JP4822053B2 - Epoxy resin composition for sealing and electronic component device - Google Patents

Description

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

  Conventionally, in the field of element sealing of electronic component devices such as transistors and ICs, resin sealing has been the mainstream in terms of productivity and cost, and epoxy resin molding materials have been widely used. This is because epoxy resins are balanced in various properties such as electrical properties, moisture resistance, heat resistance, mechanical properties, and adhesiveness with inserts. The flame-retardant of these sealing epoxy resin molding materials is mainly performed by a combination of a brominated resin such as diglycidyl ether of tetrabromobisphenol A and antimony oxide.

  In recent years, there has been a movement of laws and regulations relating to brominated compounds such as RoHS and WEEE from the viewpoint of environmental protection, and there has been a demand for non-halogenation (non-bromination) and non-antimony formation for epoxy resin molding materials for sealing. In addition, it is known that a bromo compound has an adverse effect on the high temperature storage characteristics of a plastic encapsulated IC. From this viewpoint, reduction of the amount of bromo resin is desired.

  Therefore, as a method for achieving flame retardancy without using brominated resin or antimony oxide, a method using red phosphorus (for example, see Patent Document 1) and a method using a phosphoric ester compound (for example, see Patent Document 2). ), A method using a phosphazene compound (for example, see Patent Document 3), a method using a metal hydroxide (for example, see Patent Document 4), and a method for using a metal hydroxide and a metal oxide in combination (for example, see Patent Document 5). ), Cyclopentadienyl compounds such as ferrocene (see, for example, Patent Document 6), flame retardants other than halogen and antimony, such as methods using organometallic compounds such as acetylacetonate copper (see, for example, Non-Patent Document 1). , A method of increasing the ratio of the filler (see, for example, Patent Document 7), and recently, a method of using a highly flame-retardant resin (for example, special References 8.), And the like have been attempted.

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

  However, when red phosphorus is used as the epoxy resin molding material for sealing, there is a problem of reduced moisture resistance, and when a phosphoric ester compound or phosphazene compound is used, there is a problem of reduced moldability or reduced moisture resistance due to plasticization. When using metal hydroxides, there are problems of lowering fluidity and mold releasability, and when using metal oxides or increasing the proportion of filler, there are problems of lowering fluidity. . Further, when an organometallic compound such as acetylacetonate copper is used, there is a problem that the curing reaction is inhibited and the moldability is lowered. Furthermore, the method using a highly flame-retardant resin invented so far does not sufficiently satisfy UL-94 V-0, which is required for materials of electronic component devices.

  As described above, in the method of increasing the proportion of these non-halogen, non-antimony flame retardants and fillers and the method using a highly flame-retardant resin, sealing using both a brominated resin and antimony oxide is used in both cases. The moldability, reliability, and flame retardancy equivalent to the epoxy resin molding materials for use have not been achieved.

  The present invention has been made in view of such circumstances, and is an epoxy for sealing that is non-halogen and non-antimony and has good flame retardancy without reducing reliability such as moldability, reflow resistance, moisture resistance, and high-temperature storage properties. An object of the present invention is to provide an electronic component device including a resin material and an element sealed thereby.

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

The present application relates to the following inventions.
(1) An epoxy resin composition for sealing containing (A) an epoxy resin and (B) a curing agent, and (A) an epoxy resin containing (C) a compound represented by the following general formula (I).

（一般式（Ｉ）中のＲ^１は水素原子、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、Ｒ^２ は炭素数１〜６のアルコキシ基から選ばれる。ｎは１〜２０の整数を示す。）

^{(R 1} in the general formula (I) is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, selected from alkoxy groups having 1 to 6 carbon atoms, ^{R 2} is selected from alkoxy groups having a carbon number of 1-6. n represents an integer of 1 to 20.)

(2) Single general formula compounds represented by (I) (C) R ² is a methoxy group above (1) encapsulated epoxy resin composition according in.
(3) a compound represented by the general formula (I) (C) above ^{R 1} is a methyl group in (1) or (2) encapsulated epoxy resin composition.
( 4 ) The epoxy resin composition for sealing according to any one of the above (1) to ( 3 ), wherein the epoxy equivalent of the compound (C) represented by the general formula (I) is 260 or more.
( 5 ) (C) The epoxy resin composition for sealing according to any one of the above (1) to ( 4 ), wherein the compound represented by the general formula (I) is contained in 40 to 100% by mass in the (A) epoxy resin.
( 6 ) (C) The epoxy resin composition for sealing according to any one of (1) to ( 4 ), wherein the compound represented by the general formula (I) is contained in 60 to 100% by mass in the (A) epoxy resin.
( 7 ) (A) Epoxy resin is biphenyl type epoxy resin, bisphenol F type epoxy resin, stilbene type epoxy resin, sulfur atom-containing epoxy resin, novolac type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, triphenyl The epoxy resin composition for sealing according to any one of the above (1) to ( 6 ), comprising at least one of a methane type epoxy resin, a biphenylene type epoxy resin, and a naphthol / aralkyl type epoxy resin.
( 8 ) (B) The above (1) to (B), wherein the curing agent contains at least one of biphenyl type phenol resin, aralkyl type phenol resin, dicyclopentadiene type phenol resin, triphenylmethane type phenol resin and novolac type phenol resin. 7 ) The epoxy resin composition for sealing according to any one of the above.
( 9 ) The epoxy resin composition for sealing according to any one of (1) to ( 8 ), further comprising (D) a curing accelerator.
( 10 ) The epoxy resin composition for sealing according to the above ( 9 ), wherein the (D) curing accelerator is triphenylphosphine.
( 11 ) The epoxy resin composition for sealing according to the above ( 9 ), wherein the (D) curing accelerator is an adduct of a third phosphine compound and a quinone compound.
( 12 ) The sealing epoxy resin composition according to any one of (1) to ( 11 ), further comprising (E) an inorganic filler.
( 13 ) The epoxy resin composition for sealing according to the above ( 12 ), wherein the content of the (E) inorganic filler is 60 to 95% by mass.
( 14 ) The epoxy resin composition for sealing according to the above ( 12 ), wherein the content of (E) inorganic filler is 70 to 90% by mass.
( 15 ) The epoxy resin composition for sealing according to any one of (1) to ( 14 ), further comprising (F) a coupling agent.
( 16 ) The epoxy resin composition for sealing according to the above ( 15 ), wherein the coupling agent comprises a silane coupling agent having a secondary amino group.
( 17 ) The epoxy resin composition for sealing according to the above ( 16 ), wherein the silane coupling agent having a secondary amino group contains a compound represented by the following general formula (II).

