JP2009102635A - Epoxy resin molding material for sealing, and electronic component device having element sealed with the epoxy resin molding material for sealing - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an epoxy resin molding material for sealing and an electronic component device having an element sealed with the epoxy resin molding material for sealing, maintaining excellent flame resistance and moldability such as fluidity and exhibiting excellent heat resistance to resin deterioration, member deterioration of a semiconductor insert, or the like under high temperatures. <P>SOLUTION: The epoxy resin molding material for sealing contains an amphoteric ion exchanger formed by mixing and baking (A) epoxy resin, (B) a curing agent, (C) a curing accelerator, (C) an inorganic filler and (E) yttrium oxide and zirconium phosphate. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an epoxy resin molding material for sealing, and an electronic component device including an element sealed with the epoxy resin molding material for sealing.

  Conventionally, in the field of element sealing of electronic component devices such as transistors, ICs, and LSIs, 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.

  Conventionally, electronic devices for use in the automobile field have often been required to have stricter reliability in heat resistance (temperature-resistant standing characteristics) and temperature cycle resistance compared to so-called consumer applications such as personal computers and home appliances. However, in recent years, from the viewpoint of resource saving and environmental protection, so-called hybrid vehicles, fuel cell vehicles, etc. have been actively developed. The situation where sex is required is expected. Also from the viewpoint of environmental protection, the demand for so-called non-halogenation and non-antimony conversion, such as reduction or complete elimination of halogenated epoxy resins and antimony compounds that have been used as flame retardants in sealing epoxy resin molding materials, has increased. ing. Halogenated epoxy resins and antimony compounds are also known to have an adverse effect on the high temperature storage characteristics of plastic encapsulated ICs. From this viewpoint, reduction or total elimination of halogenated epoxy resins and antimony compounds is desired.

  General techniques for increasing the heat resistance of electronic devices include techniques such as increasing the glass transition point of the package. Specifically, for example, triphenylmethane type epoxy resin and triphenylmethane are used as molding molding materials. A technique such as combining a so-called polyfunctional epoxy resin and a polyfunctional phenol resin, such as a type phenol resin, is known, but this technique often leads to an increase in impurities mainly composed of chloro ions. Although there is a report (for example, refer to Patent Document 1) that an increase in impurities such as chloro ions can be solved by using a specific ion scavenger in combination, the effect is not always sufficient.

  The sealing epoxy resin molding material composed of the above polyfunctional epoxy resin and polyfunctional phenolic resin is also relatively inferior in flame retardancy and tries to impart flame retardancy in a non-halogen / non-antimony system. In general, it is often necessary to add a large amount of flame retardant. One method for achieving flame retardancy without using a halogenated epoxy resin or an antimony compound is a method using red phosphorus (see, for example, Patent Document 2) or a method using a phosphate ester compound (for example, Patent Document 3). ), A method using a phosphazene compound (see, for example, Patent Document 4), a method using a metal hydroxide (see, for example, Patent Document 5), and a method using a metal hydroxide and a metal oxide in combination (for example, Patent Document). 6), cyclopentadienyl compounds such as ferrocene (see, for example, Patent Document 7), and methods using organometallic compounds such as acetylacetonate copper (see, for example, Patent Document 8). A method using a flame retardant, a method of increasing the proportion of the filler (see, for example, Patent Document 7), a method using a highly flame-retardant resin (for example, Patent Document) (See, for example, Patent Document 10 and Patent Document 11) and the like have been proposed, but the moldability causes a decrease in the glass transition point, respectively. However, the selection of the resin / curing agent is still limited, and satisfactory characteristics in heat resistance cannot be obtained.

  In conventional epoxy resin molding materials for sealing using halogenated epoxy resins and antimony compounds, metal nitrates with excellent adsorption ability have been used to remove halogens that corrode metal wiring. (For example, refer to Patent Document 12) In an epoxy resin molding material for non-halogenated / non-antimonized sealing, it becomes clear that the wire bonding part is corroded by nitrate ions generated after ion exchange, and rare earth as another ion exchanger. Proposals have been made to use oxides (see, for example, Patent Document 13). However, rare earth oxides sometimes deteriorate moisture resistance reliability, and it is impossible to achieve both high temperature storage resistance and moisture resistance reliability.

Japanese Patent No. 3292456 JP-A-9-227765 JP 9-235449 A JP-A-8-225714 Japanese Patent Laid-Open No. 9-241383 Japanese Patent Laid-Open No. 9-130037 JP-A-11-269349 JP 7-82343 A JP-A-11-140277 Japanese Patent Laid-Open No. 1-24503 Japanese Patent Laid-Open No. 10-338818 JP 2002-030200 A JP 2006-089717 A

  The present invention has been made in view of such circumstances, maintains good flame retardancy and moldability such as fluidity, and exhibits excellent heat resistance against resin deterioration at high temperatures and member deterioration of semiconductor inserts. An object of the present invention is to provide an epoxy resin molding material for sealing, and an electronic component device including an element sealed by the sealing epoxy resin molding material.

  As a result of intensive studies to solve the above problems, the present inventors have determined that an epoxy resin molding material for sealing containing an amphoteric ion exchanger in which yttrium oxide and zirconium phosphate are mixed and fired among ion exchangers. Has been found to be excellent in high-temperature standing resistance, and further, by using hydrotalcite in combination, moisture resistance reliability can be maintained and the above-mentioned object can be achieved, and the present invention has been completed.

The above problems are solved by the present invention described below.
(1) Contains (A) an epoxy resin, (B) a curing agent, (C) a curing accelerator, (D) an inorganic filler, and (E) an amphoteric ion exchanger in which yttrium oxide and zirconium phosphate are mixed and fired. An epoxy resin molding material for sealing.

(2) The sealing epoxy resin molding material according to (1), further comprising (F) a hydrotalcite compound represented by the general formula (1).
^{_{Mg 1-X Al X (OH}} ) 2 (A n-) X / n · mH 2 O ··· formula (1)
(However, in the general formula (1), 0 <X ≦ 0.5, m is 0 or a positive ^{number, A n-is} .n representing an n-valent anion represents a positive integer.)

(3) The sealing epoxy resin molding material according to (1) or (2), wherein the median diameter of the amphoteric ion exchanger obtained by mixing and firing (E) yttrium oxide and zirconium phosphate is 5 μm or less.

(4) (E) Any of (1) to (3) above, wherein the amphoteric ion exchanger in which yttrium oxide and zirconium phosphate are mixed and fired is contained in an amount of 0.02 to 2% by mass in the entire epoxy resin molding material. An epoxy resin molding material for sealing according to claim 1.

(5) Any of the above (2) to (4), wherein the hydrotalcite compound represented by the general formula (1) is contained in the entire epoxy resin molding material in an amount of 0.02 to 2% by mass. The epoxy resin molding material for sealing as described in 2.

(6) Content of (D) inorganic filler, (F) hydrotalcite compound represented by general formula (1), and (E) amphoteric ion exchanger in which yttrium oxide and zirconium phosphate are mixed and fired The epoxy resin molding material for sealing according to any one of the above (2) to (5), wherein the total is 60 to 95% by mass.

(7) An electronic component device including an element sealed with the sealing epoxy resin molding material according to any one of (1) to (6).

  The epoxy resin molding material for sealing according to the present invention maintains reliability such as high flame resistance, moldability, and reflow resistance while satisfying the requirements for in-vehicle use, and has high reliability such as high-temperature storage characteristics. The product can be obtained and its industrial value is great.

