JP2005350500A - Epoxy resin molding material for sealing and electronic part apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an epoxy resin molding material for sealing which imparts good package external appearances particularly to a thin package and prevents resin deposition on a mold, and an electronic part apparatus equipped with an element sealed with the same. <P>SOLUTION: The epoxy resin molding material for sealing comprises (A) an epoxy resin, (B) a curing agent, (C) a mixture obtained by preliminarily mixing an epoxy resin (C1) having an ICI (cone/plate) viscosity at 150°C of at most 0.2 Pa s, an oxidized polyolefin (C2), one or more copolymers (C3) of an α-olefin with at least one of maleic anhydride and a derivative thereof, and (D) at least one of compounds represented by general formulae (I) and (II) (wherein n is an integer of at least 0; and R<SB>1</SB>-R<SB>6</SB>are the same or different and are each one selected from among a hydrogen atom, a hydroxy group, a methoxy group, an ethoxy group and 1-6C alkyl groups). <P>COPYRIGHT: (C)2006,JPO&NCIPI

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, cost, etc., 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.

In recent years, in order to reduce the size, weight, performance, and functionality of electronic component devices, high-density mounting of elements, miniaturization of wiring, multilayering, increase in the number of pins, increase in the occupied area of the element package, etc. At the same time, from conventional DIP (Dual Inline Package), PGA (Pin Grid Aray), etc., QFP (Quad Flat Package), SOP (Small Outline Package), SOJ (Small Outline J-lead package), and more Are thinning electronic component devices to TSOP (Thin Small Outline Package), TQFP (Thin Quad Flat Package), and the like.
In many cases, a release agent is internally added to the sealing material for the purpose of smooth demolding from the mold, but the release resin basically contains an epoxy resin that constitutes an epoxy resin molding material for sealing. Since a compound that is incompatible with a curing agent or the like is used, it has an essential problem that it tends to cause a defective appearance of the package due to a dispersion failure in a resin or the like. Thinning the package is a factor that causes the flow behavior of the resin in the mold to fluctuate greatly depending on the filling position, and this contributes to the poor appearance of the package, along with the failure to disperse the release agent in the resin. It has become.
Further, as described above, a mold is used when molding the sealing material, but a groove (air vent) having a thickness of about 10 to 30 μm is processed in the mold in order to vent the air inside the mold. Existed. During molding, the resin often flows out to the air vent to form resin burrs. However, if the resin burrs remain in the mold during continuous molding, the air inside the mold is not smoothly vented, and resin filling defects, etc. There is also a problem that the problem of “unfilled” is likely to occur.

For preventing appearance defects of the package, for example, a method using a copolymer of α-olefin and maleic anhydride or a copolymer of styrene and maleic anhydride as a release agent (see, for example, Patent Document 1) )), A method of combining an esterified product of a copolymer of an α-olefin and maleic anhydride and an oxidized polyolefin (for example, see Patent Document 2 and Patent Document 3).
Japanese Patent Laid-Open No. 10-36486 JP 2001-247748 A JP 2003-64239 A

However, the effect is not always sufficient in terms of both the good package appearance and the resin remaining in the air vent when a sealing molding material made of a low molecular weight epoxy resin as a raw material is applied to a thin package.
The present invention has been made in view of such a situation, and in particular, a sealing molding material made of a low molecular weight epoxy resin as a raw material gives a good package appearance and prevents the resin residue of the air vent from remaining. And an electronic component device including an element sealed thereby.

  As a result of intensive studies to solve the above problems, the present inventors have used a sealing epoxy resin molding material in combination with a premixed release agent and a curing accelerator having a specific structure. It has been found that the above object can be achieved, and the present invention has been completed.

（一般式（I）で、ｎは０、又は１以上の整数を表す。R₁〜R₆は水素原子、水酸基、メトキシ基、エトキシ基、炭素数１〜６までのアルキル基から選ばれるものであり、互いに異なっていても同じであっても良い。）

（一般式（II）で、ｎは０、又は１以上の整数を表す。R₁〜R₆は水素原子、水酸基、メトキシ基、エトキシ基、炭素数１〜６までのアルキル基から選ばれるものであり、互いに異なっていても同じであっても良い。）
（２） （Ｃ）成分のα−オレフィンと無水マレイン酸及び無水マレイン酸誘導体の少なくともいずれかとの共重合物が下記一般式（III）で表される化合物である前記（１）に記載の封止用エポキシ樹脂成形材料、

（一般式（III）で、Ｒ_１は水素原子又は脂肪族炭化水素基を表し、Ｒ_２は水素原子、又は飽和炭化水素基、又は不飽和の炭化水素基を表し、Ｒ_３、Ｒ_４は飽和炭化水素基、又は不飽和の炭化水素基を表し、互いに同じでも異なっていても良い。Ｒ_５〜Ｒ_１０は水素原子又は飽和又は不飽和の炭化水素基を表し、互いに同じでも異なっていてもよい。ｐは正の整数を、ｑ、ｒ、ｓは０又は正の整数を表す。ただし、ｑ＝ｒ＝ｓ＝０を除く。）
（３）前記（１）又は（２）に記載の封止用エポキシ樹脂成形材料により封止された素子を備えた電子部品装置、
に関する。 The present invention
(1) (A) epoxy resin, (B) curing agent, (C) epoxy resin (C1) having an ICI viscosity at 150 ° C. of 0.2 Pa · s or less, oxidized polyolefin (C2), and α-olefin and anhydrous A mixture obtained by premixing one or more copolymers (C3) of at least one of maleic acid and maleic anhydride derivatives, (D) a compound represented by the following general formulas (I) and (II) An epoxy resin molding material for sealing containing at least one of

(In general formula (I), n represents 0 or an integer of 1 or more. R _{1 to} R ₆ are selected from a hydrogen atom, a hydroxyl group, a methoxy group, an ethoxy group, and an alkyl group having 1 to 6 carbon atoms. And they may be different or the same.)

(In formula (II), n represents 0 or an integer of 1 or more. R _{1 to} R ₆ are selected from a hydrogen atom, a hydroxyl group, a methoxy group, an ethoxy group, and an alkyl group having 1 to 6 carbon atoms. And they may be different or the same.)
(2) The sealing according to (1), wherein the copolymer of the α-olefin of component (C) and at least one of maleic anhydride and a maleic anhydride derivative is a compound represented by the following general formula (III): Epoxy resin molding material for fastening,

(In the general formula (III), R ₁ represents a hydrogen atom or an aliphatic hydrocarbon group, R ₂ represents a hydrogen atom, a saturated hydrocarbon group, or an unsaturated hydrocarbon group, and R ₃ and R ₄ represent A saturated hydrocarbon group or an unsaturated hydrocarbon group, which may be the same or different, and R _{5 to} R ₁₀ each represents a hydrogen atom or a saturated or unsaturated hydrocarbon group, and may be the same or different from each other; P is a positive integer, and q, r, and s are 0 or a positive integer, except that q = r = s = 0.
(3) An electronic component device including an element sealed with the sealing epoxy resin molding material according to (1) or (2),
About.