（ここで、Ｒ^１は水素原子、炭素数１〜６のアルキル基及び炭素数１〜２のアルコキシ基から選ばれ、Ｒ^２は炭素数１〜６のアルキル基及びフェニル基から選ばれ、Ｒ^３はメチル基又はエチル基を示し、ｎは１〜６の整数を示し、ｍは１〜３の整数を示す。）

(Where R ¹ is selected from a hydrogen atom, an alkyl group having 1 to 6 carbon atoms and an alkoxy group having 1 to ² carbon atoms, R ² is selected from an alkyl group having 1 to 6 carbon atoms and a phenyl group; ³ represents a methyl group or an ethyl group, n represents an integer of 1 to 6, and m represents an integer of 1 to ^3. )

( 18 ) An electronic component device comprising an element sealed with the sealing epoxy resin composition according to any one of (1) to ( 17 ).

  The epoxy resin composition for sealing according to the present invention can provide products such as electronic component devices having good flame retardancy, and its industrial value is great.

  The (A) epoxy resin used in the present invention includes (C) a compound represented by the following general formula (I).

（一般式（Ｉ）中のＲ^１は水素原子、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、Ｒ^２は炭素数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る。ｎは１〜２０の整数を示す。）

(R ¹ in the general formula (I) is selected from a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms, and R ² is an alkyl group having 1 to 8 carbon atoms and 1 carbon atom. Selected from alkoxy groups of -6, n represents an integer of 1-20.)

(C) R ¹ in the general formula (I) is preferably an alkyl group having 1 to 8 carbon atoms from the viewpoint of flame retardancy, and more preferably a methyl group. R ² is preferably an alkoxy group having 1 to 6 carbon atoms from the viewpoint of flame retardancy, and more preferably a methoxy group. In addition, the epoxy equivalent of the compound (C) of the general formula (I) is preferably 240 or more, more preferably 250 or more, and further preferably 260 or more from the viewpoint of flame retardancy. If the epoxy equivalent is less than 240, the flame retardancy tends to decrease. The method for measuring the epoxy equivalent is not particularly limited, but the ISO-3001 method (TEAB-perchloric acid method) or the like is generally used. (C) EXA-7320 (manufactured by Dainippon Ink & Chemicals, Inc.) in which R ¹ is a methyl group and R ² is a methoxy group is available as a compound represented by the general formula (I).

  (C) The softening point of the compound represented by the general formula (I) is preferably 40 to 200 ° C, more preferably 50 to 160 ° C, and further preferably 50 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.

  (C) 40-100 mass% is preferable in the epoxy resin whole quantity, and, as for the compounding quantity of the compound shown by general formula (I), 60-100 mass% is more preferable. If it is less than 40% by mass, the flame retardancy tends to decrease.

  A conventionally well-known epoxy resin can be used together in this invention. The epoxy resin that can be used in combination is generally used in an epoxy resin composition for sealing and is not particularly limited. For example, it has a phenol novolac type epoxy resin, an orthocresol novolac type epoxy resin, or a triphenylmethane skeleton. Phenols such as epoxy resin, cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol F and the like and / or naphthols such as α-naphthol, β-naphthol, dihydroxynaphthalene and formaldehyde, acetaldehyde, propionaldehyde, An epoxidized novolak resin obtained by condensation or cocondensation with a compound having an aldehyde group such as benzaldehyde or salicylaldehyde under an acidic catalyst. 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, xylylene skeleton, phenol / aralkyl resin containing biphenylene skeleton, epoxy of aralkyl type phenol resin such as naphthol / aralkyl resin , Trimethylolpropane type epoxy resin, terpene modified epoxy resin, linear aliphatic epoxy resin obtained by oxidizing olefinic bond with peracid such as peracetic acid, alicyclic ring Epoxy resins, include such sulfur-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.

  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 epoxy resin. Examples of the 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).

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

(Here, R ^{1 to} R ⁸ are selected from a hydrogen atom and a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, all of which may be the same or different. N is 0 to 3). Indicates an integer.)

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

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

（ここで、Ｒ^１〜Ｒ^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。）

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

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

(Here, R ^{1 to} R ⁸ are selected from a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, and a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, all of which are 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 Japan Epoxy Resin Co., Ltd.) and the like are 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 Toto Kasei Co., Ltd.) having n = 0 as a main component is commercially available.