The sealing epoxy resin molding material of the present invention comprises (A) epoxy resin, (B) curing agent, (C) curing accelerator, (D) inorganic filler, and (E) yttrium oxide and zirconium phosphate mixed and fired. It is characterized by containing an amphoteric ion exchanger.
First, (E) an amphoteric ion exchanger in which yttrium oxide and zirconium phosphate are mixed and fired (hereinafter sometimes simply referred to as “amphoteric ion exchanger”), (F) in general formula (1) The represented hydrotalcite compound will be described.

[(E) amphoteric ion exchanger]
The (E) amphoteric ion exchanger used in the present invention in which yttrium oxide and zirconium phosphate are mixed and calcined is usually a porous zeolite having an ion trapping ability. Rare earth oxides such as yttrium oxide have a high adsorption ability as an anion exchanger, and in particular, have a high adsorption selectivity for phosphoric acid. When exposed to an environment exceeding 200 ° C for a long time, red phosphorus, phosphate ester, and phosphoric acid derived from the curing accelerator added to the epoxy resin molding material for sealing increase, but oxyacids such as phosphoric acid are Deteriorates the aluminum alloy of the gold wire bonding part at high temperature. Conventionally used hydrotalcite is not sufficient as a supplementary ability, whereas yttrium oxide, which is a rare earth oxide used in the present invention, can maintain a high ion exchange ability even in a high temperature range. Furthermore, the high temperature standing resistance property can be improved by mixing 10-30 mass% of zirconium phosphate which is a cation exchanger.
When amphoteric ion exchangers are added in large quantities, the moisture resistance reliability at low temperatures tends to decrease, and the moisture resistance reliability at low temperatures is prevented from decreasing while maintaining improvement in high temperature storage properties. It is preferably 0.02 to 2% by mass in the epoxy resin composition, more preferably 0.1 to 1.5% by mass, and further preferably 0.2 to 1.0% by mass. . As the amphoteric ion exchanger, IXE-Y (a prototype product name manufactured by Toagosei Co., Ltd.) is available as a prototype.

The amphoteric ion exchanger has a median diameter of preferably 5 μm or less, more preferably 0.1 to 5 μm, and even more preferably 0.5 to 4 μm from the viewpoint of fluidity.
Here, the median diameter is the particle diameter (cumulative average diameter) at which the cumulative curve becomes 50% when the cumulative curve is obtained with the total volume of one group of particle bodies as 100%. The median diameter can be measured using a laser diffraction scattering method.

[(F) Hydrotalcite compound represented by formula (1)]
The epoxy resin molding material for sealing of the present invention preferably further contains (F) a hydrotalcite compound represented by the following general formula (1). (F) The hydrotalcite compound represented by the following general formula (1) shows high adsorption ability at a relatively low temperature even when used alone, and has high halogen ion adsorption ability which lowers moisture resistance reliability. This contributes to improvement of moisture resistance reliability in proportion to the amount added. However, when exposed to a high temperature such as 175 ° C. to 220 ° C. for a long time, there is a tendency to increase impurity ions in the hot water extract, and the adsorptive capacity in the high temperature range is insufficient, but (E) yttrium oxide and By using together with an amphoteric ion exchanger in which zirconium phosphate is mixed and fired, improvement in moisture resistance is promoted while maintaining improvement in high-temperature storage properties without increasing impurity ions.
Moreover, since curability may fall when the addition amount of the hydrotalcite compound represented by (F) General formula (1) is increased, content is 0.02-0.02 in all the epoxy resin compositions. The content is preferably 2% by mass, more preferably 0.1 to 1.5% by mass, and still more preferably 0.2 to 1% by mass.
The hydrotalcite compound represented by the following general formula (1) may be baked at a high temperature in order to reduce adsorbed water and improve ion exchange capacity.
^{_{Mg 1-X Al X (OH}} ) 2 (A n-) X / n · mH 2 O ··· formula (1)
(However, in the general formula (1), 0 <X ≦ 0.5, m is 0 or a positive ^{number, A n-is} .n representing an n-valent anion represents a positive integer.)

In the general formula ^(1), as n-valent anion represented by ^{A n- is, OH -, F -, Cl} -, Br -, NO 3 -, CO 3 2-, SO 4 2-, Fe ( CN) ₆ ³⁻ , CH ₃ COO ⁻ , oxalate ion, salicinate ion and the like. Among them, carbonate ion is preferable from the viewpoint of easy availability.
As a hydrotalcite compound represented by the general formula (1), Kyowa Chemical Industry Co., Ltd., trade name DHT-4A and the like are available.

[(A) Epoxy resin]
The epoxy resin (A) used in the present invention is generally used for an epoxy resin molding material for sealing and is not particularly limited. For example, a phenol novolac epoxy resin, an orthocresol novolac epoxy resin, triphenyl Phenols such as phenol, cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol F and / or α-naphthol, β-naphthol, dihydroxy, including epoxy resins having a methane skeleton (triphenylmethane type epoxy resin) Novola obtained by condensation or cocondensation of naphthols such as naphthalene and compounds having an aldehyde group such as formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, and salicylaldehyde in the presence of an acidic catalyst Epoxy resin (novolac epoxy resin); diglycidyl ether such as bisphenol A, bisphenol F, bisphenol S, alkyl-substituted or unsubstituted biphenol; stilbene epoxy resin; hydroquinone epoxy resin; phthalic acid, Glycidyl ester type epoxy resin obtained by reaction of polybasic acid such as dimer acid and epichlorohydrin; Glycidylamine type epoxy resin obtained by reaction of polyamine such as diaminodiphenylmethane and isocyanuric acid and epichlorohydrin; Cocondensation of dicyclopentadiene and phenols Epoxidized resin (dicyclopentadiene type epoxy resin); epoxy resin having naphthalene ring (naphthalene type epoxy resin); phenol aralkyl resin, naphthol Epoxidized aralkyl phenol resin such as rualkyl resin; biphenylene type epoxy resin; trimethylolpropane type epoxy resin; terpene modified epoxy resin; linear aliphatic epoxy resin obtained by oxidizing olefin bond with peracid such as peracetic acid An alicyclic epoxy resin; a sulfur atom-containing epoxy resin, and the like. These may be used alone or in combination of two or more.

  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 reflow resistance, and novolak type epoxy resin is preferable from the viewpoint of curability, and low moisture absorption. From the viewpoint of the above, 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, and from the viewpoint of flame retardancy, biphenylene type epoxy resin and naphthol are preferable. -Aralkyl type 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 (V). Examples of the bisphenol F type epoxy resin include an epoxy resin represented by the following general formula (VI), and a stilbene type epoxy resin. Examples of the resin include an epoxy resin represented by the following general formula (VII), and examples of the sulfur atom-containing epoxy resin include an epoxy resin represented by the following general formula (I).

（一般式（Ｖ）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。）

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

（一般式（ＶＩ）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７〜１０のアラルキル基から選ばれ、全てが同一でも異なっていてもよい。ｎは０〜３の整数を示す。）

(In General Formula (VI), R ^{1 to} R ⁸ are hydrogen atoms, alkyl groups having 1 to 10 carbon atoms, alkoxyl groups having 1 to 10 carbon atoms, aryl groups having 6 to 10 carbon atoms, and 7 to 10 carbon atoms. And all may be the same or different. N represents an integer of 0 to 3.)

（一般式（ＶＩＩ）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。）

(In General Formula (VII), R ^{1 to} R ⁸ are selected from a hydrogen atom and a substituted or unsubstituted monovalent hydrocarbon group having 1 to 5 carbon atoms, and all may be the same or different. Represents an integer of 0 to 10.)

（一般式（Ｉ）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。）

(In General Formula (I), 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 selected from (It may be the same or different. N represents an integer of 0 to 3.)