  The epoxy resin molding material for sealing according to the present invention is particularly excellent in preventing package contamination of a thin package and resin adhesion to a mold. The sealing epoxy resin molding material is used to seal electronic components such as ICs and LSIs. If it is stopped, an electronic component device having excellent reliability can be obtained, and its industrial value is great.

The epoxy resin of the component (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 or an orthocresol novolac epoxy resin is used. Phenols such as phenol, cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol F and / or naphthols such as α-naphthol, β-naphthol, dihydroxynaphthalene and formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, salicyl Epoxidized novolak resin obtained by condensing or co-condensing a compound having an aldehyde group such as aldehyde under an acidic catalyst, bisphenol A, bisphenol F, bisphenol S, diglycidyl ether such as bisphenol A / D, biphenyl type epoxy resin which is diglycidyl ether of alkyl-substituted or unsubstituted biphenol, phenols and / or naphthols and dimethoxyparaxylene or bis (methoxymethyl) biphenyl Glycidyl ester obtained by reaction of polychlorinated acid such as phenol aralkyl resin, naphthol aralkyl resin, epoxidized biphenyl aralkyl resin, stilbene type epoxy resin, hydroquinone type epoxy resin, phthalic acid, dimer acid and epichlorohydrin Type epoxy resin, diaminodiphenylmethane, isocyanuric acid and other polyamines obtained by reaction of epichlorohydrin with glycidylamine type epoxy resin, cyclopentadiene and phenol Dicyclopentadiene type epoxy resin, epoxy resin having naphthalene ring, triphenolmethane type epoxy resin, trimethylolpropane type epoxy resin, terpene modified epoxy resin, sulfur atom-containing epoxy resin, olefin bond Linear aliphatic epoxy resins, alicyclic epoxy resins obtained by oxidation of peracetic acid with peracids such as peracetic acid, and epoxies obtained by modifying these epoxy resins with silicone, acrylonitrile, butadiene, isoprene rubber, polyamide resin, etc. Examples thereof include resins, and these may be used alone or in combination of two or more.
Among these, when considering application to thin packages, from the viewpoint of fluidity and reliability, biphenyl type epoxy resins, biphenyl / aralkyl type epoxy resins, bisphenol type epoxy resins, and sulfur atom-containing epoxy resins are preferable. It is preferable to contain at least one of these resins.

  The above four types of epoxy resins may be used alone or in combination of two or more, but the blending amount is adjusted to the total amount of the epoxy resin in order to exhibit its performance. It is preferably 20% by weight or more, more preferably 30% by weight or more, and further preferably 50% by weight or more.

（一般式（IV）で、ｎは０又は１〜１０の整数を示し、A及びB中のベンゼン環、ナフタレン環及びビフェノール環上の水素原子は炭化水素基で置換されていてもよい。） 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. Novolak-type phenolic resin, phenol and / or naphthol and dimethoxyparaxylene or bis (methoxymethyl) biphenyl synthesized from phenol / aralkyl resin, naphthol / aralkyl resin, biphenyl Examples include aralkyl-type phenol resins such as aralkyl resins, dicyclopentadiene-type phenol resins, and terpene-modified phenol resins. These may be used alone or in combination of two or more.
Among them, when considering application to a thin package, particularly from the viewpoint of reliability, a phenol / aralkyl resin, a biphenyl / aralkyl resin, and a naphthol / aralkyl resin represented by the following general formula (IV) are preferable. It is preferable to contain at least one phenol resin.

(In the general formula (IV), n represents 0 or an integer of 1 to 10, and the hydrogen atom on the benzene ring, naphthalene ring and biphenol ring in A and B may be substituted with a hydrocarbon group.)

（一般式（V）で、ｎは０又は１〜１０の整数を示す。）

（一般式（VI）で、ｎは０又は１〜１０の整数を示す。）
上記一般式（Ｖ）で示されるフェノール・アラルキル樹脂としては、市販品として三井化学株式会社製商品名ＸＬＣが挙げられ、上記一般式（VI）で示されるビフェニル・アラルキル樹脂としては、市販品として明和化成株式会社製商品名ＭＥＨ−７８５１が挙げられる。 Examples of the phenol / aralkyl resin and biphenyl / aralkyl resin represented by the general formula (IV) include phenol resins represented by the following general formulas (V) and (VI).

(In general formula (V), n represents 0 or an integer of 1 to 10.)

(In general formula (VI), n represents 0 or an integer of 1 to 10.)
As a phenol aralkyl resin represented by the general formula (V), a trade name XLC manufactured by Mitsui Chemicals, Inc. may be mentioned as a commercially available product. As a biphenyl aralkyl resin represented by the general formula (VI), Meiwa Kasei Co., Ltd. product name MEH-7851 is mentioned.

（一般式（VII）で、ｎは０又は１〜１０の整数を示す。）

（一般式（VIII）で、ｎは０又は１〜１０の整数を示す。）

上記一般式（VII）で示されるナフトール・アラルキル樹脂としては、市販品として新日鐵化学株式会社製商品名ＳＮ−１７０が挙げられ、上記一般式（VIII）で示されるナフトール・アラルキル樹脂としては、市販品として新日鐵化学株式会社製商品名ＳＮ−４７５が挙げられる。また、上記一般式（V）〜（VIII）で示される化合物中の、ベンゼン環及びナフタレン環上の水素原子のいずれかを炭化水素基で置換した化合物も一般式（IV）で表される化合物に含まれる。 Examples of the naphthol / aralkyl resin represented by the general formula (IV) include resins represented by the following general formulas (VII) and (VIII).

(In general formula (VII), n represents 0 or an integer of 1 to 10.)

(In general formula (VIII), n represents 0 or an integer of 1 to 10.)

As a naphthol aralkyl resin represented by the above general formula (VII), as a commercial product, trade name SN-170 manufactured by Nippon Steel Chemical Co., Ltd. can be mentioned, and as a naphthol aralkyl resin represented by the above general formula (VIII), Moreover, Nippon Steel Chemical Co., Ltd. brand name SN-475 is mentioned as a commercial item. In addition, in the compounds represented by the general formulas (V) to (VIII), a compound in which any one of the hydrogen atoms on the benzene ring and the naphthalene ring is substituted with a hydrocarbon group is also represented by the general formula (IV). include.

