JP2008120995A - Epoxy resin composition and electronic component device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an epoxy resin composition for sealing, which is excellent in peeling resistance upon re-flow mounting while keeping moldability and successive working in good conditions and an electronic component device in which the same is used. <P>SOLUTION: The epoxy resin composition for sealing contains (A) an epoxy resin, (B) a curative, (C) an indene-styrene-phenol copolymerization oligomer, and (D) an inorganic filler, wherein 15 to 25 parts by weight of (C) the indene-styrene-phenol copolymerization oligomer is contained per 100 parts by weight of (A) the epoxy resin and 85% by weight or more of (D) the inorganic filler is contained in the epoxy resin composition. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an epoxy resin composition for an electronic component device and an electronic component device.

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

JP-A-10-330591

  However, it was not possible to obtain a sufficient effect of peeling resistance at the time of reflow mounting only by using the above copolymer oligomer.

  In order to solve the above-mentioned problems, the present invention has been intensively researched to find a material that is excellent in curability and continuous workability, but has excellent peeling resistance during reflow mounting. The inventors have found that an epoxy resin sealing material satisfying the above requirements can be obtained by adding a specific amount of a phenol copolymer oligomer, and the present invention has been completed.

The present invention relates to the following.
(1). An epoxy resin composition for sealing containing (A) an epoxy resin, (B) a curing agent, (C) an indene / styrene / phenol copolymer oligomer and (D) an inorganic filler, (A) epoxy resin 100 (C) 15 to 25 parts by mass of indene / styrene / phenol copolymer oligomer, and (D) an epoxy resin composition for sealing containing 85% by mass or more of the epoxy resin composition with respect to parts by mass .
(2). (A) The epoxy resin composition for sealing according to (1), wherein the epoxy resin contains one or more of a biphenyl type epoxy resin, a biphenylene type epoxy resin, and a sulfur atom-containing epoxy resin.
(3). (A) The epoxy resin composition for sealing according to the above (1) or (2), wherein the epoxy resin contains a novolac type epoxy resin.
(4). (B) The epoxy resin composition for sealing according to any one of (1) to (3), wherein the curing agent is a xylylene type phenol / aralkyl resin.
(5). (D) The sealing epoxy resin composition according to any one of (1) to (4), wherein the content of the inorganic filler is 90% by mass or less.
(6). An electronic component device comprising an element sealed with the sealing epoxy resin composition according to any one of (1) to (5).

  The epoxy resin composition for sealing of the present invention can provide a sealing material excellent in peel resistance during reflow mounting and an electronic component device using the same.

  The epoxy resin used in the present invention is not particularly limited. For example, it is generally used in an epoxy resin molding material for sealing electronic parts, and includes a biphenyl type epoxy resin, a biphenylene type epoxy resin, a phenol novolac type epoxy resin, Epoxy resin, bisphenol A, bisphenol F, bisphenol S, alkyl, epoxidized novolak resin synthesized from orthocresol novolac type epoxy resin, bisphenol A novolak type epoxy resin and / or naphthols and aldehydes Diglycidyl ethers such as substituted biphenols, stilbene-type epoxy resins, diaminodiphenylmethane, isocyanuric acid and other polyamines obtained by the reaction of epichlorohydrin Epoxy resins, dicyclopentadiene type epoxy resins that are epoxidized products of co-condensation resins of dicyclopentadiene and phenols, naphthalene type epoxy resins having a naphthalene ring, epoxides of naphthol / aralkyl resins, triphenylmethane type epoxy resins, Examples thereof include a methylolpropane type epoxy resin, a terpene-modified epoxy resin, a sulfur atom-containing epoxy resin, a linear aliphatic epoxy resin obtained by oxidizing an olefin bond with a peracid such as peracetic acid, and an alicyclic epoxy resin.

  Among them, biphenyl type epoxy resins, sulfur atom-containing epoxy resins and biphenylene type epoxy resins are preferable from the viewpoint of peeling resistance during reflow mounting, and novolac type epoxy resins are preferable from the viewpoint of curability. It is preferable to contain at least one kind.

