JP2008121003A - Epoxy resin molding material for use in sealing, and electronic component device using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide such an epoxy resin molding material for use in the sealing as is pulverulent and blocking-free and also is excellent in the workability on a compression molding method. <P>SOLUTION: The epoxy resin molding material for use in the sealing, containing (A) an epoxy resin, (B) a hardener and (C) an inorganic filler, is characterized in that the epoxy rein has two or more epoxy groups in one molecule and a melt viscosity at 150°C of 0.1 Pa s or less, and in that a powder of the epoxy resin molding material for use in the sealing contains a constituent with a particle size of 106 μm or more in an amount of 97% by weight or more. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention is excellent in fluidity for sealing by compression molding of an electronic component device, and particularly when applied to a fine-pitch single-side sealed package, it is powdery and has no blocking, and has excellent workability. The present invention relates to an epoxy resin molding material and an electronic component device using the same.

  Conventionally, in the field of element sealing of electronic component devices such as transistors and ICs, resin sealing has been the mainstream in terms of productivity and cost, and epoxy resin molding materials have been widely used. This is because epoxy resins are balanced in various properties such as electrical properties, moisture resistance, heat resistance, mechanical properties, and adhesiveness with inserts.

  In recent years, along with the high density mounting of electronic component devices on printed wiring boards, electronic component devices are mainly used in surface mount type packages rather than conventional pin insertion type packages. Surface-mount ICs, LSIs, etc. are thin and small packages in order to increase the mounting density and reduce the mounting height, and the volume occupied by the device package increases, resulting in a very thick package. It has become thinner.

  In addition, in order to cope with further reduction in size and weight, CSP (Quad Flat Package), SOP (Small Outline Package), and other forms of packages are easy to cope with higher pin count and CSP capable of higher density mounting. It is moving to area mounting packages such as BGA (Ball Grid Array) including (Chip Size Package). Along with the increase in speed and functionality, the package is becoming increasingly narrower, thinner, and longer in the wire to connect the chip and the substrate, in order to reduce the size and size of the device and increase the number of pins. . For the sealing of these packages, transfer molding using an epoxy resin molding material is the mainstream. For narrowing, thinning, and lengthening of gold wires, the epoxy resin molding material is highly fluidized. .

  However, in the conventional transfer molding, the molten epoxy resin molding material for sealing is poured into the mold by pressure, so that the mold wire flows and deforms due to the flow of the molding material. Although the flow of the gold wire is suppressed by increasing the fluidity of the molding material, there is a limit to increasing the fluidity of the molding material, and it is difficult to cope with further narrowing of the gold wire, narrower wire, and longer wire length. It is becoming.

In recent years, compression molding has been studied as a package molding technique that replaces transfer molding. In compression molding, an epoxy resin molding material for sealing is placed directly on the mold, and molding is performed by applying pressure so that the molten molding material is slowly pressed against the substrate, so that the molding material flows as in conventional transfer molding. There is almost no gold wire flow suppression.
JP 2000-169676 A

  In the transfer molding method, the sealing epoxy resin is supplied in tablets with a specific diameter and weight. In compression molding, the sealing epoxy resin molding material is supplied in powder, and the powder is weighed as it is. Place it on a mold, or after weighing it, shape it into a plate shape that fits the mold, place it on the mold and compress it. If the powder is blocked, problems may occur in conveyance, weighing, etc., and it has been difficult to apply to compression molding. On the other hand, from the viewpoint of fluidity and reflowability, it is necessary to apply an epoxy resin and a curing agent having a low melt viscosity, and there is a problem that the epoxy resin molding material is easily blocked. An object of the present invention is to provide an epoxy resin molding material for sealing that is powdery, has no blocking, and has excellent workability in a compression molding method.

  As a result of intensive studies to solve the above problems, the present inventors have adjusted the fine powder component of the powder to a certain amount or less, and the above-described object is achieved by an epoxy resin molding material for sealing containing a specific epoxy resin. It has been found that this can be achieved, and the present invention has been completed.