  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, among others, 3-tert-butyl-4,4'- Dihydroxy-3 ', 5,5'-trimethylstilbene and 4,4'-dihydroxy-3,3', 5,5'-tetramethylstilbene are preferred. These stilbene type phenols may be used alone or in combination of two or more.

Among the sulfur atom-containing epoxy resins represented by the general formula (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 Tohto Kasei Co., Ltd.) and the like are available as commercial products. Any one of these epoxy resins may be used alone or in combination of two or more.

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

（ここで、Ｒは水素原子及び炭素数１〜１０の置換又は非置換の一価の炭化水素基から選ばれ、ｎは０〜１０の整数を示す。）

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

  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).

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

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

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

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

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.

（ここで、Ｒは水素原子及び炭素数１〜１０の置換又は非置換の一価の炭化水素基から選ばれ、ｎは１〜１０の整数を示す。）

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

  As said compound whose R is a hydrogen atom, E-1032 (Japan Epoxy Resin 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).

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

(R ^{1 to} R ⁹ in the above formula may all be the same or different and are alkyls having 1 to 10 carbon atoms such as hydrogen atom, methyl group, ethyl group, propyl group, butyl group, isopropyl group, isobutyl group, etc. Group, methoxy group, ethoxy group, propoxy group, butoxy group, etc., C1-C10 alkoxyl group, phenyl group, tolyl group, xylyl group, etc. aryl group, benzyl group, phenethyl group Selected from aralkyl groups having 6 to 10 carbon atoms such as hydrogen atom and methyl group, and n represents an integer of 0 to 10.)

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

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

  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 (trade name, manufactured by Tohto Kasei Co., Ltd.) is 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 together 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 of Japan Epoxy Resin Co., Ltd.) and the like are available.

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

  The (B) curing agent used in the present invention is generally used in the epoxy resin composition for sealing and is not particularly limited. For example, phenol, cresol, resorcin, catechol, bisphenol A, bisphenol F, phenyl Phenols such as phenol and aminophenol and / or naphthols such as α-naphthol, β-naphthol and dihydroxynaphthalene and a compound having an aldehyde group such as formaldehyde, benzaldehyde and salicylaldehyde are condensed or cocondensed in an acidic catalyst. Phenolic aralkyl resin, biphenylene type phenol aralkyl tree synthesized from novolac type phenolic resin, phenols and / or naphthols and dimethoxyparaxylene or bis (methoxymethyl) biphenyl Dialkyl such as dicyclopentadiene type phenol novolac resin, dicyclopentadiene type naphthol novolak resin, synthesized by copolymerization from aralkyl type phenol resin such as fat, naphthol / aralkyl resin, phenol and / or naphthols and dicyclopentadiene Cyclopentadiene type phenolic resin, triphenylmethane type phenolic resin, terpene modified phenolic resin, paraxylylene and / or metaxylylene modified phenolic resin, melamine modified phenolic resin, cyclopentadiene modified phenolic resin, phenol obtained by copolymerizing two or more of these Resin etc. are mentioned. These may be used alone or in combination of two or more.

  Among these, from the viewpoint of flame retardancy and moldability, a phenol / aralkyl resin represented by the following general formula (XXXIII) is preferable.

（ここで、Ｒは水素原子及び炭素数１〜１０の置換又は非置換の一価の炭化水素基から選ばれ、ｎは０〜１０の整数を示す。）

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

  A phenol / aralkyl resin in which R in the general formula (XXXIII) is a hydrogen atom and the average value of n is 0 to 8 is more preferable. Specific examples include p-xylylene type phenol / aralkyl resins, m-xylylene type phenol / aralkyl resins, and the like. As such a compound, 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.

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

Examples of the naphthol-aralkyl resin represented by the general formula (XXXIV) 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.

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

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

Wherein R ¹ and R ² are each independently selected from a hydrogen atom and a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, n is an integer of 0 to 10, and m is 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.

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

（ここで、Ｒは水素原子及び炭素数１〜１０の置換又は非置換の一価の炭化水素基から選ばれ、ｎは１〜１０の整数を示す。）

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

  As 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.

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

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

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

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

  From the viewpoint of improving flame retardancy, the sealing epoxy resin composition of the present invention may contain acenaphthylene. Although acenaphthylene can be obtained by dehydrogenating acenaphthene, a commercially available product may be used. Further, it can be used as a polymer of acenaphthylene or a polymer of acenaphthylene and other aromatic olefins. Examples of a method for obtaining a polymer of acenaphthylene or a polymer of acenaphthylene and another aromatic olefin include radical polymerization, cationic polymerization, and anionic polymerization. In the polymerization, a conventionally known catalyst can be used, but it can also be carried out only by heat without using a catalyst. At this time, the polymerization temperature is preferably 80 to 160 ° C, more preferably 90 to 150 ° C. 60-150 degreeC is preferable and, as for the softening point of the polymer of the polymer of acenaphthylene obtained or acenaphthylene and another aromatic olefin, 70-130 degreeC is more preferable. When the temperature is lower than 60 ° C., the moldability tends to decrease due to oozing during molding, and when the temperature is higher than 150 ° C., the compatibility with the resin tends to decrease.

  Examples of other aromatic olefins to be copolymerized with acenaphthylene include styrene, α-methylstyrene, indene, benzothiophene, benzofuran, vinylnaphthalene, vinylbiphenyl, and alkyl-substituted products thereof. In addition to the above-mentioned aromatic olefins, aliphatic olefins can be used in combination as long as the effects of the present invention are not hindered. Examples of the aliphatic olefin include (meth) acrylic acid and esters thereof, maleic anhydride, itaconic anhydride, fumaric acid and esters thereof. The amount of the aliphatic olefin used is preferably 20% by weight or less, more preferably 9% by weight or less, based on the total amount of the polymerization monomers.