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

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

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

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

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

（ここで、Ｒ^１〜Ｒ^８は水素原子及び炭素数１〜５の置換又は非置換の一価の炭化水素基から選ばれ、全てが同一でも異なっていてもよい。ｎは０〜１０の整数を示す。）

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

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

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

  Examples of the biphenyl type epoxy resin represented by the general formula (I) 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.

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

Among the sulfur atom-containing epoxy resins represented by the general formula (IV), R ² , R ³ , R ⁶ and R ⁷ are hydrogen atoms, and R ¹ , R ⁴ , R ⁵ and R ⁸ are alkyl groups. An epoxy resin is preferable, and an epoxy resin in which R ² , R ³ , R ⁶ and R ⁷ are hydrogen atoms, R ¹ and R ⁸ are tert-butyl groups, and R ⁴ and R ⁵ are methyl groups is more preferable. As such a compound, YSLV-120TE (manufactured by Nippon Steel Chemical Co., Ltd.) and the like are commercially available.

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

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

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

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

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

Wherein R ¹ and R ² are each independently selected from a hydrogen atom and a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, n is an integer of 0 to 10, and m is Represents an integer of 0 to 6.)

R ¹ in the above formula (VI) is, for example, a hydrogen atom, methyl group, ethyl group, propyl group, butyl group, isopropyl group, tert-butyl group or other alkyl group, vinyl group, allyl group, butenyl group, etc. C1-C5 substituted or unsubstituted monovalent hydrocarbon groups such as alkenyl groups, halogenated alkyl groups, amino group-substituted alkyl groups, mercapto group-substituted alkyl groups, and the like. Among them, methyl groups, ethyl groups Alkyl groups and hydrogen atoms such as methyl groups and hydrogen atoms are more preferable. Examples of R ² include a hydrogen atom, an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, and a tert-butyl group, an alkenyl group such as a vinyl group, an allyl group, and a butenyl group, and an alkyl halide. Examples thereof include substituted or unsubstituted monovalent hydrocarbon groups having 1 to 5 carbon atoms such as a group, an amino group-substituted alkyl group, and a mercapto group-substituted alkyl group, and among them, a hydrogen atom is preferable.

  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 (VII), and examples of the triphenylmethane type epoxy resin include an epoxy resin represented by the following general formula (VIII).

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

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

  The naphthalene type epoxy resin represented by the general formula (VII) includes a random copolymer containing 1 constituent unit and m constituent units at random, an alternating copolymer containing alternating units, and a copolymer containing regularly. Examples thereof include block copolymers which are included in a combined or block form, and any one of these may be used alone, or two or more may be used in combination.

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

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

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

（ここで、ｎは１〜１０の整数を示す。）

(Here, n represents an integer of 1 to 10.)

  Any of the above biphenyl type epoxy resin, biphenylene 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 One type may be used alone or two or more types may be used in combination, 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. 80% by mass or more is more preferable.

  The melt viscosity at 150 ° C. of the (A) epoxy resin used in the present invention is preferably 2.0 poise or less, more preferably 1.0 poise or less, and further preferably 0.5 poise or less from the viewpoint of fluidity. Here, the melt viscosity is a viscosity measured with an ICI cone plate viscometer.

  Curing agents that can be used in the present invention are generally used for sealing epoxy resin molding materials and are not particularly limited. For example, phenol, cresol, resorcin, catechol, bisphenol A, bisphenol F, and phenylphenol. Phenols such as aminophenol and / or naphthols such as α-naphthol, β-naphthol, dihydroxynaphthalene and the like and compounds having an aldehyde group such as formaldehyde, benzaldehyde, salicylaldehyde, etc., are condensed or co-condensed in the presence of an acidic catalyst. The resulting novolak-type phenolic resin, phenols and / or naphthols and dimethoxyparaxylene or bis (methoxymethyl) biphenyl synthesized aralkyl resins such as phenol aralkyl resins and naphthol aralkyl resins Examples thereof include a rukyle type phenol resin, a dicyclopentadiene type phenol resin, and a terpene-modified phenol resin, and these may be used alone or in combination of two or more.

