JP2009249424A - Epoxy resin molding material for sealing and electronic component device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an epoxy resin molding material for sealing having excellent solder reflow resistance and securing flame retardancy and to provide an electronic component device provided with an element sealed by the same. <P>SOLUTION: The epoxy resin molding material for sealing includes (A) an epoxy resin, (B) a curing agent, (C) a silane compound, (D) a curing promotor and (E) an inorganic filler, wherein (C) the silane compound includes a silane compound (C1) represented by a specified chemical formula and a silane compound (C2) represented by a specified chemical formula and (C1) and (C2) are blended at a ratio by weight of (C2)/(C1)=0.4 to 4.7. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an epoxy resin molding material 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.

  In addition, as electronic devices have become smaller, lighter, and higher in performance, the mounting density has been increased, and electronic component devices have come to be made surface mount packages instead of conventional pin insertion types. . When a semiconductor device is attached to a wiring board, the conventional pin insertion type package is soldered from the back side of the wiring board after the pins are inserted into the wiring board, so that the package is not directly exposed to high temperatures. However, in the surface mount type package, the entire semiconductor device is processed by a solder bath, a reflow device or the like, so that it is directly exposed to soldering temperature. As a result, when the package absorbs moisture, the moisture absorption moisture rapidly expands during soldering, causing peeling of the adhesive interface and package cracks, which reduces the reliability of the package during mounting.

  In order to solve the above problems, for example, a method of adding an amine-based silane compound as a silane compound has been proposed as a method for improving the adhesion between the sealing epoxy resin molding material and the lead frame and improving the reflow resistance. (See Patent Document 9 and Patent Document 10). However, this method is not effective for improving the solder reflow resistance and adhesiveness, and also has a problem of causing a decrease in fluidity. In addition, if the fluidity of the epoxy resin molding material for sealing is low, new problems such as the occurrence of gold wire flow, voids, pinholes, etc. will occur during molding (see Non-Patent Document 2).

  Therefore, to solve this problem, an epoxy resin molding material for sealing excellent in fluidity and solder reflow resistance without reducing curability, and an electronic component device including an element sealed thereby are provided. A method has been proposed (see Patent Document 11).

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 JP-A-11-147939 JP 2001-213939 A JP 2005-247890 A Hiroshi Kato, Functional Materials, 11 (6), 34 (1991) Technical Information Association, Inc. “High Reliability of Semiconductor Encapsulation Resin” Technical Information Association, January 31, 1990, pages 172-176

  The flame retardant of the epoxy resin molding material for sealing was the problem of reduced moisture resistance when using red phosphorus as the epoxy resin molding material for sealing from the viewpoint of environmental friendliness, using phosphoric ester compounds and phosphazene compounds. In the case of plasticity, there is a problem of decrease in moldability and moisture resistance, in the case of using metal hydroxide, there is a problem of decrease in fluidity and mold releasability, in the case of using metal oxide, or a filler. When the ratio is increased, there is a problem of decrease in 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. On the other hand, when the material design is advantageous for the thermal shock test due to the effect of reducing the stress by lowering the proportion of the filler to improve the fluidity and reduce the elastic modulus, A decrease in reliability and a significant decrease in flame retardance are manifested due to an increase in the number of flame retardants.

  The present invention has been made in view of such circumstances, and is an epoxy resin molding for sealing that is non-halogen and non-antimony and has excellent solder reflow resistance and ensures flame resistance even when the proportion of the filler is low. An object of the present invention is to provide an electronic component device including a material and an element sealed by the material.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors can achieve the above object by combining a sealing epoxy resin molding material containing a specific epoxy resin and a silane coupling agent. As a result, the present invention has been completed.

The present application relates to the following inventions.
1. It contains (A) an epoxy resin, (B) a curing agent, (C) a silane compound, (D) a curing accelerator, (E) an inorganic filler, and (C) the silane compound is represented by the following general formula (I). A silane compound (C1) and a silane compound (C2) represented by the following general formula (II), wherein (C1) and (C2) are (II) / (I) = 0.4 to 4.7 An epoxy resin molding material for sealing blended in a weight ratio.

（ここで、Ｒ^１は水素原子又は炭素数１〜６の炭化水素基を示し、Ｒ^２は水素原子又は炭素数１〜６の炭化水素基を示し、ｍは１〜３の整数を示す。）

(Here, R ¹ represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, R ² represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and m represents an integer of 1 to 3). )

（ここで、Ｒ^１、はグリシジルエーテル基、メルカプト基、アミノ基、アニリノ基、イソシアネート基、アクリロキシ基及びメタクリロキシ基を示し、Ｒ^２は炭素数１〜６の炭化水素基を示し、Ｒ^３、Ｒ^４は炭素数１〜６の炭化水素基を示しｎは１〜３の整数を示す。）

(Here, R ¹ represents a glycidyl ether group, a mercapto group, an amino group, an anilino group, an isocyanate group, an acryloxy group, and a methacryloxy group, R ² represents a hydrocarbon group having 1 to 6 carbon atoms, R ³ , R ⁴ represents a hydrocarbon group having 1 to 6 carbon atoms, and n represents an integer of 1 to 3).

2. The sealing epoxy resin molding material according to item 1, further comprising (A) an epoxy resin (A1) a compound represented by the following general formula (III) and (A2) a compound represented by the following general formula (IV).