  The above-mentioned phenol-aralkyl resin, biphenyl-aralkyl resin, and naphthol-aralkyl resin may be used alone or in combination of two or more, but the blending amount is based on the total amount of the curing agent. The total is preferably 60% by weight or more, and more preferably 80% by weight or more.

  The equivalent ratio of the (A) component epoxy resin and the (B) component curing agent, that is, the ratio of the number of epoxy groups in the epoxy resin / the number of hydroxyl groups in the curing agent is not particularly limited. Is preferably set in the range of 0.5 to 2, more preferably 0.6 to 1.5. 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.

The mixture as the component (C) of the present invention, that is, an epoxy resin having an ICI viscosity at 150 ° C. of 0.2 Pa · s or less (hereinafter referred to as (C1)), an oxidized polyolefin (hereinafter referred to as (C2)), And a mixture of α-olefin and at least one of a copolymer of maleic anhydride and maleic anhydride derivative, or two or more (hereinafter referred to as (C3)), serves as a mold release agent. It is.
The epoxy resin used for the component (C) needs to have an ICI viscosity at 150 ° C. of 0.2 Pa · s or less and 0.1 Pa · s or less from the viewpoint of fluidity after premixing. preferable. If it exceeds 0.2 Pa · s, the viscosity after premixing increases, which may adversely affect the fluidity of the sealing molding material. Here, the ICI viscosity refers to a value measured with an ICI cone plate rotational viscometer.

（一般式（IX）で、Ｒ¹〜Ｒ⁸は水素原子及び炭素数１〜１０の置換又は非置換の一価の炭化水素基から選ばれ、全てが同一でも異なっていてもよい。ｎは０〜３の整数を示す。）

（一般式（X）で、Ｒ₁〜Ｒ₁₀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又は１〜３の整数を示す。）

（一般式（XI）で、Ｒ¹〜Ｒ⁸は水素原子、置換又は非置換の炭素数１〜１０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。） As an epoxy resin (C1) having an ICI viscosity of 0.2 Pa · s or less at 150 ° C., a biphenyl type epoxy resin represented by the following general formula (IX), a bisphenol type epoxy resin represented by the general formula (X), Examples thereof include a sulfur-containing type epoxy resin represented by the formula (XI).

(In General Formula (IX), 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.)

(In the general formula (X), R _{1 to} R ₁₀ 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 or 1-3.)

(In General Formula (XI), R ^{1 to} R ⁸ are selected from a hydrogen atom, 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.)

Examples of the biphenyl type epoxy resin represented by the general formula (IX) 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 resin, a product name YX-4000H manufactured by Japan Epoxy Resin Co., Ltd. is commercially available.
As the bisphenol type epoxy resin represented by the general formula (X), for example, R ¹ , R ³ , R ⁶ and R ⁸ are methyl groups, and R ² , R ⁴ , R ⁵ , R ⁷ , R ⁹ and R YSLV-80XY (trade name, manufactured by Nippon Steel Chemical Co., Ltd.) having ¹⁰ as a hydrogen atom and n = 0 as a main component is commercially available.
As the sulfur-containing epoxy resin represented by the general formula (XI), for example, R ² and R ⁷ are methyl groups, R ³ and R ⁶ are tert-butyl groups, R ¹ , R ⁴ , R ⁵ and R ⁸ is a hydrogen atom, YSLV-120TE (manufactured by Nippon Steel Chemical Co., Ltd. trade name) composed mainly of n = 0 is commercially available.
As the epoxy resin of component (C), it is preferable from the viewpoint of fluidity and reliability to use one or more of the epoxy resins represented by the general formulas (IX) to (XI).

The oxidized polyolefin (C2) used for the component (C) in the present invention is a main component for the component (C) to act as a release agent. In order to obtain the effect of the present invention, it is necessary that the polyolefin in the component (C) is an oxidized type, and this is because the carboxyl group of the oxidized polyolefin and the epoxy resin (C1) in the component (C) are This is because the reaction promotes the dispersion of the polyolefin in the component (C). The acid value of the oxidized polyolefin is preferably 5 to 50 mg KOH / g, more preferably 10 to 40 mg KOH / g, and particularly preferably 15 to 30 mg KOH / g. If the acid value is less than 5 mgKOH / g, the reaction with the epoxy resin will be insufficient, causing the possibility of dispersion failure. If the acid value exceeds 50 mgKOH / g, the affinity with the epoxy resin will increase and the mold release effect. May become insufficient. In addition, the polyolefin in this invention is a compound which has ethylene polymer, a propylene polymer, an ethylene / propylene copolymer etc. as a main component.
The oxidized polyolefin as the component (C) also preferably has an ICI viscosity at 150 ° C. of 2.0 Pa · s or less, and more preferably 1.0 Pa · s or less. If it exceeds 2.0 Pa · s, the fluidity of the epoxy resin molding material for sealing will be adversely affected, or the difference in fluidity with the base resin will increase, causing package contamination due to resin flow. Tend.

（一般式（XII）で、Ｒ_１、Ｒ_２はアルキル基、又はアリール基を表し、互いに同じでも異なっていても良い。） In the component (C) in the present invention, in addition to an epoxy resin having an ICI viscosity at 150 ° C. of 0.2 Pa · s or less and an oxidized polyolefin, one or more kinds of α-olefin, maleic anhydride and anhydrous A copolymer (C3) with at least one of maleic acid derivatives is required.
The α-olefin used in the copolymer (C3) is not particularly limited. For example, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-pentene, Undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 1-docosene, 1-tricosene, 1-tetracocene, Linear α-olefins such as 1-pentacocene, 1-hexacocene, 1-heptacene, 3-methyl-1-butene, 3,4-dimethyl-pentene, 3-methyl-1-nonene, 3,4-dimethyl- Octene, 3-ethyl-1-dodecene, 4-methyl-5-ethyl-1-octadecene, 3,4,5-triethyl-1-eicosene It is like a branched α- olefins, may be used in combination of two or more even with these alone. In addition to maleic anhydride, maleic anhydride derivatives can include compounds represented by the following general formula (XII) such as methylmaleic anhydride, dimethylmaleic anhydride, and the like. Also, two or more kinds may be combined.

(In the general formula (XII), R ₁ and R ₂ represent an alkyl group or an aryl group, and may be the same or different from each other.)

上記一般式（XIII）及び（XIV）中のＲは、水素原子又は一価の脂肪族炭化水素基を示し、ｎは１以上の整数である。ｍは、α−オレフィンと無水マレイン酸の共重合比を示し、特に制限はないが、α−オレフィンをＸモル、無水マレイン酸をＹモルとした場合、Ｘ／Ｙ、すなわち、ｍは１／５〜５／１が好ましい。 The copolymer (C3) of the α-olefin and at least one of maleic anhydride and derivatives thereof (hereinafter referred to as “maleic anhydride”) is not particularly limited, but for example, it is represented by the following general formula (XIII). And a compound represented by the following general formula (XIV), and as a commercial product, Nissan Electol D121 (product manufactured by Nippon Oil & Fats Co., Ltd.) using 1-eicosene, 1-docosene and 1-tetracocene as raw materials Name) is available.