  Among these, xylylene type phenol / aralkyl resin is preferable from the viewpoint of peeling resistance during reflow mounting.

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

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

Examples of the biphenyl type phenol resin represented by the general formula (X) include compounds in which R ^{1 to} R ⁹ are all hydrogen atoms, and in particular, from the viewpoint of melt viscosity, a condensate having n of 1 or more is used. A mixture of condensates containing 50% by mass or more is preferred. As such a compound, MEH-7785 (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 (XI) is preferable, and R in the general formula (XI) is a hydrogen atom. , A phenol / aralkyl resin having an average value of n of 0 to 8 is more preferable. Specific examples include p-xylylene type phenol / aralkyl resins, m-xylylene type phenol / aralkyl resins, and the like. Such a xylylene-type phenol-aralkyl resin is commercially available as Milex XLC-3L (manufactured by Mitsui Chemicals, Inc.). 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.

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

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

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

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

Wherein R ¹ and R ² are each independently selected from a hydrogen atom and a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, n is an integer of 0 to 10, and m is Represents an integer of 0 to 6.)

  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 (XIII).

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

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

  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.

  These curing agents can be used alone or in combination of two or more.

  In addition, the equivalent ratio of the epoxy resin and the curing agent of component (A), 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. In order to obtain a composition excellent in moldability and reflow resistance, it is preferably set in the range of 0.8 to 1.2. If it is less than 0.5 equivalent, curing of the epoxy resin becomes insufficient, and the heat resistance, moisture resistance and electrical properties of the cured product are inferior. On the other hand, if it exceeds 1.5 equivalents, the curing agent component becomes excessive and a large amount of phenolic hydroxyl group remains in the cured resin, resulting in poor electrical characteristics and moisture resistance.

The (C) indene / styrene / phenol copolymer oligomer (hereinafter also referred to as indene oligomer resin) used in the present invention includes, for example, indene such as indene and alkylindene and styrene such as styrene and alkylstyrene. It is a copolymer resin of phenols, and is obtained by cationic polymerization of these monomers using Lewis acid, Bronsted acid, or solid acid as a catalyst. The proportion of indene is preferably 60% by mass or more based on the total of the (C) indene-based oligomer resin component, and an aromatic olefin such as coumarone may be contained as another constituent monomer.
(C) The indene oligomer resin is not particularly limited, but those having a number average molecular weight of 300 to 1000 and a softening point of 50 to 160 ° C are preferable. Specific examples thereof include trade names I-100, IP-100, I-120, and IP-120 manufactured by Nippon Steel Chemical Co., Ltd. When the blending amount of the indene oligomer resin is 15 to 25 parts by mass with respect to 100 parts by mass of the epoxy resin of the component (A), the balance between the peel resistance at the time of reflow mounting, the moldability, and the continuous workability was excellent. The effect is demonstrated. More preferably, it is 20-25 mass parts.

  The curing accelerator that can be used in the present invention is not particularly limited, and is generally used for an epoxy resin molding material for sealing. For example, 1,8-diaza-bicyclo (5,4,0) undecene-7, 1,5-diaza-bicyclo (4,3,0) nonene, 5,6-dibutylamino-1,8-diaza-bicyclo Tertiary amines such as (5,4,0) undecene-7, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol and their derivatives; 2-methylimidazole, 2-phenylimidazole Imidazoles such as 2-phenyl-4-methylimidazole and derivatives thereof; organic phosphines such as tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine, and phenylphosphine; and maleic anhydride to these phosphines, Benzoquinone, diazophenyl Phosphorus compounds having intramolecular polarization formed by adding a compound having a π bond such as thiol; tetraphenylphosphonium tetraphenylborate, triphenylphosphinetetraphenylborate, 2-ethyl-4-methylimidazoletetraphenylborate, N-methyl Examples thereof include tetraphenylboron salts such as morpholine tetraphenylborate and derivatives thereof. These may be used alone or in combination of two or more.