（一般式（ＩＩＩ）中のＲ^５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、互いに同一であっても異なっていてもよい。Ｒ^５のｍは０〜４の正数を示す。また、分子式内のｎは、０〜１０の整数を示す。）

(The general formula R ⁵ in (III) is selected from a hydrocarbon group of a substituted or unsubstituted monovalent C1-10 hydrogen and carbon, identical even with good .R ⁵ be different also from each other m represents a positive number from 0 to 4. Further, n in the molecular formula represents an integer from 0 to 10.)

（一般式（ＩＶ）中のＲ^６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、互いに同一であっても異なっていてもよい。ｍは０〜４の正数を示す。）

(R ⁶ in the general formula (IV) is selected from a hydrogen atom and a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and may be the same or different. M is 0. Indicates a positive number of ~ 4.)

3. Item 3. The sealing epoxy resin molding material according to item 1 or 2, wherein the proportion of the (C) silane compound is 0.06 to 0.8% by weight relative to the sealing epoxy resin molding material.
4). Item 4. The sealing epoxy resin molding material according to Item 2 or 3, wherein the compound (A1) represented by the general formula (III) and the compound (A2) represented by the general formula (IV) are mixed in advance.
5. Content ((A1) / ((A1) + (A2))) of the compound (A1) in the compound (A1) represented by the general formula (III) and the compound (A2) represented by the general formula (IV) × Item 100) is an epoxy resin molding material for sealing according to any one of Items 2 to 4, wherein 30 to 90% by mass.
6). (E) The epoxy resin molding material for sealing in any one of claim | item 1 -5 whose content of an inorganic filler is 60-95 mass%.
7). Item 7. An electronic component device comprising an element sealed with the sealing epoxy resin molding material according to any one of Items 1 to 6.

  The epoxy resin molding material for sealing according to the present invention can provide products such as electronic component devices having good flame retardance and solder reflow resistance, and its industrial value is great. Furthermore, since flame retardancy is maintained with low filling, it is extremely effective in designing an epoxy resin molding material with reduced flow characteristics and elastic modulus.

  The (A) epoxy resin used in the present invention preferably contains (A1) a compound represented by the following general formula (III) and (A2) a compound represented by the following general formula (IV).

（一般式（ＩＩＩ）中のＲ^５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、互いに同一であっても異なっていてもよい。Ｒ^５のｍは０〜４の正数を示す。また、分子式内のｎは、０〜１０の整数を示す。）

(The general formula R ⁵ in (III) is selected from a hydrocarbon group of a substituted or unsubstituted monovalent C1-10 hydrogen and carbon, identical even with good .R ⁵ be different also from each other m represents a positive number from 0 to 4. Further, n in the molecular formula represents an integer from 0 to 10.)

（一般式（ＩＶ）中のＲ^６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、互いに同一であっても異なっていてもよい。ｍは０〜４の正数を示す。）

(R ⁶ in the general formula (IV) is selected from a hydrogen atom and a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and may be the same or different. M is 0. Indicates a positive number of ~ 4.)

  The compound (A1) represented by the general formula (III) and the compound (A2) represented by the general formula (IV) are preferably mixed in advance. In particular, since the compound (A2) represented by the general formula (IV) is difficult to produce by itself, a bisphenol F-type compound (raw material of the compound (A1) represented by the general formula (III)) and a biphenol-type compound (general formula ( It is preferable to produce an epoxy resin mixture by reacting with the epichlorohydrin in a state in which the compound (A2) represented by IV) is mixed in advance.

  Content ((A1) / ((A1) + (A2))) of the compound (A1) in the compound (A1) represented by the general formula (III) and the compound (A2) represented by the general formula (IV) × 100) is preferably 30 to 90% by mass, and more preferably 50 to 80% by mass. When it is 30% by mass or more, the fluidity is good, and when it is 90% by mass or less, the flame retardancy is good, and it becomes easy to synthesize as crystals at the time of production.

  The compound (A1) represented by the general formula (III) and the compound (A2) represented by the general formula (IV) are preferably 50 to 100% by mass, and 80 to 100% by mass based on the total amount of the (A) epoxy resin. It is more preferable that When it is 50% by weight or more, flame retardancy, fluidity and reflow resistance are improved.

Assuming that the compound (A1) represented by the general formula (III) is 70% by mass, the compound (A2) represented by the general formula (IV) is 30% by mass and all R ₁ and R ₂ are hydrogen atoms, YL-7399 manufactured by Epoxy Resin Co., Ltd. is available.

  As the (A) epoxy resin used in the present invention, a conventionally known epoxy resin can be used in combination. Usable epoxy resins include, for example, phenol novolac type epoxy resins, orthocresol novolac type epoxy resins, epoxy resins having a triphenylmethane skeleton, phenol, cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol F And / or naphthols such as α-naphthol, β-naphthol and dihydroxynaphthalene and compounds having an aldehyde group such as formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde and salicylaldehyde in an acidic catalyst. Epoxidized novolac resin obtained by the process. Diglycidyl ethers such as bisphenol A, bisphenol F, bisphenol S, alkyl-substituted or unsubstituted biphenol. Stilbene type epoxy resin, hydroquinone type epoxy resin, glycidyl ester type epoxy resin obtained by reaction of polybasic acid such as phthalic acid and dimer acid and epichlorohydrin, diaminodiphenylmethane, isocyanuric acid etc. glycidylamine obtained by reaction of 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, is like a sulfur atom-containing epoxy resins may be used in combination or in combination of two or more with these alone.