Examples of the biphenyl type epoxy resin represented by the general formula (V) include 4,4′-bis (2,3-epoxypropoxy) biphenyl or 4,4′-bis (2,3-epoxypropoxy) -3. , 3 ', 5,5'-tetramethylbiphenyl as the main component, epichlorohydrin and 4,4'-biphenol or 4,4'-(3,3 ', 5,5'-tetramethyl) biphenol An epoxy resin obtained by reacting is used. Among these, an epoxy resin mainly composed of 4,4′-bis (2,3-epoxypropoxy) -3,3 ′, 5,5′-tetramethylbiphenyl is preferable. YX-4000 (trade name, manufactured by Japan Epoxy Resin Co., Ltd.) having n = 0 as a main component is commercially available. Examples of the bisphenol F type epoxy resin represented by the general formula (VI) include, for example, R ¹ , R ³ , R ⁶ and R ⁸ are methyl groups, and R ² , R ⁴ , R ⁵ and R ⁷ are hydrogen atoms. YSLV-80XY (trade name, manufactured by Nippon Steel Chemical Co., Ltd.) having n = 0 as a main component is commercially available.

  The stilbene type epoxy resin represented by the general formula (VII) can be obtained by reacting a stilbene phenol as a raw material with epichlorohydrin in the presence of a basic substance. Examples of the raw material stilbene phenols include 3-t-butyl-4,4′-dihydroxy-3 ′, 5,5′-trimethylstilbene, 3-t-butyl-4,4′-dihydroxy-3. ', 5', 6-trimethylstilbene, 4,4'-dihydroxy-3,3 ', 5,5'-tetramethylstilbene, 4,4'-dihydroxy-3,3'-di-t-butyl-5 , 5'-dimethylstilbene, 4,4'-dihydroxy-3,3'-di-t-butyl-6,6'-dimethylstilbene, among others, 3-t-butyl-4,4'-dihydroxy -3 ', 5,5'-trimethylstilbene and 4,4'-dihydroxy-3,3', 5,5'-tetramethylstilbene are preferred. These stilbene type phenols may be used alone or in combination of two or more.

Among the sulfur atom-containing epoxy resins represented by the general formula (I), 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. Epoxy resins are preferred, and R ² , R ³ , R ⁶ and R ⁷ are hydrogen atoms, R ¹ and R ⁸ are t-butyl groups, and R ⁴ and R ⁵ are methyl groups. As such a compound, YSLV-120TE (trade name, manufactured by Tohto Kasei Co., Ltd.) and the like are available as commercial products. These epoxy resins may be used alone or in combination of two or more, but the blending amount is 20 mass in total with respect to the total amount of the epoxy resin in order to exhibit the performance. % Or more, preferably 30% by mass or more, and more preferably 50% by mass or more.

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

（一般式（ＶＩＩＩ）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。）

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

  The novolak type epoxy resin represented by the general formula (VIII) can be easily obtained by reacting a novolak type phenol resin with epichlorohydrin. Especially, as R in general formula (VIII), as a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group etc., a C1-C10 alkyl group, a methoxy group, an ethoxy group C1-C10 alkoxyl groups, such as a propoxy group and a butoxy group, are preferable, and a hydrogen atom or a methyl group is more preferable. n is preferably an integer of 0 to 3. Among the novolak epoxy resins represented by the general formula (VIII), orthocresol novolac epoxy resins are preferable. N-600 series (Dainippon Ink Chemical Co., Ltd. product name) etc. are commercially available. In the case of using a novolac type epoxy resin, the blending amount thereof is preferably 20% by mass or more, more preferably 30% by mass or more, based on the total amount of the epoxy resin in order to exhibit its performance.

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

（一般式（ＩＸ）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。）

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

R ¹ in the above formula (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 t-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 t-butyl group, an alkenyl group such as a vinyl group, an allyl group, and a butenyl group, and an alkyl halide. Examples thereof include substituted or unsubstituted monovalent hydrocarbon groups having 1 to 5 carbon atoms such as a group, an amino group-substituted alkyl group, and a mercapto group-substituted alkyl group, and among them, a hydrogen atom is preferable. HP-7200 (trade name, manufactured by Dainippon Ink and Chemicals, Inc.) is available as a commercial product. When a dicyclopentadiene type epoxy resin is used, its blending amount is preferably 20% by mass or more, more preferably 30% by mass or more, based on the total amount of the epoxy resin in order to exhibit its performance.

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

（一般式（Ｘ）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、全てが同一でも異なっていてもよい。ｐは１又は０で、ｌ、ｍはそれぞれ０〜１１の整数であって、（ｌ＋ｍ）が１〜１１の整数でかつ（ｌ＋ｐ）が１〜１２の整数となるよう選ばれる。Ｉは０〜３の整数、ｊは０〜２の整数、ｋは０〜４の整数を示す。）

(In General Formula (X), R ^{1 to} R ³ are selected from a hydrogen atom and a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, and all may be the same or different. 1 or 0, l and m are each an integer of 0 to 11, wherein (l + m) is an integer of 1 to 11 and (l + p) is an integer of 1 to 12. I is 0 to 3 And 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.

（一般式（ＸＩ）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。）

(In General Formula (XI), 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 triphenylmethane type epoxy resin represented by the general formula (XI), for example, EPPN-500 series (trade name, manufactured by Nippon Kayaku Co., Ltd.) is commercially available. These epoxy resins may be used alone or in combination of both, but the blending amount is 20% by mass or more in total with respect to the total amount of the epoxy resin in order to exhibit the performance. Preferably, the content is 30% by mass or more, and more preferably 50% by mass or more.

  The biphenyl type epoxy resin, bisphenol F type epoxy resin, stilbene type epoxy resin, sulfur atom-containing epoxy resin, novolac type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin and triphenylmethane type epoxy resin These may be used alone or in combination of two or more, but the blending amount is preferably 50% by mass or more, more preferably 60% by mass or more, based on the total amount of the epoxy resin. Preferably, 80 mass% or more is more preferable.

  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).

（上記一般式（ＸＩＩ）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７〜１０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。）

(All of R ^{1 to} R ⁹ in the general formula (XII) may be the same or different and have 1 carbon atom such as a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, or an isobutyl group. 10 to 10 alkyl groups, methoxy groups, ethoxy groups, propoxy groups, butoxy groups and the like, alkoxy groups having 1 to 10 carbon atoms, phenyl groups, tolyl groups, xylyl groups and the like aryl groups having 6 to 10 carbon atoms, and benzyl Selected from aralkyl groups having 7 to 10 carbon atoms such as a group and a phenethyl group, among which a hydrogen atom and a methyl group are preferred, and n represents an integer of 0 to 10.)

（一般式（ＸＩＩＩ）で、Ｒ^１〜Ｒ^２は水素原子及び置換又は非置換の炭素数１〜１２の一価の炭化水素基から選ばれ、それぞれ全てが同一でも異なっていてもよい。ｎは１〜１０の整数を示す。）

(In the general formula (XIII), R ^{1 and} R ² are selected from a hydrogen atom and a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, and all may be the same or different. Represents an integer of 1 to 10.)

  As a biphenylene type epoxy resin, NC-3000 (trade name, manufactured by Nippon Kayaku Co., Ltd.) is available as a commercial product. As naphthol / aralkyl type epoxy resins, ESN-175 (trade name, manufactured by Toto Kasei Co., Ltd.) and the like are commercially available. These biphenylene type epoxy resins and naphthol / aralkyl type epoxy resins may be used alone or in combination with each other, but the blending amount thereof is the total amount of the epoxy resin in order to exhibit its performance. The total content is preferably 20% by mass or more, more preferably 30% by mass or more, and still more preferably 50% by mass or more.