  Furthermore, as acenaphthylene, the acenaphthylene premixed with a part or all of (B) hardening | curing agent can also be contained. (B) A premixed mixture of a part or all of the curing agent and one or more of acenaphthylene, a polymer of acenaphthylene, and a polymer of acenaphthylene and another aromatic olefin may be used. As a premixing method, (B) and the acenaphthylene component are each finely pulverized and mixed with a mixer or the like in a solid state, a method in which both components are uniformly dissolved in a solvent that dissolves both components, and then the solvent is removed. B) and / or a method in which both are melt mixed at a temperature equal to or higher than the softening point of the acenaphthylene component, etc., but a melt mixing method in which a uniform mixture is obtained and impurities are less mixed is preferable. The melt mixing is not limited as long as the temperature is equal to or higher than the softening point of (B) and / or the acenaphthylene component, but is preferably 100 to 250 ° C, more preferably 120 to 200 ° C. Moreover, although melt mixing will not have a restriction | limiting in mixing time if both are mixed uniformly, 1 to 20 hours are preferable and 2 to 15 hours are more preferable.

  When the (B) curing agent and acenaphthylene are premixed, the acenaphthylene component may be polymerized or reacted with the (B) curing agent during mixing. In the epoxy resin composition for sealing of the present invention, from the viewpoint of improving flame retardancy due to dispersibility of the acenaphthylene component, the above-mentioned premix (acenaphthylene-modified curing agent) is 90% by weight in the (B) curing agent. It is preferable to be contained above. The amount of acenaphthylene and / or aromatic olefin polymer containing acenaphthylene contained in the acenaphthylene-modified curing agent is preferably 5 to 40% by weight, and more preferably 8 to 25% by weight. If the amount is less than 5% by weight, the flame retardancy tends to decrease, and if it exceeds 40% by weight, the moldability tends to decrease. The content of the acenaphthylene structure contained in the epoxy resin composition of the present invention is preferably 0.1 to 5% by weight and more preferably 0.3 to 3% by weight from the viewpoints of flame retardancy and moldability. If it is less than 0.1% by weight, it tends to be inferior in flame retardancy, and if it is more than 5% by weight, moldability tends to be lowered.

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

  In the sealing epoxy resin composition of the present invention, a (D) curing accelerator can be used as necessary to promote the reaction between the (A) epoxy resin and the (B) curing agent. (D) Although a hardening accelerator is generally used for the epoxy resin composition for sealing and is not particularly limited, for example, 1,8-diaza-bicyclo (5,4,0) undecene-7, 1 , 5-diaza-bicyclo (4,3,0) nonene, cycloamidine compounds such as 5,6-dibutylamino-1,8-diaza-bicyclo (5,4,0) undecene-7 and these compounds Maleic 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.

  Of these, triphenylphosphine is preferable from the viewpoint of flame retardancy and curability, and an adduct of a third phosphine compound and a quinone compound is preferable from the viewpoint of flame retardancy, curability, fluidity, and mold release. . 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.

  (D) Although the compounding quantity of a hardening accelerator will not be restrict | limited especially if the hardening acceleration effect is achieved, 0.005 to 2 weight% is preferable in the epoxy resin composition for sealing, 0 0.01 to 0.5% by weight is more preferable. If it is less than 0.005% by weight, the curability in a short time tends to be inferior, and if it exceeds 2% by weight, the curing rate tends to be too high and it tends to be difficult to obtain a good molded product.

  In this invention, (E) inorganic filler can be mix | blended as needed. 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.) and the like, and as the zinc molybdate, KEGGARD 911B, 911C, 1100 (Sherwin- (Made by Williams) etc. are each available as a commercial item.

  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 in the sealing epoxy resin composition is preferably 50% by mass or more from the viewpoints of flame retardancy, moldability, hygroscopicity, linear expansion coefficient reduction, strength improvement and reflow resistance, -95 mass% is more preferable from a flame-retardant viewpoint, and 70-90 mass% is further more preferable. If the amount is less than 60% by mass, the flame retardancy and the reflow resistance tend to be lowered. If the amount exceeds 95% by mass, the fluidity tends to be insufficient, and the flame retardancy tends to be lowered.