  The coupling agent is not particularly limited, and conventionally known coupling agents such as silane coupling agents can be used alone or in combination. For example, vinyltrichlorosilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyl Trimethoxysilane, vinyltriacetoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ- [bis (β-hydroxyethyl)] aminopropyltriethoxysilane, N-β- (aminoethyl) -Γ-aminopropyltrimethoxysilane, γ- (β-aminoethyl) aminopropyldimethoxymethylsilane, N- (trimethoxysilylpropyl) ethylenediamine, N- (dimethoxymethylsilylisopropyl) ethylenediamine, Tiltrimethoxysilane, methyltriethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, hexamethyldisilane, γ-anilinopropyltrimethoxy Silane coupling agents such as silane, vinyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, or isopropyltriisostearoyl titanate, isopropyltris (dioctylpyrophosphate) titanate, isopropyltri (N-aminoethyl-aminoethyl) titanate Tetraoctyl bis (ditridecyl phosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, bis (dio Tylpyrophosphate) oxyacetate titanate, bis (dioctylpyrophosphate) ethylene titanate, isopropyltrioctanoyl titanate, isopropyldimethacrylisostearoyl titanate, isopropyltridodecylbenzenesulfonyl titanate, isopropylisostearoyl diacryl titanate, isopropyltri (dioctylphosphate) One or more titanate coupling agents such as titanate, isopropyl tricumylphenyl titanate, and tetraisopropyl bis (dioctyl phosphite) titanate can be used in combination.

  Further, a release agent may be used, and there is no particular limitation. However, a release agent such as natural wax, synthetic wax, oxidized or non-oxidized polyolefin, such as carnauba wax and polyethylene wax may be used alone or in combination. Can be used.

  (D) Inorganic filler used in the present invention is not particularly limited, but powders such as fused silica, crystalline silica, alumina, zircon, calcium silicate, calcium carbonate, silicon carbide, aluminum nitride, boron nitride, beryllia, zirconia, etc. One or more kinds of spheres, beads obtained by spheroidizing them, single crystal fibers such as potassium titanate, silicon carbide, silicon nitride, and alumina, glass fibers, and the like can be used. Furthermore, examples of the inorganic filler having a flame retardant effect include aluminum hydroxide, magnesium hydroxide, zinc borate and the like, and these can be used alone or in combination. Among the 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. The shape of the filler is preferably spherical or nearly spherical from the viewpoint of fluidity during molding and mold wear, and particularly preferably 50% by mass or more is spherical. From the viewpoint of moisture shielding properties, mold wear, and the like, the average particle size of the filler is preferably 15 μm or less (50% by mass or more of the filler is a particle size of 15 μm or less), and particularly preferably 10 μm or less.

  The blending amount of the inorganic filler is 85% by mass or more based on the whole resin composition from the viewpoint of hygroscopicity, reduction of linear expansion coefficient, strength improvement and flame retardancy, and the upper limit is preferably 95% by mass or less, More preferably, it is 90 mass%. It is especially preferable that it is 87-90 mass%. If it is less than 85% by mass, the strength and flame retardancy are likely to decrease, and if it exceeds 95% by mass, the fluidity tends to be insufficient.

  Furthermore, as other additives, flame retardants such as brominated epoxy resins, antimony trioxide, phosphate esters, red phosphorus and melamine resins, and other nitrogen-containing compounds, stress relieving agents such as silicone oil and silicone rubber powder, Ion trapping agents such as hydrotalcite and antimony-bismuth, carbon black, organic dyes, organic pigments, coloring agents such as titanium oxide, and the like can be used as necessary.

