amount is 0.2% by mass or more, the flame retardant effect tends to be improved. If the amount exceeds 3.0% by mass, the formability and moisture resistance are deteriorated, and these phosphates ooze out during molding, thereby inhibiting the appearance. There is a case.

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

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

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

Among the phosphorus compounds represented by the general formula (XXXXV), R ^{1 to} R ³ are preferably a substituted or unsubstituted aryl group, and 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 0.01-0.2 mass% with respect to the epoxy resin composition for sealing. More preferably, it is 0.02-0.1 mass%, More preferably, it is 0.03-0.08 mass%. When it is 0.01% by mass or more, flame retardancy tends to be improved, and when it is 0.2% by mass or less, moldability and moisture resistance tend to be improved.

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

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

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

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

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

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

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

  The molar ratio of p, q, and r in the composition formula (XXXXVI) 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, it is preferable that the molar ratio p / q of p and q in the composition formula (XXXXVII) is 99/1 to 50/50.

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

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

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

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

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

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

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

  The reaction temperature at the time of synthesizing a copolycondensation product of a compound having a phenolic hydroxyl group, a triazine derivative and a compound having an aldehyde group is not particularly limited, but is preferably 60 to 120 ° C. Moreover, 3-9 are preferable and, as for pH of reaction, 4-8 are more preferable. If the pH is less than 3, the resin tends to gel during synthesis, and if it is higher than 9, copolycondensation of the phenol resin, triazine derivative and compound having an aldehyde group hardly occurs, and the produced resin has a low nitrogen content.

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

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

  The number average molecular weight of the copolycondensation product of a compound having a phenolic hydroxyl group, a triazine derivative and a compound having an aldehyde group is preferably 500 to 1,000, and more preferably 550 to 800. If it is less than 500, moldability and reflow crack resistance are lowered, and if it exceeds 1000, fluidity tends to be lowered. The weight average molecular weight is preferably 1500 to 10,000, and more preferably 1700 to 7000. When it is less than 1500, the reflow crack resistance is lowered, and when it exceeds 10,000, the fluidity tends to be lowered. Furthermore, the molecular weight distribution Mw / Mn of the copolycondensation product of the compound having a phenolic hydroxyl group, the triazine derivative and the compound having an aldehyde group is preferably 2.0 to 10.0, and preferably 3.0 to 6. 0 is more preferable. When it is less than 2.0, the reflow crack resistance is lowered, and when it exceeds 10.0, the fluidity tends to be lowered.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

(Wherein R ¹ is selected from substituted or unsubstituted monovalent or divalent hydrocarbon groups having 1 to 12 carbon atoms relative to all R ¹ in the silicon-containing polymer, R ¹ may all be the same or different.)

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

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

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

  Such a silicon-containing polymer can be obtained by the production method shown below, but a commercially available product is available under the trade name AY42-119 manufactured by Toray Dow Corning Silicone Co., Ltd.

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

  (A) The organoalkoxysilane and / or siloxane used as a raw material for the silicon-containing polymer are methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane. , Phenyltrimethoxysilane, phenyltoethoxysilane, dimethyldimethoxysilane, methylphenyldimethoxysilane, methylvinyldimethoxysilane, phenylvinyldimethoxysilane, diphenyldimethoxysilane, methylphenyldiethoxysilane, methylvinyldiethoxysilane, phenylvinyldiethoxy Silane, diphenyldiethoxysilane, dimethyldiethoxysilane, tetramethoxysilane, tetraethoxysilane, dimethoxydiethoxysilane 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyl (methyl) dimethoxysilane, 3-glycidoxypropyl (methyl) diethoxysilane, 3-glycidoxy Propyl (phenyl) dimethoxysilane, 3-glycidoxypropyl (phenyl) diethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl (methyl) dimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl (methyl) ) Diethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl (phenyl) dimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl (phenyl) diethoxysilane, and their hydrolysis condensates. It is done.

  The content of the silicon-containing polymer is preferably 0.2% by mass to 1.5% by mass, and more preferably 0.3% by mass to 1.3% by mass with respect to the entire epoxy resin composition for sealing. When the amount is less than 0.2% by mass, the effect of adding the (A) silicon-containing polymer is not observed, and when the amount exceeds 1.5% by mass, the hot hardness of the resulting epoxy resin composition for sealing tends to decrease. is there.

  In addition, in the present invention, the compound represented by the following composition formula (XXXXXXXIV) and / or the compound represented by the following composition formula (XXXXXXXV) is improved as necessary in the moisture resistance and high-temperature storage characteristics of a semiconductor element such as an IC. It can be contained from the viewpoint.