The present invention relates to the following.
1. (A) An epoxy resin, (B) a curing agent, and (C) an epoxy resin molding material for sealing containing an inorganic filler, wherein (A) the epoxy resin has two or more epoxy groups in one molecule. An epoxy resin molding material for sealing having a melt viscosity at 150 ° C. of 0.1 Pa · s or less and a component having a particle size of 106 μm or more of the powder of the epoxy resin molding material for sealing is 97% by weight or more.
2. (A) The epoxy resin molding material for sealing according to item 1, wherein the epoxy resin contains a compound represented by the following general formula (I) in an amount of 30% by weight or more based on the total epoxy resin.

（ここで、Ｒ_１〜Ｒ_４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 _{1 to} R ₄ are 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.)

3. Item 3. The sealing epoxy resin molding material according to item 1 or 2, wherein the epoxy resin contains a compound represented by the following general formula (II) in an amount of 10% by weight or more based on the total epoxy resin.

（ここで、Ｒ_１〜Ｒ_１０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 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. N is 0 to 3. Indicates an integer.)

（ここで、Ｒ_１〜Ｒ_４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。）
５． 項１〜４のいずれかに記載の封止用エポキシ樹脂成形材料で封止された素子を備えた電子部品装置。 4). (A) An epoxy resin, (B) a curing agent, and (C) an epoxy resin molding material for compression molding sealing containing an inorganic filler, wherein (A) the epoxy resin is represented by the following general formula (I) An epoxy resin molding material for sealing containing a compound in an amount of 30% by weight or more based on the whole epoxy resin.

(Here, R _{1 to} R ₄ are 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.)
5. Item 5. An electronic component device comprising an element sealed with the sealing epoxy resin molding material according to any one of Items 1 to 4.

  The epoxy resin molding material for sealing according to the present invention is excellent in fluidity for sealing by compression molding, and especially when applied to a fine-pitch single-side sealed package, it is powdery and has no blocking and good workability In addition, the flow of the gold wire can be suppressed, and its industrial value is great.

The epoxy resin molding material for sealing of the present invention contains (A) an epoxy resin, (B) a curing agent and (C) an inorganic filler, and (A) the epoxy resin contains two or more epoxies in one molecule. And the melt viscosity at 150 ° C. is 0.1 Pa · s or less, and the component of the powder of the epoxy resin molding material for sealing having a particle size of 106 μm or more is 97% by weight or more.
(A) Although 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 encapsulating electronic components, such as a biphenyl type epoxy resin, a biphenylene type epoxy resin, a phenol novolac type Epoxy resin, orthocresol novolak type epoxy resin, bisphenol A novolak type epoxy resin and other phenols and / or epoxy resins obtained by epoxidizing novolak resins synthesized from naphthols and aldehydes, bisphenol A, bisphenol F, bisphenol S, diglycidyl ethers such as alkyl-substituted biphenols, stilbene-type epoxy resins, diaminodiphenylmethane, isocyanuric acid and other polyamines obtained by the reaction of epichlorohydrin Min-type 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 include trimethylolpropane type epoxy resin, terpene modified epoxy resin, sulfur atom-containing epoxy resin, linear aliphatic epoxy resin obtained by oxidizing olefinic bonds with peracid such as peracetic acid, and alicyclic epoxy resin. .