  (E) When an inorganic filler is used, the sealing epoxy resin composition of the present invention may further contain (F) a coupling agent in order to enhance the adhesion between the resin component and the filler. preferable. (F) The coupling agent is generally used in an epoxy resin composition for sealing and is not particularly limited. For example, a silane compound having a primary and / or secondary and / or tertiary amino group And various silane compounds such as epoxy silane, mercapto silane, alkyl silane, ureido silane, and vinyl silane, titanium compounds, aluminum chelates, and aluminum / zirconium compounds. Examples of these are vinyltrichlorosilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycol. Sidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, vinyltriacetoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropyl Triethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-anilinopropyltrimethoxysilane, γ-anilinopropyltriethoxysilane, γ- (N, N-dimethyl) aminopropyltrimethoxy Silane, γ- (N, N-diethyl) aminopropyltrimethoxysilane, γ- (N, N-dibutyl) aminopropyltrimethoxysilane, γ- (N-methyl) anilinopropyltrimethoxysilane, γ- (N -Ethyl) anilinopropyltrimethoxysilane, γ- (N, N-dimethyl) aminopropyltriethoxysilane, γ- (N, N-diethyl) aminopropyltriethoxysilane, γ- (N, N-dibutyl) amino Propyltriethoxysilane, γ- (N-methyl) anilinopropyltriethoxysilane, γ- (N-ethyl) anilinopropyltriethoxysilane, γ- (N, N-dimethyl) aminopropylmethyldimethoxysilane, γ- (N, N-diethyl) aminopropylmethyldimethoxysilane, γ- (N, N-dibutyl) aminopropy Rumethyldimethoxysilane, γ- (N-methyl) anilinopropylmethyldimethoxysilane, γ- (N-ethyl) anilinopropylmethyldimethoxysilane, N- (trimethoxysilylpropyl) ethylenediamine, N- (dimethoxymethylsilylisopropyl) ) Silane coupling agents such as ethylenediamine, methyltrimethoxysilane, dimethyldimethoxysilane, methyltriethoxysilane, γ-chloropropyltrimethoxysilane, hexamethyldisilane, vinyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, isopropyl Triisostearoyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, isopropyl tri (N-aminoethyl-aminoethyl) titanate, tetraoctane Rubis (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 viewpoint of fluidity and flame retardancy. The silane coupling agent having a secondary amino group is not particularly limited as long as it is a silane compound having a secondary amino group in the molecule. For example, γ-anilinopropyltrimethoxysilane, γ-anilinopropyltriethoxysilane Γ-anilinopropylmethyldimethoxysilane, γ-anilinopropylmethyldiethoxysilane, γ-anilinopropylethyldiethoxysilane, γ-anilinopropylethyldimethoxysilane, γ-anilinomethyltrimethoxysilane, γ- Anilinomethyltriethoxysilane, γ-anilinomethylmethyldimethoxysilane, γ-anilinomethylmethyldiethoxysilane, γ-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. Of these, aminosilane coupling agents represented by the following general formula (II) are particularly preferred.

（ここで、Ｒ^１は水素原子、炭素数１〜６のアルキル基及び炭素数１〜２のアルコキシ基から選ばれ、Ｒ^２は炭素数１〜６のアルキル基及びフェニル基から選ばれ、Ｒ^３はメチル基又はエチル基を示し、ｎは１〜６の整数を示し、ｍは１〜３の整数を示す。）

(Where R ¹ is selected from a hydrogen atom, an alkyl group having 1 to 6 carbon atoms and an alkoxy group having 1 to ² carbon atoms, R ² is selected from an alkyl group having 1 to 6 carbon atoms and a phenyl group; ³ represents a methyl group or an ethyl group, n represents an integer of 1 to 6, and m represents an integer of 1 to ^3. )

  The total amount of coupling agent in the epoxy resin composition for sealing is preferably 0.037 to 4.75% by mass, more preferably 0.05 to 5% by mass, More preferably, it is -2.5 mass%. If it is less than 0.037% by mass, the adhesion to the frame tends to be lowered, and if it exceeds 4.75% by mass, the moldability of the package tends to be lowered.

  In the sealing epoxy resin composition of the present invention, conventionally known non-halogen and non-antimony flame retardants can be blended as needed for the purpose of further improving the flame retardancy. 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, phosphorus and nitrogen-containing compounds such as cyclophosphazenes, aluminum hydroxide, magnesium hydroxide, composite metal hydroxides, zinc oxide, zinc stannate, zinc borate , Compounds containing metal elements such as iron oxide, molybdenum oxide, zinc molybdate, dicyclopentadienyl iron, and the like. These may be used alone or in combination of two or more. .

  Of these, phosphate ester, phosphine oxide and cyclophosphazene are preferable from the viewpoint of fluidity. The phosphate ester is not particularly limited as long as it is an ester compound of phosphoric acid and an alcohol compound or a phenol compound. For example, trimethyl phosphate, triethyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl 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 (XXXVIII) is preferable.

  Examples of the phosphoric acid ester of the above formula (XXXVIII) include phosphoric acid esters represented by the following structural formulas (XXXIX) to (XXXIII).

  It is preferable that the addition amount of these phosphate ester exists in the range of 0.2 to 3.0 weight% in the quantity of a phosphorus atom in all the other compounding components except a filler. When it is less than 0.2% by weight, the flame retardancy tends to be low. If it exceeds 3.0% by weight, the formability and moisture resistance may be deteriorated, and these phosphate esters may ooze out during molding, thereby impairing the appearance.

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

（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 above general formula (XXXXIV), 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.

  The amount of phosphine oxide is required to be 0.01 to 0.2% by mass of phosphorus atoms in the epoxy resin composition for sealing. Preferably it is 0.02-0.1 mass%, More preferably, it is 0.03-0.08 mass%. If it is less than 0.01% by mass, the flame retardancy is lowered, and if it exceeds 0.2% by mass, the moldability and moisture resistance are lowered.

  Cyclophosphazenes include cyclic phosphazene compounds containing the following formula (XXXXV) and / or the following formula (XXXXVI) as repeating units in the main chain skeleton, or the following formulas (XXXVII) and / or different substitution positions for phosphorus atoms in the phosphazene ring. Alternatively, a compound containing the following formula (XXXXVIII) as a repeating unit can be given.

Here, m in Formula (XXXXV) and Formula (XXXXVII) 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 (XXXXVI) and Formula (XXXXVIII) 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 above formulas (XXXXV) to (XXXXVIII), 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.