  Among them, biphenyl type epoxy resin, bisphenol F type epoxy resin, stilbene type epoxy resin and sulfur atom-containing epoxy resin are preferable from the viewpoint of fluidity and reflow resistance, and novolac type epoxy resin is preferable from the viewpoint of curability, From the viewpoint of low hygroscopicity, dicyclopentadiene type epoxy resin is preferable. From the viewpoint of heat resistance and low warpage, naphthalene type epoxy resin and triphenylmethane type epoxy resin are preferable. From the viewpoint of flame retardancy, biphenylene type epoxy resin is preferable. Resins and naphthol / aralkyl epoxy resins are preferred. It is preferable to contain at least one of these epoxy resins.

  Examples of the biphenyl type epoxy resin include an epoxy resin represented by the following general formula (4). Examples of the bisphenol F type epoxy resin include an epoxy resin represented by the following general formula (V), and a stilbene type epoxy resin. Examples of the resin include an epoxy resin represented by the following general formula (VI), and examples of the sulfur atom-containing epoxy resin include an epoxy resin represented by the following general formula (VII).

（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 (4) 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.

As the bisphenol F type epoxy resin represented by the general formula (V), 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 (VI) 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 (VII), 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 (VIII).

（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 (VIII) can be easily obtained by reacting a novolak type phenol resin with epichlorohydrin. Among them, R in the general formula (VIII) is an alkyl group having 1 to 10 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, and an isobutyl group, a methoxy group, an ethoxy group, and a propoxy group. C1-C10 alkoxyl groups, such as a butoxy group, are preferable, and a hydrogen atom or a methyl group is more preferable. n is preferably an integer of 0 to 3. Among the novolak epoxy resins represented by the general formula (VIII), orthocresol novolac epoxy resins are preferable. 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 (IX).

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

（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 (X) includes a random copolymer containing 1 structural unit and m structural 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 (XII), and examples of the naphthol / aralkyl type epoxy resin include an epoxy resin represented by the following general formula (XIII).

（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 (XIV) can also be used as (A) epoxy resin.

（一般式（ＸＩＶ）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 (XIV) 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 (XIV) include epoxy resins represented by the following general formulas (XV) to (XXXIII).

  Especially, the epoxy resin shown by the said general formula (XV) is preferable from a viewpoint of a flame retardance and a moldability. As such a compound, YL-7172 (trade name of Japan Epoxy Resin Co., Ltd.) and the like are available.

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

（一般式（ＸＸＸＩＶ）中のＲ^１は水素原子、水酸基、炭素数１〜８のアルキル基、炭素数１〜６のアルコキシ基から選ばれ、全てが同一でも異なっていてもよい。Ｒ^２、Ｒ^３は水素原子、炭素数１〜６のアルキル基から選ばれ、全てが同一でも異なっていてもよい。
ｎは１〜２０の整数を示し、ｍは１〜３の整数を示す。）

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

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

（一般式（ａ）中のＲ^２、Ｒ^３は水素原子、炭素数１〜６のアルキル基から選ばれ、全てが同一でも異なっていてもよい。ｍは１〜３の整数を示す。）

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

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

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

  A conventionally well-known hardening | curing agent (B) can be used for this invention. The curing agent that can be used is not particularly limited as it is generally used for epoxy resin molding materials for sealing. For example, phenol, cresol, resorcin, catechol, bisphenol A, bisphenol F, phenylphenol, aminophenol Novolaks obtained by condensation or cocondensation of phenols such as naphthols such as α-naphthol, β-naphthol, and dihydroxynaphthalene with compounds having an aldehyde group such as formaldehyde, benzaldehyde, salicylaldehyde, etc. in the presence of an acidic catalyst Type phenolic resin, phenol / aralkyl resin synthesized from phenol and / or naphthol and dimethoxyparaxylene or bis (methoxymethyl) biphenyl, biphenylene type phenol aralkyl resin, naphtho Dicyclopentadiene such as dicyclopentadiene-type phenol novolac resin and dicyclopentadiene-type naphthol novolak resin synthesized by copolymerization from aralkyl-type phenol resins such as aralkyl resins, phenols and / or naphthols and dicyclopentadiene 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 resin obtained by copolymerizing two or more of these, etc. Is 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 (XXXV) 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 (XXXV) 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 (XXXVI).

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

（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.

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

（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.

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

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

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

R ^{1 to} R ⁹ in the above formula (XXXIX) 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 (XXXIX) include compounds in which R ^{1 to} R ⁹ are all hydrogen atoms, and in particular, from the viewpoint of melt viscosity, n is a condensation of 1 or more. A mixture of condensates containing 50% by 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.

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

  In the present invention, a compound represented by the following general formula (XXXX) can also be included.