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

  The melt viscosity at 150 ° C. of the (A) epoxy resin used in the present invention is preferably 0.2 Pa · s (2 poise) or less, more preferably 0.1 Pa · s (1 poise) or less, from the viewpoint of fluidity. 0.05 Pa · s (0.5 poise) or less is more preferable. Here, the melt viscosity is a viscosity measured with an ICI cone plate viscometer.

[(B) Curing agent]
The (B) curing agent used in the present invention is generally used for an epoxy resin molding material for sealing and is not particularly limited. For example, phenol, cresol, resorcin, catechol, bisphenol A, bisphenol F, phenyl Phenols such as phenol and aminophenol and / or naphthols such as α-naphthol, β-naphthol, and dihydroxynaphthalene and compounds having an aldehyde group such as formaldehyde, benzaldehyde, and salicylaldehyde are condensed or co-condensed in an acidic catalyst. Novolac-type phenolic resin obtained by phenol; phenol / aralkyl resin synthesized from phenol and / or naphthol and dimethoxyparaxylene or bis (methoxymethyl) biphenyl, naphthol / aralkyl resin, biphenyl Aralkyl-type phenol resins such as le-aralkyl resins; dicyclopentadiene-type phenol resins synthesized by copolymerization from phenols and / or naphthols and dicyclopentadiene; terpene-modified phenol resins; triphenylmethane-type phenol resins These may be used alone or in combination of two or more. Among them, biphenyl type phenol resin is preferable from the viewpoint of flame retardancy, aralkyl type phenol resin is preferable from the viewpoint of reflow resistance and curability, and dicyclopentadiene type phenol resin is preferable from the viewpoint of low hygroscopicity, From the viewpoints of heat resistance, low expansion rate and low warpage, a triphenylmethane type phenol resin is preferable, and from the viewpoint of curability, a novolac type phenol resin is preferable, and contains at least one of these phenol resins. Is preferred.

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

R ^{1 to} R ⁹ in the above formula (XIV) may all be the same or different and have 1 to 10 carbon atoms such as a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, and an isobutyl group. An alkyl group, a methoxy group, an ethoxy group, a propoxy group, a butoxy group or the like, an alkoxyl group having 1 to 10 carbon atoms, a phenyl group, a tolyl group, an aryl group having 6 to 10 carbon atoms such as a xylyl group, and a benzyl group, It is selected from aralkyl groups having 7 to 10 carbon atoms such as a 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 biphenyl type phenol resin represented by the general formula (XIV) 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 condensate having 1 or more. A mixture of condensates containing 50% by mass or more is preferred. As such a compound, MEH-7851 (trade name, manufactured by Meiwa Kasei Co., Ltd.) is commercially available. When a biphenyl type phenol resin is used, its 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 curing agent in order to exhibit its performance. Further preferred.

  Examples of the aralkyl type phenol resin include a phenol aralkyl resin, a naphthol aralkyl resin, and the like. A phenol aralkyl resin represented by the following general formula (XV) and a naphthol aralkyl resin represented by the following general formula (XVI) include: preferable. A phenol / aralkyl resin in which R in the general formula (XV) 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. 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.

（一般式（ＸＶ）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。）

(In general formula (XV), 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)

（一般式（ＸＶＩ）で、Ｒ^１〜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、それぞれ全てが同一でも異なっていてもよい。ｎは０〜１０の整数を示す。）

(In General Formula (XVI), R ^{1 and} R ² are selected from a hydrogen atom and a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and each may be the same or different. Represents an integer of 0 to 10.)

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

（一般式（ＸＶＩＩ）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。）

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

  When a dicyclopentadiene type phenol resin is used, 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 its performance.

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

（一般式（ＸＶＩＩＩ）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。）

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

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

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

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

  The melt viscosity at 150 ° C. of the (B) curing agent used in the present invention is preferably 0.2 Pa · s (2 poise) or less, more preferably 0.1 Pa · s (1 poise) or less from the viewpoint of fluidity. Here, melt viscosity indicates ICI viscosity.

  The equivalent ratio of (A) epoxy resin and (B) curing agent, that is, the ratio of the number of hydroxyl groups in the curing agent to the number of epoxy groups in the epoxy resin (number of hydroxyl groups in the curing agent / number of epoxy groups in the epoxy resin) is: 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.

[(C) Curing accelerator]
In the sealing epoxy resin molding material of the present invention, (C) a curing accelerator is blended in order to promote the reaction between (A) the epoxy resin and (B) the curing agent. (C) Although a hardening accelerator is generally used for the epoxy resin molding material for sealing, there is no restriction | limiting in particular, For example, 1,8-diaza-bicyclo (5,4,0) undecene-7, 1 , 5-diaza-bicyclo (4,3,0) nonene, 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. In particular, an adduct of a phosphine compound and a quinone compound is preferably included.

  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. Furthermore, an adduct of a phosphine compound and a quinone compound in which at least one alkyl group is bonded to a phosphorus atom is preferable from the viewpoints of curability, fluidity and flame retardancy. The blending amount of the curing accelerator is not particularly limited as long as the curing acceleration effect is achieved, but is preferably 0.005 to 2% by mass with respect to the epoxy resin molding material for sealing. 01-0.5 mass% is more preferable. If it is less than 0.005% by mass, the curability in a short time tends to be inferior, and if it exceeds 2% by mass, the curing rate tends to be too high and it tends to be difficult to obtain a good molded product.

[(D) Inorganic filler]
(D) An inorganic filler is mix | blended with the epoxy resin molding material for sealing of this invention. 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, 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., and as the zinc molybdate, KEGGARD 911B, 911C, 1100 ( (SherwIn-WIllIams) etc. are each commercially available.

  These inorganic fillers may be used alone or in combination of two or more. Of these, fused silica is preferable from the viewpoint of filling property and linear expansion coefficient, and alumina is preferable from the viewpoint of high thermal conductivity, and the shape of the inorganic filler is preferably spherical from the viewpoint of filling property and mold wear. The blending amount of the inorganic filler is based on the total amount of magnesium hydroxide and the epoxy resin molding material for sealing from the viewpoints of flame retardancy, moldability, hygroscopicity, reduction of linear expansion coefficient, strength improvement and reflow resistance. 50 mass% or more is preferable, 60-95 mass% is more preferable, 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.

  The epoxy resin molding material for sealing of the present invention comprises (D) an inorganic filler, (F) a hydrotalcite compound represented by the general formula (1), (E), from the viewpoint of fluidity of the resin composition. ) The total content of the amphoteric ion exchanger obtained by mixing and firing yttrium oxide and zirconium phosphate is preferably 60 to 95% by mass, more preferably 65 to 93% by mass, and 70 to 90% by mass. More preferably.

[(G) Metal oxide]
In addition to yttrium oxide, other (G) metal oxides can be used for the epoxy resin molding material for sealing of the present invention from the viewpoint of improving flame retardancy. (G) The metal oxide may be selected from metal elements in metal elements belonging to Group IA, Group IIA, Group IIIA to VIA, so-called typical metal elements, and oxides of transition metal elements belonging to Group IIIB to IIB. Preferably, it is preferably at least one of oxides of magnesium, copper, iron, molybdenum, tungsten, zirconium, manganese and calcium from the viewpoint of flame retardancy. The metal element is classified into a long-period periodic table in which the typical element is the A group and the transition element is the B group (Source: Kyoritsu Shuppan Co., Ltd., “Chemical Dictionary 4”, February 15, 1987). (Reduced plate 30th printing). The compounding amount of (G) metal oxide is preferably 0.1 to 100 parts by mass, more preferably 1 to 50 parts by mass, and 3 to 20 parts by mass with respect to 100 parts by mass of (A) epoxy resin. More preferably, it is a part. When the amount is less than 0.1 parts by mass, the flame retardancy tends to be inferior, and when the amount exceeds 100 parts by mass, the fluidity and curability tend to decrease.

