JP2006002039A - Epoxy resin molding material for encapsulation and electronic component device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an epoxy resin composition molding material for encapsulation excellent in moldability such as fluidity, flame resistance, heat resistance and thermal cycle resistance and an electronic component device equipped with an element encapsulated with the epoxy resin composition molding material. <P>SOLUTION: The epoxy resin composition molding material for encapsulation contains (A) an epoxy resin containing an epoxy resin obtained by glycidyl etherification of a dimer of at least either of hydroxynaphthalene and dihydroxynaphthalene, (B) a hardener expressed by general formula (I) (wherein, n is 0 or a positive integer; and a hydrogen atom on the benzene ring and the naphthalene ring in A and B may be substituted with a hydrocarbon group) and (C) an inorganic filler. Component (C) has at least an average particle size of ≥15 μm or a specific surface area of ≤4.5 m<SP>2</SP>/g. <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, electronic devices are also being developed in the automobile field. Electronic devices for automobiles are often required to be more reliable in terms of heat resistance and cold cycle resistance than so-called consumer applications such as personal computers and home appliances.

General techniques for increasing the heat resistance of electronic equipment include a technique for increasing the glass transition point of the package, and techniques for improving the thermal cycle resistance include thermal expansion of the semiconductor internal member and the epoxy resin molding material for sealing. A technique such as bringing the coefficients closer is mentioned.
In epoxy resin molding materials for sealing, halogenated resins such as decabromo and antimony compounds have been used as flame retardants in the past, but in recent years there has been a movement to regulate the amount of these compounds from the viewpoint of environmental protection. There is a demand for non-halogenation (non-bromo) and non-antimony. In addition, it is known that a bromo compound has an adverse effect on the high temperature storage characteristics of a plastic encapsulated IC. From this viewpoint, reduction of the amount of bromo resin is desired.

  As one of the methods for achieving flame retardancy without using brominated resin or antimony oxide, a method of adding an organic phosphorus compound (for example, see Patent Document 1), a method of using a metal hydroxide (for example, Patent Document) However, it has not been able to solve problems such as a decrease in glass transition point and an adverse effect on formability.

In an epoxy resin molding material for sealing that does not use brominated resin or antimony oxide, when trying to bring the coefficient of linear expansion of the epoxy resin molding material for sealing close to that of the semiconductor internal member in order to increase the thermal cycle resistance, In particular, it is difficult to ensure flame retardancy in a package using a copper lead frame. On the other hand, when flame retardants such as organophosphorus compounds and metal hydroxides are used to ensure flame retardancy, there are problems such as lowering the glass transition point and adversely affecting moldability. Although there are reports of Patent Document 3 and the like for improving the moldability of an epoxy resin molding material for sealing using a metal hydroxide, the effect is not always sufficient.
JP 9-235449 A Japanese Patent Laid-Open No. 9-241383 JP 2003-253093 A

  The present invention has been made in view of such a situation, and realizes good flame retardancy without using a halogenated resin or an antimony compound, and has reliability such as moldability such as fluidity, heat resistance, and heat cycle resistance. It is another object of the present invention to provide an epoxy resin molding material for sealing, and an electronic component device including an element sealed thereby.

  As a result of intensive studies in order to solve the above problems, the present inventors have determined that an epoxy resin molding material for sealing has an epoxy resin having a specific structure, a curing agent having a specific structure, and a specific property. It has been found that the above object can be achieved by using an inorganic filler having the present invention, and the present invention has been completed.

（一般式（I）で、ｎは０、又は正の整数を表し、A及びB中のベンゼン環及びナフタレン環上の水素原子は炭化水素基で置換されていてもよい。）
（２）ハロゲン系難燃剤及びアンチモン系難燃剤の含有量がいずれも成形材料全体の０.１重量％以下である前記（１）に記載の封止用エポキシ樹脂成形材料。
（３）ハロゲン系難燃剤及びアンチモン系難燃剤を含まない前記（２）に記載の封止用エポキシ樹脂成形材料、
（４）（Ｃ）無機質充填剤量が成型材料全体の７０重量％以上８８重量％以下である前記（１）〜（３）のいずれかに記載の封止用エポキシ樹脂成形材料、
（５）前記（１）〜（４）のいずれか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 relates to (1) (A) an epoxy resin containing an epoxy resin obtained by glycidyl etherification of at least one dimer of hydroxynaphthalene and dihydroxynaphthalene, (B) a compound represented by the following general formula (I) And (C) an inorganic filler, and the component (C) is an epoxy resin for sealing having an average particle size of at least 15 μm and a specific surface area of at least 4.5 m ² / g. Molding material,

(In general formula (I), n represents 0 or a positive integer, and the hydrogen atom on the benzene ring and naphthalene ring in A and B may be substituted with a hydrocarbon group.)
(2) The epoxy resin molding material for sealing according to the above (1), wherein the content of the halogen flame retardant and the antimony flame retardant is 0.1% by weight or less of the whole molding material.
(3) The epoxy resin molding material for sealing according to the above (2), which does not contain a halogen flame retardant and an antimony flame retardant,
(4) (C) The epoxy resin molding material for sealing according to any one of (1) to (3), wherein the amount of the inorganic filler is 70% by weight or more and 88% by weight or less of the entire molding material,
(5) An electronic component device including an element sealed with the sealing epoxy resin molding material according to any one of (1) to (4),
About.