R in the general formulas (XIII) and (XIV) represents a hydrogen atom or a monovalent aliphatic hydrocarbon group, and n is an integer of 1 or more. m represents a copolymerization ratio of α-olefin and maleic anhydride, and is not particularly limited. However, when α-olefin is X mol and maleic anhydride is Y mol, X / Y, that is, m is 1 / 5 to 5/1 is preferable.

In order to obtain the effect of the present invention, it is preferable to use a copolymer of an α-olefin having 10 to 40 carbon atoms and maleic anhydrides, and an α-olefin having 15 to 30 carbon atoms and maleic anhydrides can be used. More preferably, a copolymer of an α-olefin having 18 to 25 carbon atoms and maleic anhydride is particularly preferably used. Further, the polymerization ratio of α-olefin to maleic anhydride (for example, m in the above general formulas (XIII) and (XIV)) is preferably α-olefin / maleic anhydride = 1/5 to 5/1, About 3 to 3/1 is more preferable, and 1/2 to 2/1 is particularly preferable. About 1/1 of about equimolar amount is more preferable. If the α-olefin has less than 10 carbon atoms, or the polymerization ratio of the α-olefin and maleic anhydride is less than 1/5, the hydrophilicity becomes too strong, and the phase with the oxidized polyolefin release agent (C) component If the α-olefin has more than 40 carbon atoms, or the α-olefin / maleic anhydride ratio is more than 5/1, the hydrophobicity becomes too strong, and the (A) component and (C1) component epoxy There is a tendency that the compatibility with the resin is poor. The molecular weight of the component (C3) is preferably 70,000 or less, more preferably 10,000 to 50,000, and still more preferably 20,000 to 40,000 from the viewpoint of mold / package contamination prevention and moldability. Here, the molecular weight of the component (C3) refers to the weight average molecular weight 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 substance: Polystyrene flow rate: 1.0 ml / min (sample concentration: about 0.2 wt / vol%)
Injection volume: 200 μl

There is no restriction | limiting in particular as a manufacturing method of the copolymer (C3) of (alpha) -olefin and maleic anhydrides, General copolymerization methods, such as making a raw material react, can be used. For the reaction, an organic solvent or the like in which the α-olefin and maleic anhydride can be dissolved 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 further preferably 4 to 10 hours from the viewpoint of productivity. After completion of the reaction, unreacted components, solvents and the like can be removed as necessary 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.

(一般式（III）で、Ｒ_１は水素原子又は脂肪族炭化水素基を表し、Ｒ_２は水素原子、又は飽和炭化水素基、又は不飽和の炭化水素基を表し、Ｒ_３、Ｒ_４ は飽和炭化水素基、又は不飽和の炭化水素基を表し、互いに同じでも異なっていても良い。Ｒ_５〜Ｒ_１０は水素原子又は飽和又は不飽和の炭化水素基を表し、互いに同じでも異なっていてもよい。ｐは正の整数を、ｑ、ｒ、ｓは０又は正の整数を表す。ただし、ｑ＝ｒ＝ｓ＝０を除く。)
上記一般式（III）で表される化合物は、一般式（III）に記載した通りの順番の重合形態に限定されず、また、ブロック共重合物に限定もされない。また、Ｒ_１は一般式（III）中の単量体部分の二つの炭素原子のどちらと結合していても良いし、Ｒ_２は式中の単量体部分の二つの酸素原子のどちらと結合していても良い。 It is more effective to use the compound represented by the general formula (III) as a copolymer of the (C3) component α-olefin and maleic anhydrides. The p to s of the general formula (III) and the constituent ratio thereof are preferably determined according to the oxidized polyolefin (C2) of the component (C).

(In the general formula (III), R ₁ represents a hydrogen atom or an aliphatic hydrocarbon group, R ₂ represents a hydrogen atom, a saturated hydrocarbon group, or an unsaturated hydrocarbon group, and R ₃ and R ₄ represent A saturated hydrocarbon group or an unsaturated hydrocarbon group, which may be the same or different, and R _{5 to} R ₁₀ each represents a hydrogen atom or a saturated or unsaturated hydrocarbon group, and may be the same or different from each other; P is a positive integer, q, r, and s are 0 or a positive integer, except that q = r = s = 0.
The compound represented by the general formula (III) is not limited to the polymerization form in the order as described in the general formula (III), and is not limited to the block copolymer. R ₁ may be bonded to any of the two carbon atoms of the monomer part in the general formula (III), and R ₂ may be any of the two oxygen atoms of the monomer part in the formula It may be combined.