（一般式（ＸＸＸＸ）中のＲ^１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、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選ばれ、ｎは０〜１０の整数を示し、ｍは０〜１０の整数を示す。）

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

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

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

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

  The epoxy resin molding material for sealing of the present invention may contain acenaphthylene from the viewpoint of improving flame retardancy. 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 these aliphatic olefins 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 molding material for sealing of the present invention, from the viewpoint of improving the flame retardance due to the 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 molding material 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 molding material 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 molding material of the present invention, (D) a curing accelerator can be used as necessary in order to promote the reaction between (A) the epoxy resin and (B) the curing agent. (D) The curing accelerator is generally used in an epoxy resin molding material 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. Compound having intramolecular polarization, tertiary amines such as benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol and their derivatives, 2-methylimidazole, 2-phenylimidazole Phosphines such as 2-phenyl-4-methylimidazole and derivatives thereof, tributylphosphine, methyldiphenylphosphine, triphenylphosphine, tris (4-methylphenyl) phosphine, diphenylphosphine, phenylphosphine, and the like Phosphorus compounds with intramolecular polarization formed by adding a phosphine compound to a compound having a π bond, such as maleic anhydride, the above quinone compound, diazophenylmethane, and phenol resin. And tetraphenylboron salts such as nitrotetraphenylborate, triphenylphosphinetetraphenylborate, 2-ethyl-4-methylimidazoletetraphenylborate, N-methylmorpholinetetraphenylborate, and derivatives thereof. You may use it, or may use it in combination of 2 or more types.

  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) The blending amount of the curing accelerator is not particularly limited as long as the curing acceleration effect is achieved, but is preferably 0.005 to 2% by weight with respect to the sealing epoxy resin molding material. 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 the present invention, (E) an inorganic filler is blended. The inorganic filler has the effects of hygroscopicity, linear expansion coefficient reduction, thermal conductivity improvement and strength improvement, for example, fused silica, crystalline silica, alumina, zircon, calcium silicate, calcium carbonate, potassium titanate, silicon carbide, Examples thereof include powders such as silicon nitride, aluminum nitride, boron nitride, beryllia, zirconia, zircon, fosterite, steatite, spinel, mullite, and titania, or beads and glass fibers obtained by spheroidizing these. Furthermore, examples of the inorganic filler having a flame retardant effect include aluminum hydroxide, magnesium hydroxide, composite metal hydroxide, zinc borate, and zinc molybdate. Here, as the zinc borate, FB-290, FB-500 (manufactured by US Borax), FRZ-500C (manufactured by Mizusawa Chemical Co., Ltd.), etc. (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 is preferably 50% by mass or more based on the epoxy resin molding material for sealing, from the viewpoints of flame retardancy, moldability, hygroscopicity, linear expansion coefficient reduction, strength improvement and reflow resistance, 60-95 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.

  In the epoxy resin molding material for sealing of the present invention, the silane compound (C1) represented by the following general formula (I) and the following general formula (II) are used in order to enhance the adhesion between the resin component and the filler. The compounding ratio of (C1) and (C2) is a weight ratio of (II) / (I) = 0.4 to 4.7. Moreover, you may mix | blend a silane compound and a silane coupling agent other than this as needed.

（ここで、Ｒ^１は水素原子又は炭素数１〜６の炭化水素基を示し、Ｒ^２は水素原子又は炭素数１〜６の炭化水素基を示し、ｍは１〜３の整数を示す。）

(Here, R ¹ represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, R ² represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and m represents an integer of 1 to 3). )

（ここで、Ｒ^１、はグリシジルエーテル基、メルカプト基、アミノ基、アニリノ基、イソシアネート基、アクリロキシ基及びメタクリロキシ基を示し、Ｒ^２は炭素数１〜６の炭化水素基を示し、Ｒ^３、Ｒ^４は炭素数１〜６の炭化水素基を示しｎは１〜３の整数を示す。）

(Here, R ¹ represents a glycidyl ether group, a mercapto group, an amino group, an anilino group, an isocyanate group, an acryloxy group, and a methacryloxy group, R ² represents a hydrocarbon group having 1 to 6 carbon atoms, R ³ , R ⁴ represents a hydrocarbon group having 1 to 6 carbon atoms, and n represents an integer of 1 to 3).

  Furthermore, an epoxy resin molding material for sealing containing (A) an epoxy resin containing (A1) a compound represented by general formula (III) and (A2) a compound represented by general formula (IV) is preferable.