（ここで、Ｒ_１〜Ｒ_４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。）

（ここで、Ｒ_１〜Ｒ_１０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。）
式（I）のエポキシ樹脂としては、例えば、エポキシ当量２７３、軟化点５８℃、溶融粘度（１５０℃）０．１Ｐａ・ｓのビフェニレン型エポキシ樹脂（日本化薬株式会社製商品名ＮＣ−３０００）が、式（II）のエポキシ樹脂としては、例えば、エポキシ当量９２、融点６８℃、溶融粘度（１５０℃）０．０１Ｐａ・ｓのビスフェノールＦ型エポキシ樹脂（東都化成株式会社製商品名ＹＳＬＶ−８０ＸＹ）、及びエポキシ当量４６８、軟化点６４、溶融粘度（１５０℃）０．４Ｐａ・ｓのビスフェノールＡ型エポキシ樹脂（ジャパンエポキシレジン株式会社製商品名Ｅ−１００１）が入手可能である。 Among them, biphenyl type epoxy resins, bisphenol F type epoxy resins, stilbene type epoxy resins and sulfur atom-containing epoxy resins are preferable from the viewpoint of fluidity and reflow resistance, and phenol / aralkyl resins and bisphenols from the viewpoint of blocking resistance. A-type epoxy resin is preferable, and it is preferable that at least one of these epoxy resins is contained and used in combination. As these epoxy resins, epoxy resins of the following general formula (I) and / or (II) are preferred. The amount of the epoxy resin of the general formula (I) is 30% by weight or more in the whole epoxy resin in consideration of blocking properties, and the amount of the epoxy resin of the general formula (II) is 10% by weight or more in consideration of fluidity. It is preferable.

(Here, R _{1 to} R ₄ are 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.)

(Here, 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. N is 0 to 3. Indicates an integer.)
As an epoxy resin of formula (I), for example, an epoxy equivalent of 273, a softening point of 58 ° C., a melt viscosity (150 ° C.) of 0.1 Pa · s, a biphenylene type epoxy resin (trade name NC-3000 manufactured by Nippon Kayaku Co., Ltd.) However, as the epoxy resin of the formula (II), for example, a bisphenol F type epoxy resin having an epoxy equivalent of 92, a melting point of 68 ° C., and a melt viscosity (150 ° C.) of 0.01 Pa · s (trade name YSLV-80XY manufactured by Toto Kasei Co., Ltd.) ), An epoxy equivalent of 468, a softening point of 64, and a melt viscosity (150 ° C.) of 0.4 Pa · s, a bisphenol A type epoxy resin (trade name E-1001 manufactured by Japan Epoxy Resin Co., Ltd.) is available.

For the epoxy resin molding material for sealing of the present invention, conventionally known epoxy resins can be used in combination as required, other than those generally used for sealing electronic parts. Examples of the epoxy resins that can be used in combination include phenol novolac type epoxy resins, orthocresol novolac type epoxy resins, and epoxy resins having a triphenylmethane skeleton, such as phenol, cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol F. And / or naphthols such as α-naphthol, β-naphthol, and dihydroxynaphthalene and compounds having an aldehyde group such as formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, and salicylaldehyde in an acidic catalyst. And an epoxidized novolak resin obtained. Stilbene type epoxy resin, hydroquinone type epoxy resin, glycidyl ester type epoxy resin obtained by reaction of polybasic acid such as phthalic acid and dimer acid and epichlorohydrin, diaminodiphenylmethane, isocyanuric acid etc. glycidylamine obtained by reaction of epichlorohydrin Type epoxy resin, epoxidized product of co-condensation resin of dicyclopentadiene and phenol, epoxy resin having naphthalene ring, trimethylolpropane type epoxy resin, terpene modified epoxy resin, olefin bond is oxidized with peracid such as peracetic acid Examples thereof include linear aliphatic epoxy resins, alicyclic epoxy resins, sulfur atom-containing epoxy resins, and the like. These may be used alone or in combination of two or more.
(A) From the viewpoint of fluidity and reflowability, the melt viscosity at 150 ° C. of the epoxy resin may be 0.1 Pa · s or less, and when two or more epoxy resins are used in combination, the epoxy resin as a whole It may be 0.1 Pa · s or less.