[(H) coupling agent]
In order to improve the adhesiveness between the resin component and the filler, it is preferable to further add (H) a coupling agent to the sealing epoxy resin molding material of the present invention. (H) The coupling agent is generally used in an epoxy resin molding material for sealing and is not particularly limited. For example, a silane compound having a primary and / or secondary and / or tertiary amino group And various silane compounds such as epoxy silane, mercapto silane, alkyl silane, ureido silane, and vinyl silane, titanium compounds, aluminum chelates, and aluminum / zirconium compounds. Examples of these are vinyltrichlorosilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycol. Sidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, vinyltriacetoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropyl Triethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-anilinopropyltrimethoxysilane, γ-anilinopropyltriethoxysilane, γ- (N, N-dimethyl) aminopropyltrimethoxy Silane, γ- (N, N-diethyl) aminopropyltrimethoxysilane, γ- (N, N-dibutyl) aminopropyltrimethoxysilane, γ- (N-methyl) anilinopropyltrimethoxysilane, γ- (N -Ethyl) anilinopropyltrimethoxysilane, γ- (N, N-dimethyl) aminopropyltriethoxysilane, γ- (N, N-diethyl) aminopropyltriethoxysilane, γ- (N, N-dibutyl) amino Propyltriethoxysilane, γ- (N-methyl) anilinopropyltriethoxysilane, γ- (N-ethyl) anilinopropyltriethoxysilane, γ- (N, N-dimethyl) aminopropylmethyldimethoxysilane, γ- (N, N-diethyl) aminopropylmethyldimethoxysilane, γ- (N, N-dibutyl) aminopropy Rumethyldimethoxysilane, γ- (N-methyl) anilinopropylmethyldimethoxysilane, γ- (N-ethyl) anilinopropylmethyldimethoxysilane, N- (trimethoxysilylpropyl) ethylenediamine, N- (dimethoxymethylsilylisopropyl) ) Silane coupling agents such as ethylenediamine, methyltrimethoxysilane, dimethyldimethoxysilane, methyltriethoxysilane, γ-chloropropyltrimethoxysilane, hexamethyldisilane, vinyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, isopropyl Triisostearoyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, isopropyl tri (N-aminoethyl-aminoethyl) titanate, tetraoctane Rubis (ditridecylphosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, bis (dioctylpyrophosphate) oxyacetate titanate, bis (dioctylpyrophosphate) ethylene titanate, Isopropyltrioctanoyl titanate, isopropyldimethacrylisostearoyl titanate, isopropyltridodecylbenzenesulfonyl titanate, isopropylisostearoyl diacryl titanate, isopropyltri (dioctylphosphate) titanate, isopropyltricumylphenyl titanate, tetraisopropylbis (dioctylphosphite) titanate And titanate coupling agents such as A seed may be used independently or may be used in combination of 2 or more types.

  Among these, from the viewpoint of fluidity and flame retardancy, it is preferable to include a silane coupling agent, particularly a silane coupling agent having a secondary amino group. 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. Among these, it is particularly preferable to include an aminosilane coupling agent represented by the following general formula (II).

（一般式（ＩＩ）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。）

(In the general formula (II), 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, and R ² is selected from an alkyl group having 1 to 6 carbon atoms and a phenyl group. R ³ represents a methyl group or an ethyl group, n represents an integer of 1 to 6, and m represents an integer of 1 to ^3. )

  (H) The total blending amount of the coupling agent is preferably 0.037 to 5% by mass, more preferably 0.05 to 4.75% by mass with respect to the sealing epoxy resin molding material. More preferably, it is 0.1-2.5 mass%. If it is less than 0.037% by mass, the adhesion to the frame tends to be lowered, and if it exceeds 5% by mass, the moldability of the package tends to be lowered.

[(I) Compound having phosphorus atom]
From the viewpoint of improving flame retardancy, (I) a compound having a phosphorus atom can be used for the epoxy resin molding material for sealing of the present invention. (I) The compound having a phosphorus atom is not particularly limited as long as the effect of the present invention can be obtained, and is a coated or uncoated red phosphorus, a phosphorus-containing compound such as cyclophosphazene and a nitrogen-containing compound, nitrilotrismethylenephosphonic acid tricalcium salt , Phosphonates such as methane-1-hydroxy-1,1-diphosphonic acid dicalcium salt, triphenylphosphine oxide, 2- (diphenylphosphinyl) hydroquinone, 2,2-[(2- (diphenylphosphinyl ) -1,4-phenylene) bis (oxymethylene)] bis-oxirane, phosphines such as tri-n-octylphosphine oxide, phosphine oxide compounds, phosphate ester compounds, and the like. Alternatively, two or more kinds may be used in combination.

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

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

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

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

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

  Methods for producing coated red phosphorus such as red phosphorus coated with a thermosetting resin, red phosphorus coated with an inorganic compound and an organic compound are disclosed in, for example, Japanese Patent Laid-Open Nos. 62-217044 and 52-131695. A known coating method described in a gazette or the like can be used. The thickness of the coating film is not particularly limited as long as the effects of the present invention can be obtained, and the coating may be uniformly coated on the surface of red phosphorus or non-uniform. The particle size of red phosphorus is preferably 1 to 100 μm, more preferably 5 to 50 μm, in terms of average particle size (particle size with a cumulative particle size distribution of 50% by mass). When the average particle size is less than 1 μm, the phosphate ion concentration of the molded product tends to be high and the moisture resistance tends to be inferior. When the average particle size exceeds 100 μm, when used in a highly integrated and high-density semiconductor device with a narrow pad pitch, There is a tendency that defects due to deformation, short circuit, cutting, etc. are likely to occur.

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

（一般式（ＩＩＩ）で、式中の８個のＲは炭素数１〜４のアルキル基を示し、全て同一でも異なっていてもよい。Ａｒは芳香族環を示す。）

(In the general formula (III), 8 Rs in the formula are alkyl groups having 1 to 4 carbon atoms, and they may all be the same or different. Ar represents an aromatic ring.)

  When the phosphoric acid ester compound of the said Formula (III) is illustrated, the phosphoric acid ester shown by following structural formula (XX)-(XXIV) etc. will be mentioned.

  The addition amount of these phosphate ester compounds is preferably in the range of 0.2 to 3.0 mass% in terms of the amount of phosphorus atoms with respect to all the other compounding ingredients except the filler. When it is less than 0.2% by mass, the flame retardant effect tends to be low. If it exceeds 3.0% by mass, the formability and moisture resistance may be lowered, and these phosphate ester compounds may ooze out during molding, thereby impairing the appearance.

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

（一般式（ＩＶ）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、アラルキル基または水素原子を示し、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。）

(In the general formula (IV), 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 or a hydrogen atom, and they may all be the same or different. (Except when all are hydrogen atoms)

Among the phosphine compounds represented by the general formula (IV), R ^{1 to} R ³ are preferably substituted or unsubstituted aryl groups, particularly preferably phenyl groups, from the viewpoint of hydrolysis resistance. 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 tends to decrease, and if it exceeds 0.2% by mass, the moldability and moisture resistance tend to decrease.

  Cyclophosphazenes are cyclic phosphazene compounds containing the following formula (XXV) and / or the following formula (XXVI) as a repeating unit in the main chain skeleton, or the following formulas (XXVII) and different substitution positions for phosphorus atoms in the phosphazene ring. And / or a compound containing the following formula (XXVIII) as a repeating unit.