The structure of the compound represented by the general formula (III) is preferably appropriately selected according to the oxidized polyolefin (C2), but R ₁ is an alkyl group having 10 to 40 carbon atoms, and R _{2 to} R ₄ are carbon. It is preferably an alkyl group having 5 to 30 carbon atoms, R ₁ is more preferably an alkyl group having 15 to 30 carbon atoms, R _{2 to} R ₄ are preferably alkyl groups having 8 to 25 carbon atoms, and R ₁ is carbon. It is particularly preferable that the alkyl group having 18 to 25 and R _{2 to} R ₄ are alkyl groups having 10 to 20 carbon atoms. R _{5 to} R ₁₀ represent a hydrogen atom or a hydrocarbon group, and at least one of R _{5 to} R ₁₀ is preferably a hydrogen atom, and more preferably all are hydrogen atoms. Two or more compounds having different structures may be used as the compound represented by the general formula (III).
Examples of the method for selecting the structure of the compound represented by the general formula (III) include the following examples. That is, when the weight average molecular weight of the oxidized polyolefin is less than 7000, in the general formula (III), a compound satisfying q> (r + s) and 1/3 <p / (q + r + s) <3/1 It is preferable to use a compound in which either r or s is 0 and 1/2 <p / (q + r + s) <2/1, and r = s = 0 and p / (q + r + s ) Is particularly preferably around 1. On the other hand, when the weight average molecular weight of the oxidized polyolefin (C2) is 7000 or more, a compound in which q ≦ (r + s) and 1/2 <p / (q + r + s) <2/1 in the general formula (III) Is preferable, and it is more preferable to use a compound in which q = s = 0 and p / (q + r + s) is around 1.
Further, when the weight average molecular weight of the oxidized polyolefin is 7000 or more, a compound in which q = s = 0 and p / (q + r + s) is around 1, r = s = 0, and p / (q + r + s) is It is also effective to use a compound of about 1 in combination. When these two types of compounds are used in combination, the ratio of q and (r + s), which is a combination of both, is preferably 5: 1 to 1: 5, more preferably 3: 1 to 1: 3, and 2: 1 to 1. : 2 is particularly preferable. In addition, the weight average molecular weight of oxidation type polyolefin is a measured value by high temperature GPC, and the measuring method in this invention is as follows.
Measuring instrument: High temperature GPC manufactured by Waters
Solvent: Dichlorobenzene Temperature: 140 ° C
Standard material: 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 method for producing the compound represented by the general formula (III) is not particularly limited. For example, a copolymer of α-olefin and maleic anhydride is prepared in advance, and then a maleic anhydride with a monohydric alcohol. Examples thereof include a method of esterifying the acid portion and a method of ring-opening the maleic anhydride portion of the copolymer with water. The method for esterifying a copolymer of an α-olefin and maleic anhydride with a monohydric alcohol is not particularly limited, and examples thereof include general methods such as addition reaction of a monohydric alcohol to the copolymer. it can.
The monohydric alcohol used for the esterification is not particularly limited, and examples thereof include amyl alcohol, isoamyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, capryl alcohol, nonyl alcohol, decyl alcohol, undecyl alcohol, and lauryl. Linear or branched aliphatic saturated alcohols such as alcohol, tridecyl alcohol, myristyl alcohol, pentadecyl alcohol, cetyl alcohol, heptadecyl alcohol, stearyl alcohol, nonadecyl alcohol, eicosyl alcohol, hexenol, 2-hexene- Linear or branched aliphatic unsaturated alcohols such as 1-ol, 1-hexen-3-ol, pentenol, 2-methyl-1-pentenol, cyclopentanol, Examples include alicyclic alcohols such as clohexanol, aromatic alcohols such as benzyl alcohol and cinnamyl alcohol, and heterocyclic alcohols such as furfuryl alcohol. These may be used alone or in combination of two or more. Also good.

In order to obtain the effect of the present invention, as component (C), epoxy resin (C1) having an ICI viscosity at 150 ° C. of 0.2 Pa · s or less, oxidized polyolefin (C2), α-olefin and maleic anhydrides It is necessary to use after pre-mixing the copolymer (C3). The ratio of the preliminary mixing is preferably such that the ratio of the epoxy resin (component (C1)) to the oxidized polyolefin (component (C2)) is (C1) / (C2) = 30/1 to 1/5 weight ratio. 20/1 to 1/3 weight ratio is more preferable, and 10/1 to 1/2 weight ratio is particularly preferable. The ratio of the component (C2) to the copolymer (component (C3)) is preferably (C2) / (C3) = 10/1 to 1/5 weight ratio. The weight ratio is more preferably 3% by weight, and particularly preferably 3/1 to 1/2 weight ratio.
As a specific example of the premixing method, the ratio of (C1) epoxy resin and (C2) oxidized polyolefin is 2/1, and these are premixed at 150 to 180 ° C. for 2 to 6 hours, and then (C3) copolymer Can be added such that the ratio of (C2) to oxidized polyolefin is (C2) / (C3) = 2/1, and mixing is further performed for 15 minutes to 4 hours.

  The blending amount of the component (C) is preferably about 0.03 to 5% by weight, more preferably about 0.05 to 3% by weight of the total molding material of the (C2) oxidized polyolefin. The content is preferably 0.1 to 2% by weight. If the amount is less than 0.03% by weight, the mold releasability may be insufficient, and if the amount exceeds 5% by weight, the effect on package contamination may be insufficient.

（一般式（I）で、ｎは０、又は１以上の整数を表す。R₁〜R₆は水素原子、水酸基、メトキシ基、エトキシ基、炭素数１〜６までのアルキル基から選ばれるものであり、互いに異なっていても同じであっても良い。）

（一般式（II）で、ｎは０、又は１以上の整数を表す。R₁〜R₆は水素原子、水酸基、メトキシ基、エトキシ基、炭素数１〜６までのアルキル基から選ばれるものであり、互いに異なっていても同じであっても良い。）
上記一般式（Ｉ）、一般式（II）で表される化合物がその効果を発揮する為には、封止用エポキシ樹脂成形材料のベース樹脂である（Ａ）成分や（Ｂ）成分に良好に分散することが必要であり、その為には軟化点が６０〜１３０℃程度であることが好ましく、７０〜１２０℃程度であることがより好ましく、８０〜１１０℃であることが特に好ましい。一般式（Ｉ）、一般式（II）の構造で言えば、R_１〜R_６のすべてが水素原子であるトリフェニルホスフィン・フェノールアラルキル付加物、トリフェニルホスフィン・フェノールノボラック付加物等を用いることが好ましく、いずれも軟化点の観点からはnが１０以下であることがより好ましく、ｎが５以下であることが特に好ましい。ｎが１０を超えると軟化点の上昇を招き、樹脂中への良好な分散が困難となり、成形性の点で不利となる可能性がある。 In this invention, it is necessary to use the compound represented by the following general formula (I) or general formula (II) as a (D) hardening accelerator individually or in combination. The compounds represented by general formula (I) and general formula (II) may be used in combination.

(In formula (I), n represents 0 or an integer of 1 or more. R _{1 to} R ₆ are selected from a hydrogen atom, a hydroxyl group, a methoxy group, an ethoxy group, and an alkyl group having 1 to 6 carbon atoms. And they may be different or the same.)

(In formula (II), n represents 0 or an integer of 1 or more. R _{1 to} R ₆ are selected from a hydrogen atom, a hydroxyl group, a methoxy group, an ethoxy group, and an alkyl group having 1 to 6 carbon atoms. And they may be different or the same.)
In order for the compounds represented by the above general formula (I) and general formula (II) to exert their effects, they are good for the components (A) and (B) that are the base resins of the epoxy resin molding material for sealing. For this purpose, the softening point is preferably about 60 to 130 ° C, more preferably about 70 to 120 ° C, and particularly preferably 80 to 110 ° C. Speaking of the structures of general formula (I) and general formula (II), use a triphenylphosphine / phenol aralkyl adduct, triphenylphosphine / phenol novolac adduct, etc., in which all of R _{1 to} R ₆ are hydrogen atoms. In any case, from the viewpoint of the softening point, n is more preferably 10 or less, and n is particularly preferably 5 or less. If n exceeds 10, the softening point is increased, and it is difficult to disperse the resin in the resin, which may be disadvantageous in terms of moldability.