（０＜Ｘ≦０．５、ｍは正の数）

(0 <X ≦ 0.5, m is a positive number)

（０．９≦ｘ≦１．１ ０．６≦ｙ≦０．８ ０．２≦ｚ≦０．４）

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

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

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

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

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

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

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

  An example of an electronic component device provided with such an element is a semiconductor device. Specifically, an element such as a semiconductor chip is fixed on a lead frame (island, tab) and 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), TQ TCP (Tape Carrier Package), a wiring board or glass in which a semiconductor chip lead-bonded to a resin carrier type IC such as P (Thin Quad Flat Package) or a tape carrier is sealed with the epoxy resin composition for sealing of the present invention COB (Chip On Board), COG (Chip On Glass), in which a semiconductor chip connected to the wiring formed above by wire bonding, flip chip bonding, solder or the like is sealed with the sealing epoxy resin composition of the present invention. Active devices such as semiconductor chips, transistors, diodes, thyristors and / or capacitors, resistors connected to semiconductor devices mounted on bare chips, etc., wiring formed on wiring boards and glass, wire bonding, flip chip bonding, solder, etc. A semiconductor chip is mounted on an interposer substrate on which a hybrid IC in which a passive element such as a body and a coil is sealed with the sealing epoxy resin composition of the present invention and a terminal for connecting an MCM (Multi Chip Module) motherboard is formed, and bumps Alternatively, after connecting the semiconductor chip and the wiring formed on the interposer substrate by wire bonding, the semiconductor chip mounting side is sealed with the sealing epoxy resin composition of the present invention, BGA (Ball Grid Array), CSP (Chip Size Package) ), MCP (Multi Chip Package), and the like. In addition, even if these semiconductor devices are stacked type packages in which two or more elements are stacked on a mounting substrate, the epoxy resin composition for sealing two or more elements at a time It may be a batch mold type package sealed with.

EXAMPLES Next, although an Example demonstrates this invention, the scope of the present invention is not restrict | limited to these Examples.
(Examples 1 to 26, Comparative Examples 1 to 11)
As an epoxy resin,
[Epoxy resin 1]: Epoxy resin of the above general formula (I) having an epoxy equivalent of 251 and a softening point of 60 ° C. (trade name HP-5000, manufactured by DIC Corporation),
[Epoxy resin 2]: biphenyl type epoxy resin (trade name Epicoat YX-4000H manufactured by Mitsubishi Chemical Corporation) having an epoxy equivalent of 196 and a melting point of 106 ° C.
[Epoxy resin 3]: Bisphenol F-type epoxy resin having an epoxy equivalent of 186 and a melting point of 108 ° C. (trade name YSLV-80XY, manufactured by Nippon Kayaku Epoxy Manufacturing Co., Ltd.)
[Epoxy Resin 4]: Epoxy Equivalent 245, Sulfur Atom-Containing Epoxy Resin with a Melting Point of 110 ° C. (trade name YSLV-120TE manufactured by Nippon Kayaku Epoxy Manufacturing Co., Ltd.)
[Epoxy resin 5]: biphenylene type epoxy resin having an epoxy equivalent of 273 and a softening point of 58 ° C. (trade name NC-3000, manufactured by Nippon Kayaku Co., Ltd.)
[Epoxy resin 6]: Epoxy equivalent 190 and o-cresol novolac type epoxy resin having a softening point of 65 ° C. (trade name YDCN-500 manufactured by Nippon Kayaku Epoxy Manufacturing Co., Ltd.)
As a curing agent,
[Hardening 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 phenolic resin having a hydroxyl group equivalent of 199 (Maywa Kasei Co., Ltd. trade name MEH-7851) Co., Ltd. trade name Millex XLC-3L),
[Curing agent 3]: Phenol novolak resin (trade name H-1 manufactured by Meiwa Kasei Co., Ltd.) having a softening point of 80 ° C. and a hydroxyl group equivalent of 106,
As a curing accelerator,
[Curing Accelerator 1]: Triphenylphosphine,
[Curing accelerator 2]: Adduct of triphenylphosphine and 1,4-benzoquinone,
As an additive,
[Phosphorus compound 1]: cyclic phosphazene compound of the above general formula (XXXX), component (D) having a phosphorus atom content of 13% by mass (trade name SPE-100, manufactured by Otsuka Chemical Co., Ltd.),
[Phosphorus compound 2]: The cyclic phosphazene compound of component (D) having a phosphorus atom content of 12% by mass, wherein three of R ^{1 to} R ^{6 in} the above general formula (XXXXII) are hydroxyl groups and all the remaining are hydrogen atoms (Trade name SPH-100 manufactured by Otsuka Chemical Co., Ltd.)
[Phosphorus compound 3]: Triphenyl phosphate having a phosphorus atom content of 9% by mass,
[Sulfur compound 1]: Sulfur atom-containing silane coupling agent (trade name Z-6940 manufactured by Toray Dow Corning Silicone Co., Ltd.)
As a coupling agent
[Epoxysilane]: γ-glycidoxypropyltrimethoxysilane,
[Anilinosilane]: secondary amino group-containing silane coupling agent (γ-anilinopropyltrimethoxysilane),
As a flame retardant,
[Antimony trioxide]: antimony trioxide,
[Brominated epoxy resin]: bisphenol A brominated epoxy resin having an epoxy equivalent of 397, a softening point of 69 ° C. and a bromine content of 49% by mass (YDB-400 manufactured by Nippon Kayaku Epoxy Co., Ltd.),
As an inorganic filler,
[Fused silica]: Spherical fused silica having an average particle size of 14.5 μm and a specific surface area of 2.8 m ² / g,
As other additives,
[Carnauba Wax]: product name HW-E manufactured by Clariant
[Carbon black]: trade name MA-100 manufactured by Mitsubishi Chemical Corporation
Were mixed in parts by mass shown in Tables 1 to 4, and roll kneading was carried out under conditions of a kneading temperature of 80 ° C. and a kneading time of 10 minutes to produce Examples 1 to 26 and Comparative Examples 1 to 11.