  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. Phenolic aralkyl resin, biphenylene type phenol aralkyl synthesized from novolac type phenolic resin, phenols and / or naphthols and dimethoxyparaxylene or bis (methoxymethyl) biphenyl Resins, aralkyl-type phenol resins such as naphthol / aralkyl resins, dicyclopentadiene-type phenol novolac resins, dicyclopentadiene-type naphthol novolak resins, etc. synthesized by copolymerization from phenols and / or naphthols and dicyclopentadiene Cyclopentadiene type phenolic resin, triphenylmethane type phenolic resin, terpene modified phenolic resin, paraxylylene and / or metaxylylene modified phenolic resin, melamine modified phenolic resin, cyclopentadiene modified phenolic resin, phenol obtained by copolymerizing these two or more Resin etc. are mentioned. These may be used alone or in combination of two or more.

（ここで、Ｒ_１〜Ｒ_４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。） Among them, from the viewpoint of fluidity and reflowability, aralkyl-type phenol resins such as phenol-aralkyl resin, biphenylene-type phenol-aralkyl resin, and naphthol-aralkyl resin are preferable. From the viewpoint of blocking, the melt viscosity at 150 ° C. Phenol-aralkyl resins that are 0.2 Pa · s or higher are preferred. Examples of the phenol-aralkyl resin include a phenol resin of the formula (III).

(Here, R _{1 to} R ₄ are 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 equivalent ratio of (A) epoxy resin and (B) curing agent, that is, the ratio of the number of hydroxyl groups in the curing agent to the number of epoxy groups in the epoxy resin (number of hydroxyl groups in the curing agent / number of epoxy groups in the epoxy resin) is: Although there is no restriction | limiting in particular, In order to suppress each unreacted part small, it is preferable to set to the range of 0.5-2, and 0.6-1.3 are more preferable. In order to obtain a sealing epoxy resin molding material excellent in moldability and reflow resistance, it is more preferably set in the range of 0.8 to 1.2.

  In the epoxy resin molding material for sealing of the present invention, a curing accelerator can be used as necessary in order to accelerate the reaction between (A) the epoxy resin and (B) the curing agent. The curing accelerator is generally used in an epoxy resin molding material for sealing and is not particularly limited. For example, 1,8-diaza-bicyclo (5,4,0) undecene-7, 1,5- Cycloamidine compounds such as diaza-bicyclo (4,3,0) nonene, 5,6-dibutylamino-1,8-diaza-bicyclo (5,4,0) undecene-7, and maleic anhydride to these compounds, 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2, Add a quinone compound such as 3-dimethoxy-1,4-benzoquinone and phenyl-1,4-benzoquinone, diazophenylmethane, a compound having a π bond such as a phenol resin. Compounds having intramolecular polarization, tertiary amines such as benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol and their derivatives, 2-methylimidazole, 2-phenylimidazole, 2- Imidazoles such as phenyl-4-methylimidazole and derivatives thereof, phosphine compounds such as tributylphosphine, methyldiphenylphosphine, triphenylphosphine, tris (4-methylphenyl) phosphine, diphenylphosphine, phenylphosphine, and these phosphine compounds. Phosphorus compound with intramolecular polarization formed by adding a compound having a π bond such as maleic anhydride, the above quinone compound, diazophenylmethane, phenol resin, tetraphenylphosphonium Examples include tetraphenylboron salts such as tetraphenylborate, triphenylphosphinetetraphenylborate, 2-ethyl-4-methylimidazoletetraphenylborate, N-methylmorpholine tetraphenylborate, and derivatives thereof, and these are used alone. Alternatively, two or more kinds may be used in combination.

  The blending amount of the curing accelerator is not particularly limited as long as the curing acceleration effect is achieved, but is preferably 0.005 to 2% by weight with respect to the sealing epoxy resin molding material. 01 to 0.5% by weight is more preferable. If it is less than 0.005% by weight, the curability in a short time tends to be inferior, and if it exceeds 2% by weight, the curing rate tends to be too high and it tends to be difficult to obtain a good molded product.

  (C) The inorganic filler has effects of hygroscopicity, linear expansion coefficient reduction, thermal conductivity improvement and strength improvement, such as fused silica, crystalline silica, alumina, zircon, calcium silicate, calcium carbonate, potassium titanate, Examples thereof include powders such as silicon carbide, silicon nitride, aluminum nitride, boron nitride, beryllia, zirconia, zircon, fosterite, steatite, spinel, mullite, and titania, or spherical beads and glass fibers. Furthermore, examples of the inorganic filler having a flame retardant effect include aluminum hydroxide, magnesium hydroxide, composite metal hydroxide, zinc borate, and zinc molybdate.