  For example, various silane compounds such as silane compounds having primary and / or secondary and / or tertiary amino groups, epoxy silane, mercapto silane, alkyl silane, ureido silane, vinyl silane, titanium compounds, aluminum chelates, aluminum / Zirconium compounds and the like. Examples of these are vinyltrichlorosilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycol. Sidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, vinyltriacetoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropyl Triethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-anilinopropyltrimethoxysilane, γ-anilinopropyltriethoxysilane, γ- (N, N-dimethyl) aminopropyltrimethoxy Silane, γ- (N, N-diethyl) aminopropyltrimethoxysilane, γ- (N, N-dibutyl) aminopropyltrimethoxysilane, γ- (N-methyl) anilinopropyltrimethoxysilane, γ- (N -Ethyl) anilinopropyltrimethoxysilane, γ- (N, N-dimethyl) aminopropyltriethoxysilane, γ- (N, N-diethyl) aminopropyltriethoxysilane, γ- (N, N-dibutyl) amino Propyltriethoxysilane, γ- (N-methyl) anilinopropyltriethoxysilane, γ- (N-ethyl) anilinopropyltriethoxysilane, γ- (N, N-dimethyl) aminopropylmethyldimethoxysilane, γ- (N, N-diethyl) aminopropylmethyldimethoxysilane, γ- (N, N-dibutyl) aminopropy Rumethyldimethoxysilane, γ- (N-methyl) anilinopropylmethyldimethoxysilane, γ- (N-ethyl) anilinopropylmethyldimethoxysilane, N- (trimethoxysilylpropyl) ethylenediamine, N- (dimethoxymethylsilylisopropyl) ) Silane coupling agents such as ethylenediamine, methyltrimethoxysilane, dimethyldimethoxysilane, methyltriethoxysilane, γ-chloropropyltrimethoxysilane, hexamethyldisilane, vinyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, isopropyl Triisostearoyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, isopropyl tri (N-aminoethyl-aminoethyl) titanate, tetraoctane Rubis (ditridecyl phosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, bis (dioctyl pyrophosphate) oxyacetate titanate, bis (dioctyl pyrophosphate) ethylene titanate, Isopropyltrioctanoyl titanate, isopropyldimethacrylisostearoyl titanate, isopropyltridodecylbenzenesulfonyl titanate, isopropylisostearoyl diacryl titanate, isopropyltri (dioctylphosphate) titanate, isopropyltricumylphenyl titanate, tetraisopropylbis (dioctylphosphite) titanate And titanate coupling agents such as A seed may be used independently or may be used in combination of 2 or more types.

  Of these, a silane coupling agent having a secondary amino group is preferred from the viewpoints of fluidity, gold wire deformation reduction, and flame retardancy. The silane coupling agent having a secondary amino group is not particularly limited as long as it is a silane compound having a secondary amino group in the molecule. For example, γ-anilinopropyltrimethoxysilane, γ-anilinopropyltriethoxysilane Γ-anilinopropylmethyldimethoxysilane, γ-anilinopropylmethyldiethoxysilane, γ-anilinopropylethyldiethoxysilane, γ-anilinopropylethyldimethoxysilane, γ-anilinomethyltrimethoxysilane, γ- Anilinomethyltriethoxysilane, γ-anilinomethylmethyldimethoxysilane, γ-anilinomethylmethyldiethoxysilane, γ-anilinomethylethyldiethoxysilane, γ-anilinomethylethyldimethoxysilane, N- (p- Methoxyphenyl) -γ-aminopropyltrimeth Sisilane, N- (p-methoxyphenyl) -γ-aminopropyltriethoxysilane, N- (p-methoxyphenyl) -γ-aminopropylmethyldimethoxysilane, N- (p-methoxyphenyl) -γ-aminopropylmethyl Diethoxysilane, N- (p-methoxyphenyl) -γ-aminopropylethyldiethoxysilane, N- (p-methoxyphenyl) -γ-aminopropylethyldimethoxysilane, γ- (N-methyl) aminopropyltrimethoxy Silane, γ- (N-ethyl) aminopropyltrimethoxysilane, γ- (N-butyl) aminopropyltrimethoxysilane, γ- (N-benzyl) aminopropyltrimethoxysilane, γ- (N-methyl) aminopropyl Triethoxysilane, γ- (N-ethyl) aminopropyltriethoxy Lan, γ- (N-butyl) aminopropyltriethoxysilane, γ- (N-benzyl) aminopropyltriethoxysilane, γ- (N-methyl) aminopropylmethyldimethoxysilane, γ- (N-ethyl) aminopropyl Methyldimethoxysilane, γ- (N-butyl) aminopropylmethyldimethoxysilane, γ- (N-benzyl) aminopropylmethyldimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, γ- ( β-aminoethyl) aminopropyltrimethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane and the like. Of these, aminosilane coupling agents represented by the following general formula (3) 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 blending amount of the coupling agent is preferably 0.037 to 4.75% by mass, more preferably 0.05 to 5% by mass with respect to the sealing epoxy resin molding material. More preferably, it is 1-2.5 mass%. If it is less than 0.037% by mass, the adhesion to the frame tends to be lowered, and if it exceeds 4.75% by mass, the moldability of the package tends to be lowered.

  In the sealing epoxy resin molding material of the present invention, conventionally known non-halogen and non-antimony flame retardants can be blended as necessary 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 (XXXXI) is preferable.

  Examples of the phosphate ester of the above formula (XXXXI) include phosphate esters represented by the following structural formulas (XXXXII) to (XXXXVI).

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

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

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

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

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

  Cyclophosphazenes include cyclic phosphazene compounds containing the following formula (XXXXVIII) and / or the following formula (XXXXIX) as repeating units in the main chain skeleton, or the following formulas (XXXX) and / or different substitution positions with respect to phosphorus atoms in the phosphazene ring. Alternatively, a compound containing the following formula (XXXXXX) as a repeating unit can be given.

Here, m in Formula (XXXVIII) and Formula (XXXIX) 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 (XXXX) and Formula (XXXXXI) 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 (XXXXVIII) to (XXXXXI), 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 groups 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 A hydroxyl 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 molding material, an aryl group is preferable, and a phenyl group or a hydroxyphenyl group is more preferable.