The characteristics of the produced epoxy resin compositions for sealing of Examples 1 to 26 and Comparative Examples 1 to 11 were determined by the following tests. The results are shown in Tables 5-8.
(1) Spiral flow Using a spiral flow measurement mold in accordance with EMMI-1-66, a sealing epoxy resin composition was molded by a transfer molding machine at a mold temperature of 180 ° C., a molding pressure of 6.9 MPa, and a curing time. Molding was performed for 90 seconds, and the flow distance (cm) was determined.

(2) Hardness 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. Post-curing was performed and flame retardancy was evaluated according to the UL-94 test method.

(4) Glass transition temperature The epoxy resin composition for sealing is molded into a 2 mm × 2 mm × 19 mm cylindrical shape under the molding conditions of (1) above, and further post-cured at 180 ° C. for 5 hours. The temperature dependence of the amount of expansion was measured using (manufactured by Rigaku Corporation TMA8140), and the glass transition temperature was determined from the intersection of the tangent line on the low temperature side and the high temperature side from the bending point.

(5) Reflow resistance (5.1) Cu lead frame 8mm x 10mm x 0.4mm silicon chip mounted 80mm flat package (QFP) with outer dimensions of 20mm x 14mm x 2mm (Lead frame material: copper alloy, Die pad top surface and lead tip silver-plated product) are molded and post-cured using the epoxy resin composition for sealing under the condition (1) above, and humidified at 85 ° C. and 85% RH. Then, reflow treatment was performed at a predetermined time of 240 ° C. for 10 seconds, the presence or absence of cracks was observed, and the number of crack generation packages with respect to the number of test packages (5) was evaluated.
(5.2) PPF lead frame Reflow resistance is the same as (5.1) except that PPF (core material: copper alloy, three-layer (Ni / Pd / Au) plated product) is used for the lead frame. Evaluation was performed.

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

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

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

  Of Comparative Examples 1 to 11 in which both the epoxy resin represented by the general formula (I) of the component (A) and the cyclic phosphazene compound represented by the general formula (II) of the component (D) are not blended, Comparative Example 1 3 to 9 and 11 are inferior in reflow resistance. In particular, Comparative Examples 1, 7 and 11 are greatly inferior. Moreover, Comparative Examples 3-5, 7 and 8 are inferior in flame retardancy and do not achieve UL-94 V-0. Moreover, Comparative Examples 3-6 and 9 are inferior in curability. Furthermore, Comparative Examples 2, 9, and 10 are inferior in moisture resistance and high temperature storage characteristics. Comparative Example 11 has poor high temperature storage characteristics.

  On the other hand, Examples 1 to 26 containing both the epoxy resin represented by the general formula (I) of the component (A) and the cyclic phosphazene compound represented by the general formula (II) of the component (D) are resistant to resistance. Reflowability is good, all achieve UL-94 V-0, flame retardancy is good, and moldability is also good. Furthermore, it has excellent reliability such as moisture resistance and high temperature storage.

Claims (6)

(A) An epoxy resin represented by the following general formula (I), (B) a curing agent, (C) an inorganic filler, and (D) a cyclic phosphazene compound represented by the following general formula (II) Resin composition.

(In the general formula (I), R ¹ and R ² are selected from a hydrogen atom, an alkyl group having 1 to 6 carbon atoms and an alkoxy group having 1 to 2 carbon atoms, and may be the same or different from each other. Represents an integer of 0 to 10.)

(In general formula (II), n is an integer of 3 to 5, and R ¹ and R ² are selected from an alkyl group or an aryl group having 1 to 4 carbon atoms, and may be the same or different from each other.)   The content of the cyclic phosphazene compound as component (D) is such that the amount of phosphorus atoms is 0.2 to 3.0% by mass relative to the total amount of the blending components excluding the inorganic filler (C). The epoxy resin composition for sealing according to 1.   The epoxy resin composition for sealing according to claim 1 or 2, wherein n of the cyclic phosphazene compound of component (D) is 3. The epoxy resin composition for sealing according to any one of claims 1 to 3, wherein all of n R ¹ and n R ² of the cyclic phosphazene compound of component (D) are phenyl groups. The cyclic phosphazene compound of component (D), wherein at least one of n R ¹ and n R ² is a hydroxyphenyl group, and all the others are phenyl groups. An epoxy resin composition for sealing.   The electronic component apparatus provided with the element sealed with the epoxy resin composition for sealing in any one of Claims 1-5.