  Moreover, although there is no restriction | limiting in particular as a C1-C4 alkylene group or arylene group shown by A in said Formula (XXXXV)-Formula (XXXXVIII), For example, a methylene group, ethylene group, propylene group, 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 (XXXXV) to (XXXXVIII), a copolymer of the above formula (XXXXV) and the above formula (XXXXVI), or the above formula (XXXXVII) and the above formula (XXXXVIII). 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 (XXXXIX), a copolymer of the following formula (XXXX), and the like.

（ここで、式（ＸＸＸＸＩＸ）中のｍは、０〜９の整数で、Ｒ^１〜Ｒ^４はそれぞれ独立に水素又は水酸基を示す。）

(Here, m in the formula (XXXIX) is an integer of 0 to 9, and R ^{1 to} R ⁴ each independently represent hydrogen or a hydroxyl group.)

Here, m and n in the formula (XXXX) 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 ⁸ are each independently hydrogen or a hydroxyl group. Chosen from. In addition, the cyclic phosphazene compound represented by the above formula (XXXX) includes the following m repeating units (a) and n repeating units (b) alternately, in blocks, or randomly. Any of these may be used, but those randomly included are preferred.

Among them, a polymer having m of 3 to 6 as a main component in the above formula (XXXIX), or R ^{5 to} R ⁸ are all hydrogen or one is a hydroxyl group in the above formula (XXXX), and m / n is 1 The main component is a copolymer of / 2 to 1/3 and m + n of 3 to 6. As a commercially available phosphazene compound, SPE-100 (trade name, manufactured by Otsuka Chemical) is available.

  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 (XXXXXXI).

（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 (XXXXXXI) is 0, that is, a compound represented by the following composition formula (XXXXII) 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、ｍ、ｎ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, m, n, and l represent positive numbers.)

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

  The molar ratio of p, q, and r in the composition formula (XXXXXXI) is not particularly limited as long as the effects of the present invention can be obtained, but r = 0, and the molar ratio p / q of p and q is 99/1 to Preferably it is 50/50. That is, the molar ratio m / n of m and n in the composition formula (XXXXII) is preferably 99/1 to 50/50.

Examples of commercially available products include water in which M ¹ in the above composition formula (XXXXII) is magnesium, M ² is zinc, m is 7, n is 3, 10 is 1, 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”, February 15, 1987) (Reduced plate 30th printing).

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

  Although there is no restriction | limiting in particular in the compounding quantity of a composite metal hydroxide, 0.5-20 mass% is preferable in an epoxy resin composition for sealing, 0.7-15 mass% is more preferable, 1.4-12 More preferred is mass%. If it is less than 0.5% by mass, the flame retardancy tends to be insufficient, and if it exceeds 20% by mass, the fluidity and reflow resistance tend to be lowered.

  As the compound having a triazine ring, a compound obtained by co-condensation polymerization of a compound having a phenolic hydroxyl group, a triazine derivative and a compound having an aldehyde group is preferable from the viewpoint of flame retardancy and adhesiveness to a copper frame. Examples of the compound having a phenolic hydroxyl group include alkylphenols such as phenol, cresol, xylenol, ethylphenol, butylphenol, nonylphenol, 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 100 parts by weight of the compound having a phenolic hydroxyl group is preferably 1 to 30 parts by weight, and more preferably 5 to 20 parts by weight. If it is less than 1 part by weight, the flame retardancy is poor. The compounding amount (molar ratio) of the compound having an aldehyde group with respect to the triazine derivative is not particularly limited.

  The reaction temperature at the time of synthesizing a copolycondensation product of a compound having a phenolic hydroxyl group, a triazine derivative and a compound having an aldehyde group is not particularly limited, but is preferably 60 to 120 ° C. Moreover, 3-9 are preferable and, as for pH of reaction, 4-8 are more preferable. If the pH is less than 3, the resin 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% or less. If it exceeds 3%, the moldability tends to decrease.

  Moreover, it is preferable that the softening point of the obtained copolycondensation product is 40-150 degreeC. When it is less than 40 ° C., it is easy to block, and when it exceeds 150 ° C., the kneadability of the composition is lowered. Examples of co-condensation 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 (XXXXIII) to (XXXXVIII).

  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 250 ° 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. 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 weight of the polycondensate) 3) The triazine derivative is preferably 3 to 50 parts by weight and more preferably 4 to 30 parts by weight with respect to 100 parts by weight. Moreover, it is preferable to set it as 5-100 weight part with respect to 100 weight part of polycondensates (phenol resin), and, as for the compound which has an aldehyde group, it is more preferable to set it as 6-50 weight part. By setting the triazine derivative (b) 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 (c) which has an aldehyde group, formaldehyde, formalin, paraformaldehyde, etc. are mentioned, for example.

In the present invention, a silicon-containing polymer may be contained. 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 (c) 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. In this case, examples of the alkoxy group 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価の炭化水素基から選ばれ、ケイ素含有重合物中の全Ｒ^１はすべてが同一でも異なっていてもよい。）

(Here, R ¹ is selected from substituted or unsubstituted monovalent hydrocarbon groups having 1 to 12 carbon atoms with respect to all R ¹ in the silicon-containing polymer, and all R ¹ in the silicon-containing polymer is All may 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. And a methyl group or a phenyl group is preferable.