  These inorganic fillers may be used alone or in combination of two or more. Of these, fused silica is preferable from the viewpoint of filling property and linear expansion coefficient, and alumina is preferable from the viewpoint of high thermal conductivity, and the shape of the inorganic filler is preferably spherical from the viewpoint of filling property and mold wear.

  The blending amount of the inorganic filler is preferably 60 to 95% by mass with respect to the epoxy resin composition for sealing, from the viewpoints of fluidity, moldability, hygroscopicity, linear expansion coefficient reduction, strength improvement and reflow resistance. 70 to 90% by mass is more preferable. If the amount is less than 60% by mass, the flame retardancy and the reflow resistance tend to be lowered. If the amount exceeds 95% by mass, the fluidity tends to be insufficient, and the flame retardancy tends to be lowered.

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

  Of these, a silane coupling agent having a secondary amino group is preferred from the viewpoint of fluidity. The total blending amount of the coupling agent is preferably 0.037 to 4.75% by mass, more preferably 0.05 to 5% by mass with respect to the epoxy resin composition for sealing. More preferably, it is 1-2.5 mass%. If it is less than 0.037% by mass, the adhesion to the frame tends to be lowered, and if it exceeds 4.75% by mass, the moldability of the package tends to be lowered.

  In the sealing epoxy resin molding material of the present invention, a conventionally known flame retardant can be blended as necessary for the purpose of further improving the flame retardancy. For example, bromine compounds such as brominated epoxy resins, antimony compounds such as antimony trioxide, red phosphorus and phosphate esters coated with thermosetting resins such as red phosphorus and zinc oxide, and thermosetting resins such as phenolic resins, phosphine oxides Phosphorus compounds such as melamine, melamine derivatives, melamine-modified phenol resins, compounds having a triazine ring, nitrogen-containing compounds such as cyanuric acid derivatives and isocyanuric acid derivatives, phosphorus and nitrogen-containing compounds such as cyclophosphazene, aluminum hydroxide, hydroxylation Examples thereof include compounds containing metal elements such as magnesium, composite metal hydroxide, zinc oxide, zinc stannate, zinc borate, iron oxide, molybdenum oxide, zinc molybdate, and dicyclopentadienyl iron. May be used alone or in combination of two or more.

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

  The gel time of the epoxy resin composition for sealing of the present invention is preferably 40 to 100 seconds and more preferably 40 to 70 seconds at the molding temperature. If it is less than 40 seconds, the viscosity of the molding material rises between the time when the molding material is placed on the mold and the resin is melted until it is compression-molded, causing a wire flow. On the other hand, if it exceeds 100 seconds, curing is insufficient, causing a release failure, and productivity is also inferior.

The particle size of the powder of the epoxy resin composition for sealing of the present invention is 97% by weight or more for components of 106 μm or more. If the component of 106 μm or more is less than 97% by weight, it takes time until the molding material is placed on the mold and the resin melts, causing blocking. As a method for adjusting the particle size of the powder of the epoxy resin composition for sealing, for example, it is placed on a sieve having a mesh size of 106 μm (diameter 200 mm, JIS Z-8801 compliant), set in a sieve shaker, and the shaker number 200 rpm. And shake for 10 minutes.
However, when the epoxy resin contains the compound represented by the general formula (I) in an amount of 30% by weight or more based on the whole epoxy resin, the particle size of the powder may be less than 97% by weight for components having a particle size of 106 μm or more. This is because when the compound represented by the general formula (I) is contained in an amount of 30% by weight or more of the entire epoxy resin, an excellent blocking property can be obtained even if the particle size of the powder is less than 97% by weight of a component of 106 μm or more.