  Further, the alkylene group or arylene group having 1 to 4 carbon atoms represented by A in the above formulas (XXXXVIII) to (XXXXXI) is not particularly limited, but for example, a methylene group, an ethylene group, a propylene group, an isopropylene group. , Butylene group, isobutylene group, phenylene group, tolylene group, xylylene group, naphthylene group, and the like. From the viewpoint of heat resistance and moisture resistance of the epoxy resin molding material, 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 (XXXXVIII) to (XXXXXI), a copolymer of the above formula (XXXXVIII) and the above formula (XXXIX), or the above formula (XXXX) and the above formula (XXXXXXI). 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 (XXXXII) and a copolymer of the following formula (XXXXIII).

（ここで、式（ＸＸＸＸＸＩＩ）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 (XXXXII) 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 above formula (XXXXIII) 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 (XXXXIII) includes the following m repeating units (a) and n repeating units (b) alternately, in a block form, or randomly. Any of these may be used, but those randomly included are preferred.

Among them, a polymer having m of 3 to 6 as the main component in the above formula (XXXXII), or R ^{5 to} R ⁸ are all hydrogen or one of the hydroxyl groups in the above formula (XXXXIII), and m / n is 1 / The main component is preferably a copolymer having 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 using a composite metal hydroxide as a flame retardant, the composite metal hydroxide is preferably a compound represented by the following composition formula (XXXXIV).
p (M ¹ aOb) · q (M ² cOd) · r (M ³ eOf) · mH ₂ O (XXXXIV)
(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.)

Especially, the compound whose r in the said compositional formula (XXXXIV) is 0, ie, the compound shown by the following compositional formula (XXXXV), is further more preferable.
p (M ¹ aOb) · q (M ² cOd) · lH ₂ O (XXXXXXXV)
(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 above composition formulas (XXXXIV) and (XXXXV) 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 (XXXXIV) 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 (XXXXV) is preferably 99/1 to 50/50.

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

  In addition, the classification of metal elements is a long-period type periodic rate table in which the typical element is the A subgroup and the transition element is the B subgroup (Source: Kyoritsu Shuppan Co., Ltd., “Chemical Dictionary 4”, 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 with respect to the epoxy resin molding material for sealing, 0.7-15 mass% is more preferable, 1.4- 12 mass% is more preferable. If it is less than 0.5% by mass, the flame retardancy tends to be insufficient, and if it exceeds 20% by mass, the fluidity and reflow resistance tend to be lowered.

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

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

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

  The reaction temperature at the time of synthesizing a copolycondensation product of a compound having a phenolic hydroxyl group, a triazine derivative and a compound having an aldehyde group is not particularly limited, but is preferably 60 to 120 ° C. Moreover, 3-9 are preferable and, as for pH of reaction, 4-8 are more preferable. If the pH is less than 3, the resin 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., blocking is easy, and when it exceeds 150 ° C., the kneadability of the composition is lowered. Examples of copolycondensation products of the compound having a phenolic hydroxyl group, a triazine derivative and a compound having an aldehyde group include those represented by the following structural formulas (XXXXVI) to (XXXXXXXI).

  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. Generally, it is preferable that the temperature is 80 to 220 ° C., desirably 100 to 180 ° C., the pressure is 100 mmHg or less, desirably 60 mmHg or less, and the time is 0.5 to 10 hours.

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

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

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

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

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

  X in the general formula (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 molding material 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 molding material 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 molding material obtained tends to decrease. When the temperature is higher than 120 ° C., the dispersibility of the silicon-containing polymer in the sealing epoxy resin molding material 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 molding material for sealing and the fluidity of the resulting epoxy resin molding material 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 sealing epoxy resin molding material, it is preferable to use organoalkoxysilane and / or siloxane as a raw material. In this case, it is preferable to add an acid, a base, or an organometallic compound as a catalyst for promoting the reaction.

  (A) The organoalkoxysilane and / or siloxane used as the 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, more preferably 0.3% by weight to 1.3% by weight, based on the entire epoxy resin molding material 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 molding material for sealing tends to decrease. .

Further, in the present invention, the compound represented by the following composition formula (XXXXXXXII) and / or the compound represented by the following composition formula (XXXXXXXIII) is improved as needed in the moisture resistance and high-temperature storage characteristics of a semiconductor element such as an IC. It can be contained from the viewpoint.
Mg _1-X Al _X (OH) ₂ (CO ₃ ) _{x / 2} · mH ₂ O (XXXXXXXII)
(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 (XXXXXXXII) is available as Kyowa Chemical Industry Co., Ltd. brand name DHT-4A as a commercial item. Moreover, the compound of the said formula (XXXXXXXIII) is available as a commercial item as Toa Gosei Co., Ltd. brand name IXE500. Further, other anion exchangers can be added as necessary. The anion exchanger is not particularly limited, and conventionally known anion exchangers can be used. Examples thereof include hydrated oxides of elements selected from magnesium, aluminum, titanium, zirconium, antimony, and the like. Alternatively, two or more kinds can be used in combination.

  Furthermore, the epoxy resin molding material for sealing of the present invention includes, 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 molding material 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, and (B) the compound of the said general formula (II) as a hardening | curing agent, it is 80-120 degreeC normally, Preferably it is 10 to 90-120 degreeC. It is preferable to stir and mix for 60 minutes, more preferably 20 to 40 minutes.