  In the present invention, in addition to the general formula (I) and general formula (II), a curing accelerator that is usually used in an epoxy resin molding material for sealing is used in combination without limitation, as long as the effects of the present invention are not lost. can do. Examples of curing accelerators that can be used in combination include, for example, 1,8-diaza-bicyclo (5,4,0) undecene-7, 1,5-diaza-bicyclo (4,3,0) nonene, Cycloamidine compounds such as 6-dibutylamino-1,8-diaza-bicyclo (5,4,0) undecene-7, and these compounds include maleic anhydride, 1,4-benzoquinone, 2,5-toluquinone, 1, 4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, phenyl-1, Benzyldimethylamine, a compound having intramolecular polarization formed by adding a quinone compound such as 4-benzoquinone, a compound having a π bond such as diazophenylmethane or phenol resin Tertiary amine compounds such as triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol, and derivatives thereof, imidazole compounds such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, and the like Derivatives, tributylphosphine, methyldiphenylphosphine, triphenylphosphine, tris (4-methylphenyl) phosphine, diphenylphosphine, phenylphosphine, and other organic phosphines, and maleic anhydride, quinone compounds, diazophenylmethane Organic phosphorus compounds such as compounds having intramolecular polarization, tetraphenylphosphonium tetraphenyl borate, triphenylphosphine tetraphenyl volley , 2-ethyl-4-methylimidazole tetraphenyl borate, etc. tetraphenyl boron salts and derivatives thereof such as N- methylmorpholine tetraphenylborate and the like.

  The compounding amount of the compound represented by the general formula (I) and / or the general formula (II) as the component (D) is not particularly limited as long as the effect of promoting the curing is achieved. 0.1-15 weight% is preferable with respect to resin (A), More preferably, it is 1-10 weight%. If it is less than 0.1% by weight, the curability in a short time tends to be inferior. If it exceeds 15% by weight, the curing rate tends to be too fast, and it tends to be difficult to obtain a good molded product due to unfilling or the like. Moreover, when using together hardening accelerators other than (D) component, after making the compounding quantity of (D) component into 50 weight% or more of the whole hardening accelerator, those compounding total amounts shall enter said range. Is preferred.

In the present invention, it is also possible to add an inorganic filler for hygroscopicity, reduction of linear expansion coefficient, improvement of thermal conductivity and improvement of strength. Examples of the inorganic filler include fused silica, crystalline silica, alumina, zircon, calcium silicate, calcium carbonate, potassium titanate, silicon carbide, silicon nitride, aluminum nitride, boron nitride, beryllia, zirconia, zircon, fosterite, steer. Examples thereof include powders such as tight, 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, zinc borate, and zinc molybdate. These inorganic fillers may be used alone or in combination of two or more. Among the above inorganic fillers, fused silica is preferable from the viewpoint of reducing the linear expansion coefficient, and alumina is preferable from the viewpoint of high thermal conductivity, and the filler shape is spherical from the viewpoint of fluidity during molding and mold wear. Is preferred.
The blending amount of the inorganic filler is preferably 70% by weight or more based on the epoxy resin molding material for sealing, from the viewpoint of moldability, hygroscopicity, reduction of linear expansion coefficient and strength improvement, and is in the range of 75 to 96% by weight. Is more preferable, and 80 to 92% by weight is more preferable. If it is less than 70% by weight, the reliability tends to decrease, and if it exceeds 96% by weight, the moldability tends to decrease.

  The sealing epoxy resin molding material of the present invention includes higher fatty acid waxes such as stearic acid and montanic acid, and higher fatty acid ester waxes such as stearic acid ester and montanic acid ester as long as the effects of the present invention can be achieved. In addition to the component (C), conventionally known release agents such as higher fatty acid amide waxes such as stearic acid amide and montanic acid amide can be used in combination.

An anion exchanger can be added to the sealing epoxy resin molding material of the present invention from the viewpoint of improving the moisture resistance and high temperature storage characteristics of a semiconductor element such as an IC. The anion exchanger is not particularly limited and conventionally known anion exchangers can be used. For example, hydrotalcite, hydrous oxide of an element selected from antimony, bismuth, zirconium, titanium, tin, magnesium, and aluminum These can be used, and these can be used alone or in combination of two or more. Of these, hydrotalcite and bismuth hydrous oxide represented by the following general formula (XV) are preferable.
(Chemical Formula 17)
Mg _1-X Al _X (OH) ₂ (CO ₃ ) _{X / 2} · mH ₂ O (XV)
(0 <X ≦ 0.5, m is a positive integer)
The amount of the anion exchanger is not particularly limited as long as it is sufficient to capture ionic impurities such as halogen ions, but is preferably 0.1 to 30% by weight with respect to the epoxy resin of component (A). 1-10 weight% is more preferable, and 2-5 weight% is further more preferable. If the blending amount is less than 0.1% by weight, trapping of ionic impurities tends to be insufficient, and if it exceeds 30% by weight, there is no significant difference in the effect compared to the amount less than that, which is economically disadvantageous.

In the epoxy resin molding material for sealing of the present invention, epoxy silane, mercapto silane, amino silane, alkyl silane, ureido silane, vinyl silane, etc. are used as necessary to enhance the adhesion between the resin component and the inorganic filler. Various known coupling agents such as various silane compounds, titanium compounds, aluminum chelates, and aluminum / zirconium compounds can be added. 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-aminopropyltriethoxysilane, γ-anilinopropyltrimethoxysilane, γ-ani Linopropylmethyldimethoxysilane, γ- [bis (β-hydroxyethyl)] aminopropyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, γ- (β-aminoethyl) aminopropi Dimethoxymethylsilane, N- (trimethoxysilylpropyl) ethylenediamine, N- (dimethoxymethylsilylisopropyl) ethylenediamine, methyltrimethoxysilane, dimethyldimethoxysilane, methyltriethoxysilane, N-β- (N-vinylbenzylaminoethyl) Silane coupling agents such as γ-aminopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, hexamethyldisilane, vinyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, isopropyltriisostearoyl titanate, isopropyltris ( Dioctyl pyrophosphate) titanate, isopropyl tri (N-aminoethyl-aminoethyl) titanate, tetraoctyl bis (ditridecyl phosphite) Titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, bis (dioctylpyrophosphate) oxyacetate titanate, bis (dioctylpyrophosphate) ethylene titanate, isopropyltrioctanoyl titanate, isopropyl Titanate coupling agents such as dimethacrylisostearoyl titanate, isopropyl tridodecylbenzenesulfonyl titanate, isopropyl isostearoyl diacryl titanate, isopropyl tri (dioctyl phosphate) titanate, isopropyl tricumyl phenyl titanate, tetraisopropyl bis (dioctyl phosphite) titanate Even if these are used alone, two or more are combined. It can have.
The amount of the coupling agent is preferably 0.05 to 5% by weight, more preferably 0.1 to 2.5% by weight, based on the inorganic filler. If it is less than 0.05% by weight, the moisture resistance tends to decrease, and if it exceeds 5% by weight, the moldability of the package tends to decrease.