  The softening point of such a silicon-containing polymer is preferably set to 40 ° C to 120 ° C, and more preferably set to 50 ° C to 100 ° C. When the temperature is lower than 40 ° C., the mechanical strength of the cured epoxy resin composition obtained tends to decrease. When the temperature is higher than 120 ° C., the dispersibility of the silicon-containing polymer in the epoxy resin composition for sealing is low. It tends to decrease. As a method for adjusting the softening point of the silicon-containing polymer, the molecular weight of the silicon-containing polymer, the constituent bond units (for example, (c) to (e) content ratio, etc.), and the type of organic group bonded to the silicon atom are set. In 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 weight to 1.5% by weight, and more preferably 0.3% by weight to 1.3% by weight, based on the entire epoxy resin composition for sealing. When the amount is less than 0.2% by weight, the effect of addition of the (A) silicon-containing polymer is not observed, and when the amount is more than 1.5% by weight, the hot hardness of the resulting epoxy resin composition for sealing tends to decrease. .

  In the present invention, if necessary, the compound (G) represented by the following composition formula (XXXXIX) and / or the compound (H) represented by the following composition formula (XXXXXXX) may be converted into moisture resistance of a semiconductor element such as an IC. It can be contained from the viewpoint of improving the high temperature storage characteristics.

（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 (XXXXXXIX) is available as a commercial item as Kyowa Chemical Industry Co., Ltd. brand name DHT-4A. Moreover, the compound of the said formula (XXXXXXX) is available as a brand name IXE500 by Toa Gosei Co., Ltd. as a commercial item. 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 sealing epoxy resin composition of the present invention is preferably used by previously melt-mixing (A) an epoxy resin and (B) a curing agent from the viewpoint of flame retardancy. The method of melt mixing is not particularly limited, but it is heated to a temperature at which both or one of them is melted, stirred and mixed until uniform. At this time, it is preferable to set the optimum conditions by confirming the reactivity using GPC (gel permeation chromatography), FT-IR or the like so as not to gel. (A) When using the compound of the said general formula (I) as an epoxy resin, (B) When using the compound of the said general formula (II) as a hardening | curing agent, Preferably it is 80-120 degreeC, More preferably, it is 90-120 degreeC. And stirring and mixing for 10 to 60 minutes, particularly preferably 20 to 40 minutes.

  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 into the dimension and weight 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 limited to these Examples.
(Examples 1-20, Comparative Examples 1-10)
As an epoxy resin, a compound represented by general formula (I) having an epoxy equivalent of 251 and a softening point of 60 ° C., R ¹ is a methyl group, and R ² is a methoxy group (trade name EXA manufactured by Dainippon Ink & Chemicals, Inc. -7320) (epoxy resin 1), a compound represented by the general formula (I) having an epoxy equivalent of 264, a softening point of 61 ° C, R ¹ is a methyl group, and R ² is a methoxy group (Dainippon Ink and Chemicals, Inc.) Company name EXA-7321) (epoxy resin 2), compound represented by general formula (I) having an epoxy equivalent of 243 and a softening point of 54 ° C., wherein R ¹ is a hydrogen atom and R ² is a methoxy group (large Nippon Ink Chemical Co., Ltd. trade name EXA-7325) (epoxy resin 3), epoxy equivalent 190, softening point 65 ° C. o-cresol novolac type epoxy resin (product of Toto Kasei Co., Ltd.) YDCN-500) (epoxy resin 4), epoxy equivalent 196, melting point 106 ° C. biphenyl type epoxy resin (trade name Epicoat YX-4000H manufactured by Japan Epoxy Resin Co., Ltd.) (epoxy resin 5), epoxy equivalent 245, melting point 110 ° C. Sulfur atom-containing epoxy resin (trade name YSLV-120TE manufactured by Toto Kasei Co., Ltd.) (epoxy resin 6) and 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 7), phenol aralkyl resin having a softening point of 70 ° C. and a hydroxyl group equivalent of 175 as a curing agent (trade name Mirex XLC-3L, manufactured by Mitsui Chemicals, Inc.) (hardening agent 1), phenol having a softening point of 80 ° C. and a hydroxyl group equivalent of 106 Novolac resin (trade name H-1 manufactured by Meiwa Kasei Co., Ltd.) Agent 2) and a biphenylene type phenol resin having a hydroxyl equivalent of 199 and a softening point of 67 ° C. (Maywa Kasei Co., Ltd. trade name MEH-7851) (curing agent 3), triphenylphosphine (curing accelerator 1) as a curing accelerator, tri Addition product of phenylphosphine and 1,4-benzoquinone (curing accelerator 2), γ-glycidoxypropyltrimethoxysilane (epoxysilane) as coupling agent, silane coupling agent containing secondary amino group (γ- Anilinopropyltrimethoxysilane (anilinosilane), aromatic condensed phosphate ester (trade name PX-200, manufactured by Daihachi Chemical Co., Ltd.), triphenylphosphine oxide, cyclophosphazene (trade name SPE-100, manufactured by Otsuka Chemical Co., Ltd.) ), Magnesium hydroxide / zinc hydroxide solid solution composite metal hydroxide (Tatejo) Gaku Kogyo Co., Ltd. trade name Echomag Z-10), antimony trioxide and epoxy equivalent 397, softening point 69 ° C., bromine content 49% by mass bisphenol A brominated epoxy resin (YDB-400 manufactured by Toto Kasei Co., Ltd.), Spherical fused silica having an average particle size of 14.5 μm and a specific surface area of 2.8 m ² / g as an inorganic filler, and carnauba wax (manufactured by Clariant) and carbon black (trade name MA-100, manufactured by Mitsubishi Chemical Corporation) as other additives. ) Were mixed in parts by mass shown in Tables 1 to 3, 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 20 and Comparative Examples 1 to 10.