Here, m in the formula (XXV) and the formula (XXVII) 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 which 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 (XXVI) and Formula (XXVIII) 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 (XXV) to (XXVIII), the alkyl group or aryl group having 1 to 12 carbon atoms which may have a substituent represented by R ^{1 to} R ⁸ is not particularly limited. Alkyl groups such as ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group and tert-butyl group, aryl groups such as phenyl group, 1-naphthyl group and 2-naphthyl group, o-tolyl Group, m-tolyl group, p-tolyl group, 2,3-xylyl group, 2,4-xylyl group, o-cumenyl group, m-cumenyl group, p-cumenyl group, mesityl group, etc. , Aryl group-substituted alkyl groups such as benzyl group and phenethyl group, etc., and further substituents for these include alkyl groups, alkoxyl groups, aryl groups, hydroxyl groups, 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. Moreover, there is no restriction | limiting in particular as a C1-C4 alkylene group or arylene group shown by A in said Formula (XXV)-Formula (XXVIII), For example, a methylene group, ethylene group, propylene group, isopropylene group , Butylene group, isobutylene group, phenylene group, tolylene group, xylylene group, naphthylene group, biphenylene group, and the like. From the viewpoint of heat resistance and moisture resistance of the epoxy resin molding material, an arylene group is preferable, and a phenylene group is more preferable. preferable.

  The cyclic phosphazene compound is a polymer of any one of the above formulas (XXV) to (XXVIII), a copolymer of the above formula (XXV) and the above formula (XXVI), or the above formula (XXVII) and the above formula (XXVIII). 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 (XXIX) and a copolymer of the following formula (XXX).

（ここで、一般式（ＸＸＩＸ）中のｎは、０〜９の整数で、Ｒ^１〜Ｒ^６はそれぞれ独立に水素原子又は水酸基を示す。）

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

Here, m and n in the general formula (XXX) are integers of 0 to 9, and R ^{1 to} R ⁶ are each independently selected from a hydrogen atom or a hydroxyl group. In addition, the cyclic phosphazene compound represented by the general formula (XXX) includes the following m repeating units (a) and n repeating units (b) alternately, blocks including, randomly Any of these may be included, but those randomly included are preferred.

（上記繰り返し単位（ａ）中のＲ^１〜Ｒ^６はそれぞれ独立に水素原子または水酸基から選ばれる。）

(R ^{1 to} R ⁶ in the repeating unit (a) are each independently selected from a hydrogen atom or a hydroxyl group.)

Among them, the main component is a polymer having n of 3 to 6 in the formula (XXIX), or R ^{1 to} R ⁶ are all hydrogen atoms or one is a hydroxyl group in the formula (XXX), and n / m is The main component is a copolymer of 1/2 to 1/3 and n + m of 3 to 6. In addition, as a commercially available phosphazene compound, SPE-100 (trade name, manufactured by Otsuka Chemical Co., Ltd.) and the like are available.

  (I) Although the compounding quantity of the compound which has a phosphorus atom does not have a restriction | limiting in particular, 0.01-50 mass% is preferable with the quantity of a phosphorus atom with respect to all the other compounding components except (D) inorganic filler, 0.1-10 mass% is more preferable, and 0.5-3 mass% is further more preferable. If the blending amount is less than 0.01% by mass, the flame retardancy tends to be insufficient, and if it exceeds 50% by mass, the moldability and moisture resistance tend to decrease.

[Other ingredients]
In the present invention, from the viewpoint of releasability, (J) a linear oxidized polyethylene having a weight average molecular weight of 4,000 or more, and (K) a copolymer of an α-olefin having 5 to 30 carbon atoms and maleic anhydride. May be further incorporated by esterification with a monohydric alcohol having 5 to 25 carbon atoms. (J) The linear oxidized polyethylene having a weight average molecular weight of 4,000 or more serves as a release agent. Here, the linear polyethylene refers to polyethylene having a carbon number of the side chain alkyl chain of about 10% or less of the carbon number of the main chain alkyl chain, and is generally classified as polyethylene having a penetration of 2 or less. Is done. The oxidized polyethylene means polyethylene having an acid value. The weight average molecular weight of the component (J) is preferably 4,000 or more from the viewpoint of releasability, and preferably 30,000 or less from the viewpoint of adhesion and prevention of mold / package contamination. 5,000 to 20,000 is more preferable, and 7,000 to 15,000 is more preferable. Here, the weight average molecular weight refers to a value measured by high temperature GPC (gel permeation chromatography). In addition, the high temperature GPC measuring method in this invention is as follows.
Measuring device: High-temperature GPC manufactured by Waters
Solvent: Dichlorobenzene Temperature: 140 ° C
Standard substance: Polystyrene Column: Product name PLgel MIXED-B manufactured by Polymer Laboratories
10 μm (7.5 mm × 300 mm) × 2 flow rate: 1.0 ml / min (sample concentration: 0.3 wt / Vol%)
(Injection volume: 100 μl)

  The acid value of component (J) is not particularly limited, but is preferably 2 to 50 mg / KOH, more preferably 10 to 35 mg / KOH from the viewpoint of releasability. (J) Although there is no restriction | limiting in particular in the compounding quantity of a component, 0.5-10 mass% is preferable with respect to (A) epoxy resin, and 1-5 mass% is more preferable. If the blending amount is less than 0.5% by mass, the releasability tends to decrease, and if it exceeds 10% by mass, the effect of improving adhesiveness and mold / package dirt may be insufficient.

  A compound obtained by esterifying (K) a copolymer of an α-olefin having 5 to 30 carbon atoms and maleic anhydride with a monohydric alcohol having 5 to 25 carbon atoms used in the present invention also serves as a release agent. Thus, both the straight-chain oxidized polyethylene (I) and the epoxy resin (A) are highly compatible, and are effective in preventing deterioration of adhesiveness and mold / package contamination.

  The α-olefin having 5 to 30 carbon atoms used for the component (K) is not particularly limited, and examples thereof include 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene and 1-decene. 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 1-docosene, 1-tricosene, 1 -Linear α-olefins such as tetracocene, 1-pentacocene, 1-hexacocene, 1-heptacocene, 3-methyl-1-butene, 3,4-dimethyl-pentene, 3-methyl-1-nonene, 3,4 -Dimethyl-octene, 3-ethyl-1-dodecene, 4-methyl-5-ethyl-1-octadecene, 3,4,5-triethyl-1- Examples include branched α-olefins such as eicosene, and these may be used alone or in combination of two or more. Among these, a linear α-olefin having 10 to 25 carbon atoms is preferable, and a linear α-olefin having 15 to 25 carbon atoms such as 1-eicosene, 1-docosene and 1-tricosene is more preferable.

  The monovalent alcohol having 5 to 25 carbon atoms used for the component (K) is not particularly limited. For example, amyl alcohol, isoamyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, capryl alcohol, nonyl alcohol, decyl are used. Linear or branched aliphatic saturated alcohols such as alcohol, undecyl alcohol, lauryl alcohol, tridecyl alcohol, myristyl alcohol, pentadecyl alcohol, cetyl alcohol, heptadecyl alcohol, stearyl alcohol, nonadecyl alcohol, and eicosyl alcohol Linear or branched aliphatic unsaturated alcohols such as hexenol, 2-hexen-1-ol, 1-hexen-3-ol, pentenol, 2-methyl-1-pentenol, Examples thereof include alicyclic alcohols such as clopentanol and cyclohexanol, aromatic alcohols such as benzyl alcohol and cinnamyl alcohol, and heterocyclic alcohols such as furfuryl alcohol. You may use it in combination. Among these, a linear alcohol having 10 to 20 carbon atoms is preferable, and a linear aliphatic saturated alcohol having 15 to 20 carbon atoms is more preferable.