  EXAMPLES Next, although an Example demonstrates this invention, the scope of the present invention is not limited to these Examples.

Examples 1-5, Comparative Examples 1-4
The following components were blended in the weight parts shown in Table 1, respectively, roll kneaded under conditions of a kneading temperature of 80 ° C. and a kneading time of 10 minutes, and pulverized with a power mill to prepare an epoxy resin molding material for sealing. For Examples 1 to 3, after pulverizing with a power mill, it was further placed on a sieve (diameter 200 mm, conforming to JIS Z-8801) with an aperture of 106 μm, and this was set in a sieve shaker and shaken at a shaker number of 200 rpm for 10 minutes. The towed epoxy resin molding material was produced.

As an epoxy resin, a biphenyl type epoxy resin having an epoxy equivalent of 192, a melting point of 109 ° C., and a melt viscosity (150 ° C.) of 0.01 Pa · s (epoxy resin 1, product name Epicoat YX-4000, 4,4 ′ manufactured by Japan Epoxy Resins Co., Ltd.) -Bis (2,3-epoxypropoxy) -3,3 ', 5,5'-tetramethylbiphenyl-based epoxy resin), epoxy equivalent 92, melting point 68 ° C, melt viscosity (150 ° C) 0.01Pa S bisphenol F type epoxy resin (epoxy resin 2, trade name YSLV-80XY, manufactured by Toto Kasei Co., Ltd., in formula (II), R ₁ , R ₃ , R ₆ and R ₈ are methyl groups, R ₂ , R _{4, R 5,} R 7, are _{R 9} and R ₁₀ are hydrogen atoms, n = 0 the main component a bisphenol F type epoxy resin), epoxy equivalent 273, softening point 58 ° C., a melt viscosity (0.99 ° C.) 1 Pa · s biphenylene type epoxy resin (Epoxy resin 3, Nippon Kayaku Co., Ltd., trade name NC-3000, aralkyl type epoxy resin having a biphenylene group of general formula (I)), epoxy equivalent 468, softening point 64, the melt viscosity (0.99 ° C.) 0.4 Pa · s bisphenol a type epoxy resin (epoxy resin 4, Japan epoxy resins Co., Ltd. trade name E-1001, _{R 9} and R ₁₀ is a methyl group) was used.

  As a curing agent, a hydroxyl group equivalent of 175, a softening point of 66, a melt viscosity (150 ° C.) of 0.11 Pa · s phenol aralkyl resin (curing agent 1, trade name MEH-7800-SS manufactured by Meiwa Kasei Co., Ltd.), hydroxyl group equivalent of 100, Softening point 83 ° C., melt viscosity (150 ° C.) 0.1 Pa · s phenol resin (curing agent 2, trade name MEH-7500-3S manufactured by Meiwa Kasei Co., Ltd.), hydroxyl group equivalent 175, softening point 70 ° C., melt viscosity ( 150 ° C.) 0.17 Pa · s phenol aralkyl resin (curing agent 3, trade name “Mirex XLC-3L” manufactured by Mitsui Chemicals, Inc.) was used.

A 1: 1 adduct (curing accelerator) of triphenylphosphine and 1,4-benzoquinone was used as a curing accelerator.
As the inorganic filler, spherical fused silica (filler 1) having an average particle diameter of 37.0 μm and spherical fused silica (filler 2) having an average particle diameter of 32.0 μm were used.
As the flame retardant, antimony trioxide and brominated epoxy resin (YDB-400 manufactured by Tohto Kasei Chemical Co., Ltd., softening point 69 ° C., bromine content 49% by mass) were used.
As a coupling agent, γ-glycidoxypropyltrimethoxysilane (trade name KBM-573, manufactured by Shin-Etsu Chemical Co., Ltd.) was used.
As other additives, carnauba wax (manufactured by Clariant) and carbon black (trade name MA-600, manufactured by Mitsubishi Chemical Corporation) were used.