  The epoxy resin molding material for sealing of the present invention can be prepared by any method as long as various raw materials can be uniformly dispersed and mixed. However, 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 of sealing an electronic component device such as a semiconductor device using the epoxy resin molding material for sealing of the present invention as a sealing material, a low-pressure transfer molding method is the most common, but an 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 an epoxy resin molding material 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, a resistor, or a coil is mounted on the mounting substrate, and necessary portions are sealed with the sealing epoxy resin molding material 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 molding material 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), T FP (Thin Quad Flat Package) or other resin-encapsulated IC, TCP (Tape Carrier Package) in which a semiconductor chip lead-bonded to a tape carrier is encapsulated with the sealing epoxy resin molding material of the present invention, a wiring board or glass 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 molding material of the present invention. Active devices such as semiconductor chips, transistors, diodes, thyristors and / or capacitors connected to semiconductor devices mounted on bare chips such as semiconductor chips, wiring boards and wiring formed on glass using wire bonding, flip chip bonding, solder, etc. A semiconductor chip is mounted on an interposer substrate on which a hybrid IC in which passive elements such as resistors and coils are encapsulated with the sealing epoxy resin molding material of the present invention and terminals for MCM (Multi Chip Module) motherboard connection are formed. After connecting the semiconductor chip and the wiring formed on the interposer substrate by bump or wire bonding, the semiconductor chip mounting side is sealed with the sealing epoxy resin molding material of the present invention, BGA (Ball Grid Array), CSP (Chip) Size Package) and MCP (Multi Chip Package). In addition, these semiconductor devices are epoxy resin molding materials for sealing two or more elements at a time, even in a stacked type package in which two or more elements are mounted on a mounting substrate. 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 1-7, Comparative Examples 1-9
As an epoxy resin, the component (A1) of the general formula (III) having an epoxy equivalent of 261 and the component (A2) of the following general formula (IV) are contained as (III) / ((III) + (IV) × 100 = 70) Epoxy resin (YL-7399 manufactured by Japan Epoxy Resin Co., Ltd.) (epoxy resin 1), biphenyl type epoxy resin having an epoxy equivalent of 196 and a melting point of 106 ° C. (trade name Epicoat YX-4000H manufactured by Japan Epoxy Resin Co., Ltd.) (epoxy resin 2 ), Epoxy equivalent 245, melting point 110 ° C. sulfur atom-containing epoxy resin (trade name YSLV-120TE manufactured by Toto Kasei Co., Ltd.) (epoxy resin 3), epoxy equivalent 252, naphthol zylock type epoxy resin (Toto Kasei) having melting point 70 ° C. Product name ESN-175) (epoxy resin 4), a curing agent Biphenylene skeleton type phenol resin (Maywa Kasei Co., Ltd., trade name MEH-7851) (curing agent 1) having an acid group equivalent of 199 and a softening point of 89 ° C., an adduct of triphenylphosphine and 1,4-benzoquinone (curing accelerator 1 ), As a coupling agent, diphenyldimethoxysilane (KBM202SS manufactured by Shin-Etsu Chemical Co., Ltd.) (coupling agent 1), γ-glycidoxypropyltrimethoxysilane (epoxysilane), which is a component of general formula (I), (Toray Industries, Inc.) A-187) manufactured by Dow Silicone Co., Ltd. (coupling agent 2), methyltrimethoxysilane (A-163 manufactured by Toray Dow Silicone Co., Ltd.) (coupling agent 3), mercaptosilane (KBM-873 manufactured by Shin-Etsu Chemical Co., Ltd.) (Coupling agent 4), anilinosilane (KBM573 manufactured by Shin-Etsu Chemical Co., Ltd.) Example 1 to 7 and Comparative Examples 1 to 9 were prepared by blending the agent 5) in parts by mass shown in Tables 1 to 3 and roll kneading under conditions of a kneading temperature of 80 ° C. and a kneading time of 10 minutes. Hereafter, the compounding composition of Examples 1-7, Comparative Examples 1-4, and Comparative Examples 5-9 is shown to Tables 1-3.

The properties of the produced epoxy resin molding materials for sealing of Examples 1 to 7, Comparative Examples 1 to 4, and Comparative Examples 5 to 9 were determined by the following tests. The results are shown in Tables 4-6.
(1) Spiral flow Using a mold for spiral flow measurement according to EMMI-1-66, the epoxy resin molding material for sealing was molded at a mold temperature of 180 ° C., molding pressure of 6.9 MPa, and curing time. Molding was performed for 90 seconds, and the flow distance (cm) was determined.

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

(3) Water absorption rate A specimen having a diameter of 50 mm and a thickness of 3 mm in accordance with JIS K6911 test piece of (2) above is prepared, humidified under the conditions of 85 ° C./85% RH, and taken out after 168 hours to measure the weight. The water absorption was determined.

(4) Glass transition temperature (Tg) and linear expansion coefficient (α ₁ , α ₂ )
Glass transition from the inflection point of the linear expansion curve measured using a thermomechanical analyzer (TAS-100) manufactured by Rigaku Denki Co., Ltd. using a test piece having a shape of 19 mm × 3 mm × 3 mm under the condition of a heating rate of 5 ° C./min. The temperature (hereinafter abbreviated as Tg) was determined. In addition, linear expansion coefficients (hereinafter, the former is abbreviated as α ₁ and the latter as α ₂ ) were respectively determined from the slope of Tg or less and the slope of Tg or more.