  The copolymer of the α-olefin having 5 to 30 carbon atoms and maleic anhydride in the component (K) of the present invention is not particularly limited, and examples thereof include compounds represented by the following general formula (XXXI), The compound shown by (XXXII) etc. is mentioned, As a commercial item, Nissan Electol WPB-1 (Nippon Yushi Co., Ltd. brand name) etc. which use 1-eicocene, 1-docosene, and 1-tetracocene as a raw material etc. are obtained. Is possible.

（一般式（ＸＸＸＩ）および（ＸＸＸＩＩ）で、Ｒは炭素数３〜２８の一価の脂肪族炭化水素基から選ばれ、ｎは１以上の整数、ｍは正の数を示す。）

(In the general formulas (XXXI) and (XXXII), R is selected from monovalent aliphatic hydrocarbon groups having 3 to 28 carbon atoms, n is an integer of 1 or more, and m is a positive number.)

  M in the above general formulas (XXXI) and (XXXII) represents the number of moles of α-olefin copolymerized with respect to 1 mole of maleic anhydride, and is not particularly limited, but is preferably 0.5 to 10, .9 to 1.1 are more preferable.

There is no restriction | limiting in particular as a manufacturing method of the copolymer of (H) component, A general copolymerization method can be used. For the reaction, an organic solvent in which the α-olefin and maleic anhydride are soluble may be used. Although there is no restriction | limiting in particular as an organic solvent, Toluene is preferable and an alcohol solvent, an ether solvent, an amine solvent, etc. can also be used. Although reaction temperature changes also with the kind of organic solvent to be used, it is preferable to set it as 50-200 degreeC from a reactive and productivity viewpoint, and 80-120 degreeC is more preferable. The reaction time is not particularly limited as long as a copolymer is obtained, but it is preferably 1 to 30 hours, more preferably 2 to 15 hours, and more preferably 4 to 10 hours from the viewpoint of productivity. Is more preferable. After completion of the reaction, if necessary, unreacted components, solvents and the like can be removed under heating and reduced pressure. The condition is that the temperature is 100 to 220 ° C., more preferably 120 to 180 ° C., the pressure is 13.3 × 10 ³ Pa or less, more preferably 8 × 10 ³ Pa or less, and the time is 0.5 to 10 hours. It is preferable. Moreover, you may add reaction catalysts, such as an amine catalyst and an acid catalyst, to reaction. The pH of the reaction system is preferably about 1 to 10.

The method of esterifying the copolymer of component (H) with a monohydric alcohol having 5 to 25 carbon atoms is not particularly limited, and is a general method such as addition reaction of a monohydric alcohol to the copolymer. Can be used. The reaction molar ratio of the copolymer and the monohydric alcohol is not particularly limited and can be arbitrarily set. However, the degree of hydrophilicity can be controlled by adjusting the reaction molar ratio. It is preferable to set appropriately according to the epoxy resin molding material for sealing. For the reaction, an organic solvent or the like in which the copolymer is soluble may be used. Although there is no restriction | limiting in particular as an organic solvent, Toluene is preferable and an alcohol solvent, an ether solvent, an amine solvent, etc. can also be used. Although reaction temperature changes also with the kind of organic solvent to be used, it is preferable to set it as 50-200 degreeC from a reactive and productivity viewpoint, and 80-120 degreeC is more preferable. The reaction time is not particularly limited, but is preferably 1 to 30 hours, more preferably 2 to 15 hours, and still more preferably 4 to 10 hours from the viewpoint of productivity. After completion of the reaction, if necessary, unreacted components, solvents and the like can be removed under heating and reduced pressure. The condition is that the temperature is 100 to 220 ° C., more preferably 120 to 180 ° C., the pressure is 13.3 × 10 ³ Pa or less, more preferably 8 × 10 ³ Pa or less, and the time is 0.5 to 10 hours. It is preferable. Moreover, you may add reaction catalysts, such as an amine catalyst and an acid catalyst, to reaction. The pH of the reaction system is preferably about 1 to 10.

  (K) As a compound which esterified the copolymer of the alpha olefin of component and maleic anhydride with monohydric alcohol, the diester shown by following formula (a) or (b), and a formula ( The compound etc. which contain in a structure 1 or more types chosen from the monoester shown by c)-(f) as a repeating unit are mentioned. Moreover, even if it contains the non-ester represented by the formula (g) or (h), it may contain a structure in which maleic anhydride is ring-opened to have two —COOH groups. Examples of such a compound include (1) one in which the main chain skeleton is composed of any one of formulas (a) to (f), and (2) the formula (a) to (f) in the main chain skeleton. Those containing at least two of these randomly, those containing regularly, those containing in block form, and (3) any one or more of formulas (a) to (f) in the main chain skeleton Examples include those containing at least one of formulas (g) and (h) at random, those containing regularly, those containing in block form, and the like. These may be used alone or in combination of two or more. Also good. And (4) those containing the formulas (g) and (h) in the main chain skeleton at random, those containing the formula (g) and (h) in a block form, and (5) the main chain skeleton represented by the formula (g) or ( Either or both of h) and those constituted alone may be included.

（上記式（ａ）〜（ｈ）で、Ｒ^１は炭素数３〜２８の一価の脂肪族炭化水素基、Ｒ^２は炭
素数５〜２５の一価の炭化水素基から選ばれ、ｍは正の数を示す。）

(In the above formulas (a) to (h), R ¹ is selected from monovalent aliphatic hydrocarbon groups having 3 to 28 carbon atoms, R ² is selected from monovalent hydrocarbon groups having 5 to 25 carbon atoms, m Indicates a positive number.)

  M in the above formulas (a) to (h) indicates how many moles of α-olefin are copolymerized with respect to 1 mole of maleic anhydride, and there is no particular limitation, but 0.5 to 10 is preferable. 9 to 1.1 is more preferable.

The monoesterification rate of the component (H) can be appropriately selected depending on the combination with the component (K), but is preferably 20% or more from the viewpoint of releasability, and the component (K) is represented by the formula (c) The compound which contains 20 mol% or more combining any 1 type (s) or 2 or more types of monoester shown by (f) is preferable, and the compound containing 30 mol% or more is more preferable. In addition, the weight average molecular weight of the component (K) is preferably 5,000 to 100,000, more preferably 10,000 to 70,000, from the viewpoint of mold / package contamination prevention and moldability. 000 to 50,000 is more preferable. If the weight average molecular weight is less than 5,000, the effect of preventing mold / package stains tends to be low, and if it exceeds 100,000, the softening point of the compound increases and the kneadability tends to be poor. Here, the weight average molecular weight is a value measured by normal temperature GPC. The measuring method of the weight average molecular weight by normal temperature GPC in the present invention is as follows.
Measuring instrument: LC-6C manufactured by Shimadzu Corporation
Column: shodeX KF-802.5 + KF-804 + KF-806
Solvent: THF (tetrahydrofuran)
Temperature: Room temperature (25 ° C)
Standard material: Polystyrene flow rate: 1.0 ml / min (sample concentration: about 0.2 wt / Vol%)
Injection volume: 200 μl

  Although the compounding quantity of (H) component does not have a restriction | limiting in particular, 0.5-10 mass% is preferable with respect to (A) epoxy resin, and 1-5 mass% is more preferable. If the blending amount is less than 0.5% by mass, the releasability tends to decrease, and if it exceeds 10% by mass, the reflow resistance tends to decrease.