The produced epoxy resin molding materials for sealing of Examples and Comparative Examples were evaluated by the following tests. The results are shown in Table 2.
The epoxy resin molding material for sealing was molded at 180 ° C. for 90 seconds. Further, post-curing was performed at 180 ° C. for 5 hours.
(1) Spiral flow (fluidity index)
Using a mold for spiral flow measurement conforming to EMMI-1-66, the epoxy resin molding material for sealing was transferred by a transfer molding machine under conditions of a mold temperature of 175 ° C., a molding pressure of 6.9 MPa, and a curing time of 90 seconds. It shape | molded and calculated | required the flow distance (cm).
(2) Gel time Place 0.5 g of the weighed sample (sealing epoxy resin molding material) on the center of a hot plate heated to 175 ° C, and use a metal spatula heated to 175 ° C to make a circular material with a diameter of about 5 cm. When the fluidity of the material ceased, the end point was determined, and the time (s) from the time when the material was placed on the hot plate to the end point was measured to obtain the gel time.
(3) Powder particle size 50 g of epoxy resin molding material powder for sealing is placed on a sieve (diameter 200 mm, JIS Z-8801 compliant) with an aperture of 106 μm, set in a sieve shaker, and shaken at 200 rpm for 10 minutes. After shaking tow, the weight of the powder remaining on the sieve is measured, and the weight% is taken as a component of 106 μm or more.
(4) Blocking property 10 g of the epoxy resin molding material powder for sealing was put in an aluminum cup having a diameter of 50 mm and left in a thermostatic bath set at 20 ° C. or 25 ° C. for 12 hours, and the state of powder blocking was observed. Judgment was made as follows: ◯: no blocking, Δ: lightly touched to break the lump, ×: lightly touched to lump.

The epoxy resin molding materials of Comparative Examples 1 to 3 in which the component having a powder particle size of 106 μm or more is less than 97% by weight are very inferior in blocking properties (4/6 is x). Further, the epoxy resin molding material of Comparative Example 4 containing an epoxy resin having a melt viscosity at 150 ° C. exceeding 0.1 Pa · s is very inferior in fluidity (spiral flow value: 122 cm).
On the other hand, the epoxy resin molding material of the present invention according to Examples 1 to 3 containing an epoxy resin having a melt viscosity of more than 0.1 Pa · s at 150 ° C. and having a powder particle size of 106 μm or more is 97% by weight or more. In addition, the fluidity is excellent (spiral flow value: 146 to 183 cm), and the blocking property is good (4/6 is ◯).
Moreover, the epoxy resin molding material of this invention by Examples 4-5 containing the epoxy resin shown by general formula (I) has favorable blocking property (3/4 is (circle)).

Claims (5)

An epoxy resin molding material for sealing containing (A) an epoxy resin, (B) a curing agent and (C) an inorganic filler,
The (A) epoxy resin has two or more epoxy groups in one molecule, and a melt viscosity at 150 ° C. is 0.1 Pa · s or less,
An epoxy resin molding material for sealing in which a component having a particle size of 106 μm or more of the powder of the epoxy resin molding material for sealing is 97% by weight or more. The epoxy resin molding material for sealing according to claim 1, wherein the (A) epoxy resin contains a compound represented by the following general formula (I) in an amount of 30% by weight or more based on the total epoxy resin.

(Here, R _{1 to} R ₄ are 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.) The epoxy resin molding material for sealing according to claim 1 or 2, wherein the (A) epoxy resin contains a compound represented by the following general formula (II) in an amount of 10% by weight or more based on the total epoxy resin.

(Here, 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. N is 0 to 3. Indicates an integer.) (A) An epoxy resin, (B) a curing agent, and (C) an epoxy resin molding material for compression molding sealing containing an inorganic filler, wherein the (A) epoxy resin is represented by the following general formula (I) An epoxy resin molding material for sealing containing 30% by weight or more of the compound to be cured.

(Here, R _{1 to} R ₄ are 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.)   The electronic component apparatus provided with the element sealed with the epoxy resin molding material for sealing in any one of Claims 1-4.