The characteristics of the produced epoxy resin compositions for sealing of Examples 1 to 20 and Comparative Examples 1 to 10 were determined by the following tests. The results are shown in Tables 4-6.
(1) Spiral flow Using a spiral flow measurement mold in accordance with EMMI-1-66, 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) Reflow resistance An 80-pin flat package (QFP) (lead frame material: copper alloy, lead tip silver-plated product) with an external dimension of 20 mm x 14 mm x 2 mm mounted with an 8 mm x 10 mm x 0.4 mm silicon chip. Then, molding and post-curing using the epoxy resin composition for sealing under the conditions of (3) above, humidifying under conditions of 85 ° C. and 85% RH, and conditions of 240 ° C. and 10 seconds every predetermined time Then, reflow treatment was performed, 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) Moisture resistance External dimensions of 20 mm x 14 mm x 2.7 mm mounted with a 6 mm x 6 mm x 0.4 mm test silicon chip on which an aluminum wiring with a line width of 10 µm and a thickness of 1 µm is mounted on a 5 µm thick oxide film An 80-pin flat package (QFP) is molded and post-cured using the epoxy resin composition for sealing under the above conditions (3), pre-treated, humidified, and aluminum is added every predetermined time. The disconnection failure due to wiring corrosion was examined, and the number of defective packages relative to the number of test packages (10) was evaluated.

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

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

  Comparative Examples 1 to 3 in which the compound represented by the general formula (I) of the present invention is not blended are inferior in flame retardancy and do not achieve UL-94 V-0. Moreover, comparative examples 7-9 are inferior in moisture resistance among the comparative examples 7-10 which mix | blended the compound shown by the said general formula (I), and mix | blended various flame retardants. Further, Comparative Example 10 is inferior in fluidity. Further, although Comparative Examples 4 and 5 achieved V-0, the curability (hardness during heating) was inferior, and Comparative Example 6 was inferior in high-temperature storage characteristics.

On the other hand, Examples 1 to 20 including the compound represented by the general formula (I) all achieved UL-94 V-0, have good flame retardancy, and good moldability. Furthermore, it is excellent in reflow resistance, and is excellent in reliability such as moisture resistance and high temperature storage.

Claims (18)

An epoxy resin composition for sealing containing (A) an epoxy resin, (B) a curing agent, and (A) an epoxy resin containing (C) a compound represented by the following general formula (I).

^{(R 1} in the general formula (I) is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, selected from alkoxy groups having 1 to 6 carbon atoms, ^{R 2} is selected from alkoxy groups having a carbon number of 1-6. n represents an integer of 1 to 20.) Compound represented by formula (I) (C) according to claim 1 encapsulated epoxy resin composition according R ² is a methoxy group in. The epoxy resin composition for sealing according to claim 1 or 2 , wherein R ¹ in the compound (C) represented by the general formula (I) is a methyl group. The epoxy resin composition for sealing according to any one of claims 1 to 3 , wherein the epoxy equivalent of the compound (C) represented by the general formula (I) is 260 or more. (C) The epoxy resin composition for sealing according to any one of claims 1 to 4, wherein the compound represented by the general formula (I) is contained in 40 to 100% by mass in the (A) epoxy resin. (C) The epoxy resin composition for sealing according to any one of claims 1 to 4, wherein the compound represented by the general formula (I) is contained in 60 to 100% by mass in the (A) epoxy resin. (A) Epoxy resin is biphenyl type epoxy resin, bisphenol F type epoxy resin, stilbene type epoxy resin, sulfur atom-containing epoxy resin, novolac type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, triphenylmethane type The epoxy resin composition for sealing according to any one of claims 1 to 6 , comprising at least one of an epoxy resin, a biphenylene type epoxy resin and a naphthol / aralkyl type epoxy resin. (B) curing agent is a biphenyl type phenol resin, aralkyl type phenol resins, dicyclopentadiene type phenol resin, according to claim 1 to 7, wherein any one that contains at least one triphenylmethane type phenol resin and novolak phenol resin An epoxy resin composition for sealing. The epoxy resin composition for sealing according to any one of claims 1 to 8, further comprising (D) a curing accelerator. (D) The epoxy resin composition for sealing according to claim 9 , wherein the curing accelerator is triphenylphosphine. The epoxy resin composition for sealing according to claim 9, wherein (D) the curing accelerator is an adduct of a third phosphine compound and a quinone compound. Further (E) containing an inorganic filler according to claim 1 to 11 for sealing epoxy resin composition according to any one. (E) Content of an inorganic filler is 60-95 mass%, The epoxy resin composition for sealing of Claim 12 characterized by the above-mentioned. (E) Content of an inorganic filler is 70-90 mass%, The epoxy resin composition for sealing of Claim 12 characterized by the above-mentioned. Further (F) according to claim 1-14 encapsulated epoxy resin composition according to any one containing a coupling agent. The epoxy resin composition for sealing according to claim 15, wherein the coupling agent contains a silane coupling agent having a secondary amino group. The epoxy resin composition for sealing according to claim 16, wherein the silane coupling agent having a secondary amino group contains a compound represented by the following general formula (II).

(Where R ¹ is selected from a hydrogen atom, an alkyl group having 1 to 6 carbon atoms and an alkoxy group having 1 to ² carbon atoms, R ² is selected from an alkyl group having 1 to 6 carbon atoms and a phenyl group; ³ represents a methyl group or an ethyl group, n represents an integer of 1 to 6, and m represents an integer of 1 to ^3. ) Electronic component device comprising a sealed device with encapsulated epoxy resin composition according to any one of claims 1 to 17.