  From the viewpoint of reflow resistance and mold / package contamination, at least one of the component (J) and the component (K), which is a release agent in the present invention, is the component (A) during the preparation of the epoxy resin molding material of the present invention. Premixing with part or all of the epoxy resin is preferred. When at least one of the component (J) and the component (K) is premixed with the component (A), the dispersibility in these base resins increases, and there is an effect of preventing deterioration of reflow resistance and mold / package contamination. . The premixing method is not particularly limited, and any method may be used as long as at least one of the component (J) and the component (K) is dispersed in the epoxy resin of the component (A). Examples thereof include a method of stirring at room temperature to 220 ° C. for 0.5 to 20 hours. From the viewpoints of dispersibility and productivity, the temperature is preferably 100 to 200 ° C., more preferably 150 to 170 ° C., and the stirring time is preferably 1 to 10 hours, more preferably 3 to 6 hours. At least one of the component (J) and the component (K) for premixing may be premixed with the total amount of the component (A), but sufficient effects can be obtained by premixing with a part of the component. In that case, the amount of the (A) component to be premixed is preferably 10 to 50% by mass of the total amount of the (A) component. In addition, by premixing any one of the (J) component and the (K) component with the (A) component, an effect of improving dispersibility can be obtained, but both the (J) component and the (K) component are It is preferable to pre-mix with the component (A) because the effect is higher. The order of addition of the three components in the case of premixing is not particularly limited, and even if all of them are added and mixed at the same time, either (J) component or (K) component is added and mixed first with (A) component Then, the remaining components may be added and mixed.

  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, melamine, melamine derivatives, melamine-modified phenolic resins, compounds having a triazine ring, nitrogen-containing compounds such as cyanuric acid derivatives and isocyanuric acid derivatives, aluminum hydroxide, zinc stannate, zinc borate, zinc molybdate, dicyclopentadienyl Examples thereof include compounds containing metal elements such as iron, and these may be used alone or in combination of two or more.

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

  The epoxy resin 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 1-2, Comparative Examples 1-3)
An epoxy resin having an epoxy equivalent of 245 and a melting point of 110 ° C., a sulfur atom-containing epoxy resin (trade name YSLV-80XY: Epoxy Resin 1 manufactured by Toto Kasei Co., Ltd.), a triphenylmethane type having a softening point of 83 ° C. and a hydroxyl group equivalent of 103 Phenol resin (Maywa Kasei Co., Ltd., trade name MEH-7500: Curing agent 1), Biphenyl aralkyl resin having a softening point of 67 ° C. and a hydroxyl group equivalent of 203 (Maywa Kasei Co., Ltd., trade name MEH-7785: Curing agent 2) , An adduct of tributylphosphine and 1,4-benzoquinone (curing accelerator 1) as a curing accelerator, yttrium oxide (trade name: Yttrium (III) manufactured by Shin-Etsu Chemical Co., Ltd.) as an ion exchanger, yttrium oxide and phosphoric acid Zirconium mixed fired product (amphoteric ion exchanger; median diameter: 4 μm, Toagosei Co., Ltd.) Company made, prototype product name IXE-Y), hydrotalcite _{(Mg 0.7 Al 0.3 (OH)} 2 (CO 3 2-) 0.15 · 0.5H 2 O, manufactured by Kyowa Chemical Industry Co., Ltd., trade name DHT-4A), cup Γ-glycidoxypropyltrimethoxysilane (epoxysilane) as a ring agent, spherical fused silica having an average particle size of 14.5 μm and a specific surface area of 2.8 m ² / g as an inorganic filler, and carnauba wax (release) as other additives Molding agent 1), linear average polyethylene oxide having a weight average molecular weight of 8,800, a penetration of 1, an acid value of 30 mg / KOH (component (J): release agent 2: trade name PED153 manufactured by Clariant), and carbon black (Mitsubishi Chemical Co., Ltd., trade name MA-100) was blended in parts by mass shown in Table 1, and roll kneading was carried out under conditions of a kneading temperature of 80 ° C. and a kneading time of 10 minutes. To 2 to obtain an epoxy resin molding material for sealing of the comparative Examples 1-3. In addition, the blank in Table 1 indicates no blending, and the blending unit is parts by mass.

The properties of the produced epoxy resin molding materials for sealing of Examples 1-2 and Comparative Examples 1-3 were determined by the following tests. The results are shown in Table 2.
(1) Spiral flow Using a spiral flow measurement mold in accordance with EMMI-1-66, a sealing epoxy resin composition was molded by a transfer molding machine at a mold temperature of 180 ° C., a molding pressure of 6.9 MPa, and a curing time. Molding was performed for 90 seconds, and the flow distance (cm) was determined.

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

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

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

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

(5) High temperature storage characteristics 42 mm alloy lead with partial silver plating on 5 mm x 9 mm x 0.4 mm test silicon chip with aluminum wiring with 10 μm line width and 1 μm thickness on 5 μm thick oxide film A 16-pin DIP (Dual Inline Package), which is mounted on the frame using silver paste and connected to the chip's bonding pads and inner leads with Au wire at 200 ° C by a thermonic wire bonder, is used as an epoxy resin for sealing Molded and post-cured using the composition under the condition (3) above, stored in a high-temperature bath at 175 ° C. and 200 ° C., taken out every predetermined time, conducted a continuity test, and the number of test packages ( The high temperature storage characteristics were evaluated by the number of poorly conductive packages for 10).

  From the results shown in Table 2, yttrium oxide and zirconium phosphate were mixed and fired as compared with the case where the conventionally used hydrotalcite was used (Comparative Example 2) and the case where yttrium oxide was used (Comparative Example 3). When the amphoteric ion exchanger is used (Example 1), the high temperature storage resistance is excellent, and the fluidity and flame retardancy are not significantly different from those when the ion exchanger is not included (Comparative Example 1). Maintained. However, when only the amphoteric ion exchanger in which yttrium oxide and zirconium phosphate are mixed and fired is used, the moisture resistance reliability is lowered. Therefore, this problem can be improved by further using hydrotalcite (Example 2), and the high temperature storage resistance is improved while maintaining fluidity and flame retardancy.

Claims (7)

  (A) An epoxy resin, (B) a curing agent, (C) a curing accelerator, (D) an inorganic filler, and (E) an amphoteric ion exchanger in which yttrium oxide and zirconium phosphate are mixed and fired. An epoxy resin molding material for sealing. Furthermore, the epoxy resin molding material for sealing of Claim 1 containing the hydrotalcite type compound represented by (F) general formula (1).
^{_{Mg 1-X Al X (OH}} ) 2 (A n-) X / n · mH 2 O ··· formula (1)
(However, in the general formula (1), 0 <X ≦ 0.5, m is 0 or a positive ^{number, A n-is} .n representing an n-valent anion represents a positive integer.)   (E) The epoxy resin molding material for sealing according to claim 1 or 2, wherein the median diameter of the amphoteric ion exchanger obtained by mixing and firing yttrium oxide and zirconium phosphate is 5 µm or less.   (E) The amphoteric ion exchanger in which yttrium oxide and zirconium phosphate are mixed and fired is contained in 0.02 to 2% by mass in all epoxy resin molding materials. Epoxy resin molding material for sealing.   (F) The sealing according to any one of claims 2 to 4, wherein the hydrotalcite compound represented by the general formula (1) is contained in the entire epoxy resin molding material in an amount of 0.02 to 2% by mass. Epoxy resin molding material for fastening.   The total content of (D) inorganic filler, (F) hydrotalcite compound represented by general formula (1), and (E) amphoteric ion exchanger in which yttrium oxide and zirconium phosphate are mixed and fired is 60 to 95 mass% The epoxy resin molding material for sealing according to any one of claims 2 to 5.   The electronic component apparatus provided with the element sealed with the epoxy resin molding material for sealing of any one of Claims 1-6.