  Further, in the epoxy resin molding material for sealing of the present invention, as other additives, flexible agents such as silicone oil and silicone rubber powder, brominated epoxy resin, antimony trioxide, antimony tetroxide, antimony pentoxide Known organic or inorganic compounds containing halogen atoms such as antimony atoms, nitrogen atoms or phosphorus atoms, flame retardants such as metal hydroxides, carbon black, organic dyes, organic pigments, titanium oxide, red lead, bengara, etc. Colorants, imidazole, triazole, tetrazole, triazine, etc. and their derivatives, anthranilic acid, gallic acid, malonic acid, malic acid, maleic acid, aminophenol, quinoline, etc. and their derivatives, aliphatic acid amide compounds, dithiocarbamates Add adhesion promoters such as thiadiazole derivatives as necessary Door can be.

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. A method of sufficiently cooling and pulverizing after mixing and melting and kneading with a mixing roll, a kneader, an extruder or the like can be mentioned. It is easy to use if it is tableted with dimensions and weight that match the molding conditions.
Moreover, the epoxy resin molding material for sealing of the present invention can be dissolved in various organic solvents and used as a liquid epoxy resin molding material for liquid sealing. This liquid epoxy resin molding material for liquid sealing can be used on a plate or a film. It can also be used as an epoxy resin molding material for sealing in the form of a sheet or film obtained by coating thinly and scattering the organic solvent under conditions that do not allow the resin curing reaction to proceed so much.

  As an electronic component device obtained by sealing an element with the sealing epoxy resin molding material obtained in the present invention, a lead frame, a wired tape carrier, a wiring board, glass, a silicon wafer, a support member such as a semiconductor Electronic components equipped with active elements such as chips, transistors, diodes, thyristors, etc., and passive elements such as capacitors, resistors, coils, etc., and the necessary parts are sealed with the sealing epoxy resin molding material of the present invention Examples thereof include devices. As such an electronic component device, for example, a semiconductor element is fixed on a lead frame, and a terminal portion and a lead portion of an element such as a bonding pad are connected by wire bonding or bump, and then the epoxy resin for sealing of the present invention is used. DIP (Dual Inline Package), PLCC (Plastic Leaded Chip Carrier), QFP (Quad Flat Package), SOP (Small Outline Package), SOJ (Small Outline J-) General resin-encapsulated ICs such as lead package (TSP), TSOP (Thin Small Outline Package), and TQFP (Thin Quad Flat Package), and semiconductor chip connected to the tape carrier with bumps are molded with epoxy resin for encapsulation. TCP (Tape Carrier Package) sealed with materials, wire bonding, flip chip bonding to wiring formed on wiring boards and glass COB (Chip On) in which active elements such as semiconductor chips, transistors, diodes, thyristors and / or passive elements such as capacitors, resistors, coils, etc., which are connected by solder or the like, are sealed with the sealing epoxy resin molding material of the present invention. Board) module, hybrid IC, multi-chip module, an element mounted on an organic substrate on which terminals for wiring board connection are formed, and after connecting the element and the wiring formed on the organic substrate by bump or wire bonding, Examples thereof include BGA (Ball Grid Array) and CSP (Chip Size Package) in which the element is sealed with a sealing epoxy resin molding material. Moreover, the epoxy resin molding material for sealing of the present invention can also be used effectively for printed circuit boards.

As a method for sealing an element using the epoxy resin molding material for sealing of the present invention, a low-pressure transfer molding method is the most common, but an injection molding method, a compression molding method, or the like may be used. When the sealing epoxy resin molding material is liquid or pasty at normal temperature, a dispensing method, a casting method, a printing method, and the like can be given.
Also, not only a general sealing method for directly sealing an element with a resin, but also a hollow package system in which an epoxy resin molding material for sealing an electronic component is not in direct contact with the element, sealing for a hollow package Also suitable for use as an epoxy resin molding material.

Examples 1-4 and Comparative Examples 1-7
As an epoxy resin of component (A), an epoxy equivalent of 196, a biphenyl type epoxy resin having a melting point of 106 ° C. (trade name Epicoat YX-4000H manufactured by Japan Epoxy Resin Co., Ltd.),
As a curing agent for the component (B), a phenol-aralkyl resin (trade name: Millex XL-225, manufactured by Mitsui Chemicals, Inc.) having a softening point of 70 ° C. was prepared.
(C) Component (C1) Epicote YX-4000H (ICI viscosity at 150 ° C. of 0.01 Pa · s), (C2) Oxidized polyethylene having an ICI viscosity at 150 ° C. of 0.05 Pa · s and a weight average molecular weight of 5000 (Mitsui Chemicals, Inc., trade name Hi-wax 4202E), and (C3) below in formula (III) r = s = 0 , p / q = 1/1, R 5, R 6 are hydrogen, _{R 1} is carbon Weight ratio of (C1) / (C2) / (C3) = 4/2/1 for a compound (Nippon Yushi Co., Ltd., trade name Nissan Electol D121) which is a mixture of saturated hydrocarbon groups of formulas 18, 20, and 22. Release agent 1 premixed with
Epicoat YX-4000H, oxidized polyethylene (trade name PE-A, manufactured by Dainichi Chemical Co., Ltd.) having an ICI viscosity at 150 ° C. of 0.5 Pa · s and a weight average molecular weight of 7000, and q in the following general formula (III) = S = 0, p / r = 1/1, R _{7 and} R ₈ are hydrogen atoms, R ₁ is a saturated hydrocarbon group having 18, 20, and 22 carbon atoms, and R ₂ is a saturated hydrocarbon group having 12 carbon atoms. Release agent 2 in which a compound is premixed at 4/2/1,
As a comparative mold release agent for component (C), comparative mold release agent 1 was prepared by premixing Epicoat YX-4000H and high wax 4202E at a ratio of 2/1.
(D) a compound having a general formula (I) in which R _{1 to} R ₆ are hydrogen atoms and n = 3 to 4 (softening point 110 ° C., curing accelerator 1) as a curing accelerator of component (D),
A compound in which R _{1 to} R ₆ are hydrogen atoms and n = 3 to 4 in the general formula (II) (softening point 110 ° C., curing accelerator 2),
(D) Triphenylphosphine (melting point 85 ° C., comparative curing accelerator 1) as a comparative curing accelerator of the component,
Adduct of triphenylphosphine and p-benzoquinone (comparative curing accelerator 2),
A phenol novolak adduct of 1,8-diaza-bicyclo (5,4,0) undecene-7 (softening point 135 ° C., comparative curing accelerator 3) was prepared.
Spherical fused silica having an average particle size of 17.5 μm and a specific surface area of 3.8 m ² / g as an inorganic filler, γ-glycidoxypropyltrimethoxysilane (epoxysilane) as a coupling agent, antimony trioxide and epoxy as a flame retardant Bisphenol A-type brominated epoxy resin (trade name ESB-400T manufactured by Sumitomo Chemical Co., Ltd.) having an equivalent weight of 375, a softening point of 80 ° C. and a bromine content of 48% by weight, and carbon black (trade name MA- manufactured by Mitsubishi Chemical Corporation) as a colorant. 100).