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

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

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

Examples of the present invention will be described below, but the present invention is not limited thereto.
(Examples 1-10, Comparative Examples 1-9)
First, various materials shown in Tables 1 and 2 were premixed (dry blended), then kneaded with a biaxial roll (roll surface temperature of about 80 ° C.) for 10 minutes, cooled and pulverized to produce a resin composition.

注）配合量 質量部

Note) Blending amount Mass part

注）配合量 質量部

Note) Blending amount Mass part

The materials listed in Tables 1 and 2 are as follows.
As an epoxy resin,
Epoxy resin 1: biphenyl type epoxy resin having an epoxy equivalent of 196 and a melting point of 106 ° C. (trade name Epicoat YX-4000H manufactured by Japan Epoxy Resin Co., Ltd.)
Epoxy resin 2: biphenylene type epoxy resin having an epoxy equivalent of 273 and a softening point of 58 ° C. (trade name NC-3000 manufactured by Nippon Kayaku Co., Ltd.)
Epoxy resin 3: Sulfur atom-containing epoxy resin having an epoxy equivalent of 245 and a melting point of 110 ° C. (trade name YSLV-120TE manufactured by Toto Kasei Co., Ltd.)
Epoxy resin 4: bisphenol F type epoxy resin (trade name YSLV-80XY, manufactured by Toto Kasei Co., Ltd.)
Curing agent 1: phenol aralkyl resin having a softening point of 70 ° C. and a hydroxyl group equivalent of 175 (trade name: Millex XLC-3L, manufactured by Mitsui Chemicals, Inc.)
Curing agent 2: Biphenylene type phenol resin having a softening point of 80 ° C. and a hydroxyl group equivalent of 199 (trade name MEH-7851 manufactured by Meiwa Kasei Co., Ltd.)
Curing accelerator: Adduct of triphenylphosphine and 1,4-benzoquinone Epoxy silane: γ-glycidoxypropyltrimethoxysilane (trade name A-187 manufactured by Toray Dow Corning Co., Ltd.)
Polyethylene wax: PED-191 (manufactured by Clariant Japan Co., Ltd.)
Carnauba wax: (Clariant)
Carbon black: MA-100 (trade name, manufactured by Mitsubishi Chemical Corporation)
Inden oligomer resin: I-100 (manufactured by Nippon Steel Chemical Co., Ltd.)
Fused spherical silica: Spherical fused silica having an average particle size of 14.5 μm and a specific surface area of 2.8 m ² / g

The epoxy resin compositions for sealing of Examples and Comparative Examples were evaluated by the following tests. The sealing epoxy resin composition was molded using a transfer molding machine under conditions of a mold temperature of 180 ° C., a molding pressure of 6.9 MPa, and a curing time of 90 seconds.
(1) Spiral flow A mold conforming to EMM11-66 was set in a transfer molding machine, an epoxy resin composition for sealing was molded under the above conditions, and the flow distance (cm) was determined.
(2) Hardness during heating Set the burr measurement mold (mold with width of 5mm, depth of 50, 30, 20, 10, 5, 2μm) on the transfer molding machine and seal epoxy under the above conditions The resin composition was molded, and after 10 seconds from the opening of the mold, the resin reservoir was measured with a Shore D hardness meter.
(3) Flame retardancy Using a mold for molding a test piece having a thickness of 1/32 inch, the epoxy resin composition for sealing was molded under the molding conditions of (1) above, and further at 180 ° C. for 5 hours. Post-curing was performed and flame retardancy was evaluated according to the UL-94 test method.
(4) Reflow resistance LQFP80 pin with outer dimensions of 20mm x 14mm x 1.4mm mounted with 6mm x 8mm x 0.4mm silicon chip (Lead frame material: copper alloy, die pad upper surface and lead tip silver plated product) Is molded and post-cured using the epoxy resin composition for sealing under the conditions of (3) above, humidified under the conditions of 85 ° C. and 85% RH168h, and 260 ° C. for 10 seconds and further Reflow treatment was performed at 270 ° C for 10 seconds, where heat resistance is severe, and the presence or absence of delamination at the interface between the die pad upper surface and the silver plating treatment at the tip of the lead frame and the sealing material was observed. ) With respect to the number of peeled packages.
(5) Continuous workability Continuous workability is achieved by using an epoxy resin composition for sealing LQFP216 pins (lead frame material: copper alloy + nickel / palladium + gold-plated product) with external dimensions of 20 mm x 20 mm x 1.4 mm. Molding was performed at a mold temperature of 175 ° C. and a curing time of 60 seconds up to a maximum of 300 shots, and the number of shots until filling of the package cavity contents due to clogging of the air vent portion was measured.
The test results are summarized in Table 3 and Table 4.