(5) Bending test (elastic modulus)
Using Tensilon manufactured by A & D, a three-point support bending test according to JIS-K-6911 was performed at room temperature (25 ° C.) and 260 ° C., and the flexural modulus was obtained from the following formula. For the measurement, a test piece having dimensions of 70 mm × 10 mm × 3 mm was used.

(6) Flame retardancy Using a mold for molding a test piece having a thickness of 1/16 inch, an epoxy resin molding material for sealing is 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.

(7) Reflow resistance 80mm flat package (QFP) (lead frame material: copper alloy, lead tip silver-plated product) with outer dimensions of 20mm x 14mm x 2mm mounted with 8mm x 10mm x 0.4mm silicon chip Molded under the condition (3) above using a sealing epoxy resin molding material, post-cured, humidified under conditions of 85 ° C. and 85% RH, and 240 ° C. for 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 (10) was evaluated.

  When Examples 1 to 4 are compared, the amount of coupling agent 1 that is optimal for solder reflow resistance can be determined by the amount of coupling agent 1 added. In the case of Comparative Example 8 that does not include the coupling agent 1, the effect on the solder reflow resistance is not sufficiently exhibited, and the flame retardancy tends to decrease as seen in the UL test. On the contrary, when there is more addition amount than Example 4, it exists in the tendency for sclerosis | hardenability to worsen. Therefore, the addition amount of the coupling agent is preferably 1 to 7 parts by mass with respect to 100 parts by mass of the epoxy in the ratio by weight of the inorganic filler, and 3 to 5 parts by mass considering moldability and flame retardancy. Is more preferable.

  Moreover, when the effect was confirmed with the material containing the epoxy resin 3, the comparative example 5 which does not contain Example 5 and the epoxy resin 1 which contain both the epoxy resin 1 and the coupling agent 1, and the coupling agent 1 and Comparing Comparative Example 1 and Comparative Example 3 containing neither epoxy resin 1 nor coupling agent 1, both flame retardancy and reflow resistance are good in Example 5.

  The same tendency is also observed in the material system including the epoxy resin 4. This is a comparison between Example 6, Comparative Example 2, Comparative Example 4, and Comparative Example 6. In Example 6 in which the epoxy resin 1 and the coupling agent 1 were used in combination, both the reflow resistance and flame retardancy were good. It can be seen that these characteristics can be improved by using both the epoxy resin 1 and the coupling agent 1 together.

  Furthermore, comparing the four materials of Example 2, Example 7, Comparative Example 7 and Comparative Example 9, the latter two materials are inferior in reflow resistance to the former two materials. Further, when the former two materials are compared, Example 2 is more excellent in flame retardancy and reflow resistance than Example 7, so that in the resin system of epoxy resin 1, coupling agent 1 is used as coupling agent. It is better to use the entire amount of coupling agent 1 than to replace half by 3.

Claims (7)

It contains (A) an epoxy resin, (B) a curing agent, (C) a silane compound, (D) a curing accelerator, (E) an inorganic filler, and (C) the silane compound is represented by the following general formula (I). A silane compound (C1) and a silane compound (C2) represented by the following general formula (II), wherein (C1) and (C2) are (II) / (I) = 0.4 to 4.7 An epoxy resin molding material for sealing blended in a weight ratio.

(Here, R ¹ represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, R ² represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and m represents an integer of 1 to 3). )

(Here, R ¹ represents a glycidyl ether group, a mercapto group, an amino group, an anilino group, an isocyanate group, an acryloxy group, and a methacryloxy group, R ² represents a hydrocarbon group having 1 to 6 carbon atoms, R ³ , R ⁴ represents a hydrocarbon group having 1 to 6 carbon atoms, and n represents an integer of 1 to 3). The sealing epoxy resin molding material according to claim 1, further comprising (A) an epoxy resin comprising (A1) a compound represented by the following general formula (III) and (A2) a compound represented by the following general formula (IV). .

(The general formula R ⁵ in (III) is selected from a hydrocarbon group of a substituted or unsubstituted monovalent C1-10 hydrogen and carbon, identical even with good .R ⁵ be different also from each other m represents a positive number from 0 to 4. Further, n in the molecular formula represents an integer from 0 to 10.)

(R ⁶ in the general formula (IV) is selected from a hydrogen atom and a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and may be the same or different. M is 0. Indicates a positive number of ~ 4.)   The epoxy resin molding material for sealing according to claim 1 or 2, wherein the proportion of the (C) silane compound is 0.06 to 0.8% by weight relative to the epoxy resin molding material for sealing.   The epoxy resin molding material for sealing according to claim 2 or 3, wherein the compound (A1) represented by the general formula (III) and the compound (A2) represented by the general formula (IV) are mixed in advance.   Content ((A1) / ((A1) + (A2))) of the compound (A1) in the compound (A1) represented by the general formula (III) and the compound (A2) represented by the general formula (IV) × 100) is 30-90 mass%, The epoxy resin molding material for sealing in any one of Claims 2-4.   (E) Content of an inorganic filler is 60-95 mass%, The epoxy resin molding material for sealing in any one of Claims 1-5.   The electronic component apparatus provided with the element sealed with the epoxy resin molding material for sealing in any one of Claims 1-6.