（一般式（I）で、ｎは０、又は１以上の整数を表す。R₁〜R₆は水素原子、水酸基、メトキシ基、エトキシ基、炭素数１〜６までのアルキル基から選ばれるものであり、互いに異なっていても同じであっても良い。）

（一般式（II）で、ｎは０、又は１以上の整数を表す。R₁〜R₆は水素原子、水酸基、メトキシ基、エトキシ基、炭素数１〜６までのアルキル基から選ばれるものであり、互いに異なっていても同じであっても良い。）

(一般式（III）で、Ｒ_１は水素原子又は脂肪族炭化水素基を表し、Ｒ_２は水素原子、又は飽和炭化水素基、又は不飽和の炭化水素基を表し、Ｒ_３、Ｒ_４は飽和炭化水素基、又は不飽和の炭化水素基を表し、互いに同じでも異なっていても良い。Ｒ_５〜Ｒ_１０は水素原子又は飽和又は不飽和の炭化水素基を表し、互いに同じでも異なっていてもよい。ｐは正の整数を、ｑ、ｒ、ｓは０又は正の整数を表す。ただし、ｑ＝ｒ＝ｓ＝０を除く。) These were blended in parts by weight shown in Table 1 and Table 2, respectively, and roll kneading was carried out under conditions of a kneading temperature of 80 ° C. and a kneading time of 10 minutes to produce epoxy resin molding materials for sealing of Examples and Comparative Examples. . In addition, as the release agent 1 and 2 of the component (C), after the YX-4000H and the oxidized polyolefin are mixed with stirring at 170 ° C. for 4 hours, the compound represented by the general formula (III) is added. Further, it was obtained by stirring and mixing at 170 ° C./15 minutes. Moreover, the comparative mold release agent 1 of (C) component was obtained by stirring and mixing YX-4000H and oxidized polyolefin for 170 degreeC / 4 hours, respectively.
Moreover, the weight average molecular weight of the oxidation type polyolefin of (C) component is a measured value in high temperature GPC, and the measuring method is as follows.
Measuring instrument: High temperature GPC manufactured by Waters
Solvent: Dichlorobenzene Temperature: 140 ° C
Standard material: 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

(In formula (I), n represents 0 or an integer of 1 or more. R _{1 to} R ₆ are selected from a hydrogen atom, a hydroxyl group, a methoxy group, an ethoxy group, and an alkyl group having 1 to 6 carbon atoms. And they may be different or the same.)

(In formula (II), n represents 0 or an integer of 1 or more. R _{1 to} R ₆ are selected from a hydrogen atom, a hydroxyl group, a methoxy group, an ethoxy group, and an alkyl group having 1 to 6 carbon atoms. And they may be different or the same.)

(In the general formula (III), R ₁ represents a hydrogen atom or an aliphatic hydrocarbon group, R ₂ represents a hydrogen atom, a saturated hydrocarbon group, or an unsaturated hydrocarbon group, and R ₃ and R ₄ represent A saturated hydrocarbon group or an unsaturated hydrocarbon group, which may be the same or different, and R _{5 to} R ₁₀ each represents a hydrogen atom or a saturated or unsaturated hydrocarbon group, and may be the same or different from each other; P is a positive integer, q, r, and s are 0 or a positive integer, except that q = r = s = 0.

The produced epoxy resin molding materials for sealing of Examples and Comparative Examples were evaluated by the following tests. The evaluation results are shown in Tables 3 and 4.
(Package dirt, presence or absence of resin adhesion to the air vent (LQFP))
Using a TOWA press (Y series manufactured by Towa Seiki Co., Ltd., package thickness 1.4 mm for LQFP144p), 300 shots are continuously molded under conditions of 180 ° C, 6.9 MPa, 60 seconds. By visually observing the molded product sampled every 50 shots, the presence or absence and degree of package contamination were confirmed. In addition, the presence or absence of burrs on the mold air vent during continuous molding was confirmed.

Comparative Examples 1 and 2 in which the component (C) was removed from the present invention were inferior to package contamination, and Comparative Examples 3 to 7 in which the component (D) was removed were uncured or inferior to air vent burr adhesion.
On the other hand, it can be seen that Examples 1 to 4 including all of the components (A) to (D) are excellent in both package contamination and air vent burr adhesion.

Claims (3)

(A) epoxy resin, (B) curing agent, (C) epoxy resin (C1) having an ICI viscosity at 150 ° C. of 0.2 Pa · s or less, oxidized polyolefin (C2), and α-olefin and maleic anhydride A mixture obtained by premixing one or more copolymers (C3) of at least one of maleic anhydride derivatives, (D) at least one of the compounds represented by the following general formulas (I) and (II), An epoxy resin molding material for sealing containing

(In formula (I), n represents 0 or an integer of 1 or more. R _{1 to} R ₆ are selected from a hydrogen atom, a hydroxyl group, a methoxy group, an ethoxy group, and an alkyl group having 1 to 6 carbon atoms. And they may be different or the same.)

(In formula (II), n represents 0 or an integer of 1 or more. R _{1 to} R ₆ are selected from a hydrogen atom, a hydroxyl group, a methoxy group, an ethoxy group, and an alkyl group having 1 to 6 carbon atoms. And they may be different or the same.) The epoxy resin for sealing according to claim 1, wherein the copolymer of the α-olefin of component (C) and at least one of maleic anhydride and a maleic anhydride derivative is a compound represented by the following general formula (III): Molding material.

(In General Formula (III), R ₁ represents a hydrogen atom or an aliphatic hydrocarbon group, R ₂ represents a hydrogen atom, a saturated hydrocarbon group, or an unsaturated hydrocarbon group, and R ₃ and R ₄ are saturated. Represents a hydrocarbon group or an unsaturated hydrocarbon group, and may be the same or different from each other, R _{5 to} R ₁₀ represent a hydrogen atom or a saturated or unsaturated hydrocarbon group, and may be the same or different from each other; P is a positive integer, q, r, and s are 0 or a positive integer, except for q = r = s = 0.   The electronic component apparatus provided with the element sealed with the epoxy resin molding material for sealing of Claim 1 or 2.