*１： エアベント詰まり起因ではなく、流動性不足起因の未充填が発生。

* 1: Not due to air vent clogging but not due to insufficient fluidity.

  Comparative Examples 1 to 3 and 5 (C) indene / styrene / phenol copolymer oligomer of the present invention are not used or the blending amount is less than 15 parts by mass with respect to 100 parts by mass of the epoxy resin of component (A). -7 is inferior in peeling resistance in reflow resistance evaluation.

  In addition, Comparative Examples 4 and 8 in which (C) the indene / styrene / phenol copolymer oligomer blending amount exceeds 25 parts by mass with respect to 100 parts by mass of the epoxy resin of the component (A) are in the peel resistance in the reflow resistance evaluation. Is a good result but inferior in continuous workability.

  Moreover, the comparative example 9 whose compounding quantity of (D) inorganic filler is less than 85 mass% is slightly inferior in peeling resistance in reflow resistance evaluation, and inferior in flame retardance.

  On the other hand, Examples 1-10 which use 15-25 mass parts of (C) indene styrene phenol phenol copolymer oligomer of this invention with respect to 100 mass parts of (A) component epoxy resins are all resistant. It shows good results in peel resistance in reflow evaluation.

  In Examples 1 to 4 and 7 to 9, (C) the indene / styrene / phenol copolymer oligomer content is 15 to 25 parts by mass with respect to 100 parts by mass of the epoxy resin (A), and the epoxy resin is It is composed of biphenyl type epoxy resin, biphenylene type epoxy resin, or epoxy resin that is a sulfur atom-containing epoxy resin, and the curing agent is a combination of xylylene type phenol aralkyl resin, and most excellent in peel resistance in reflow resistance evaluation Shows a good result. Furthermore, Examples 1-6 and 8-10 whose content of an inorganic filler is 90 mass% or less have shown the result excellent also from the viewpoint of fluidity | liquidity.

  The epoxy resin composition for sealing according to the present invention can provide a product such as an electronic component device having good reflow resistance, moldability and continuous workability, and its industrial value is great.

Claims (6)

  An epoxy resin composition for sealing containing (A) an epoxy resin, (B) a curing agent, (C) an indene / styrene / phenol copolymer oligomer and (D) an inorganic filler, (A) epoxy resin 100 (C) 15 to 25 parts by mass of indene / styrene / phenol copolymer oligomer, and (D) an epoxy resin composition for sealing containing 85% by mass or more of the epoxy resin composition with respect to parts by mass .   (A) The epoxy resin composition for sealing according to claim 1, wherein the epoxy resin contains at least one of biphenyl type epoxy resin, biphenylene type epoxy resin, and sulfur atom-containing epoxy resin.   (A) The epoxy resin composition for sealing according to claim 1 or 2, wherein the epoxy resin contains a novolac type epoxy resin.   (B) The epoxy resin composition for sealing according to any one of claims 1 to 3, wherein the curing agent is a xylylene type phenol-aralkyl resin.   (D) Content of an inorganic filler is 90 mass% or less, The epoxy resin composition for sealing in any one of Claims 1-4.   An electronic component device provided with the element sealed with the epoxy resin composition for sealing in any one of Claims 1-5.