  The epoxy resin molding material for sealing according to the present invention is excellent in moldability such as fluidity, reliability such as flame retardancy, heat resistance, cold cycle resistance, etc., and using this epoxy resin molding material for sealing If an electronic component such as an IC or LSI is sealed, an electronic component device having excellent moldability and reliability can be obtained, and its industrial value is great.

  In the present invention, an epoxy resin obtained by glycidyl etherification of at least one dimer of hydroxynaphthalene and dihydroxynaphthalene as (A) an epoxy resin in order to realize both a high glass transition point and high flame retardancy. It is necessary to contain singly or in combination of two or more. In order to realize a high glass transition point, it is preferable to use a trifunctional epoxy resin obtained by glycidyl etherification of a dimer of hydroxynaphthalene and dihydroxynaphthalene, and obtained by glycidyl etherification of a dihydroxynaphthalene dimer. It is more preferable to use a tetrafunctional epoxy resin, and a mixture thereof may be used. As an epoxy resin mainly composed of an epoxy resin obtained by glycidyl etherification of a dihydroxynaphthalene dimer, HP-4701 (trade name, manufactured by Dainippon Ink & Chemicals, Inc.) is available.

  In order to sufficiently obtain the effects of the present invention, the epoxy resin obtained by glycidyl etherification of the dimer is preferably 40% by weight or more of the total component (A), more preferably 50% by weight or more. It is preferably 60% by weight or more. If it is less than 40% by weight, it tends to be difficult to achieve both a high glass transition point and high flame retardancy.

  In the present invention, as the component (A), in addition to an epoxy resin obtained by glycidyl etherification of the dimer, an epoxy resin generally used for an epoxy resin molding material for sealing can be used in combination without any particular limitation. It is. Examples of resins that can be used in combination include phenol novolac type epoxy resins, orthocresol novolac type epoxy resins, and other phenols such as phenol, cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol F, and / or α-naphthol, β An epoxidized novolak resin obtained by condensation or cocondensation of naphthols such as naphthol and dihydroxynaphthalene and a compound having an aldehyde group such as formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, and salicylaldehyde under an acidic catalyst; Diglycidyl ethers such as bisphenol A, bisphenol F, bisphenol S, bisphenol A / D, and diglycidyl ethers of alkyl-substituted or unsubstituted biphenols Biphenyl type epoxy resin that is ether, epoxidized products such as phenol aralkyl type resin and biphenyl aralkyl type resin synthesized from phenol and dimethoxyparaxylene or bis (methoxymethyl) biphenyl, stilbene type epoxy resin, hydroquinone type epoxy resin Glycidyl ester type epoxy resins obtained by reaction of polybasic acids such as phthalic acid and dimer acid with epichlorohydrin, glycidyl amine type epoxy resins obtained by reaction of polyamines such as diaminodiphenylmethane and isocyanuric acid and epichlorohydrin, cyclopentadiene and phenols Dicyclopentadiene-type epoxy resin, naphthol-aralkyl-type resin epoxide, triphenolmethane-type epoxy resin Trimethylolpropane type epoxy resin, terpene-modified epoxy resin, linear aliphatic epoxy resin obtained by oxidizing olefin bond with peracid such as peracetic acid, alicyclic epoxy resin, and these epoxy resins as silicone, acrylonitrile, Examples thereof include epoxy resins modified with butadiene, isoprene-based rubber, polyamide-based resin, and the like.

（一般式（I）で、ｎは０、又は正の整数を表し、A及びB中のベンゼン環及びナフタレン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 of the present invention needs to contain a compound represented by the following general formula (I) singly or in combination of two or more, particularly from the viewpoint of flame retardancy.

(In general formula (I), n represents 0 or a positive integer, and the hydrogen atom on the benzene ring and naphthalene ring in A and B may be substituted with a hydrocarbon group.)

（一般式（II）で、ｎは０又は１〜１０の整数を示す。）

（一般式（III）で、ｎは０又は１〜１０の整数を示す。）

（一般式（IV）で、ｎは０又は１〜１０の整数を示す。）

（一般式（Ｖ）で、ｎは０又は１〜１０の整数を示す。）
上記一般式（II）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（III）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。又、上記一般式（IV）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（Ｖ）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（II）〜（Ｖ）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（I）で表される化合物に含まれる。 Examples of the compound represented by the general formula (I) include a phenol / aralkyl resin represented by the general formula (II), a biphenyl / aralkyl resin represented by the general formula (III), a general formula (IV), and a general formula The naphthol aralkyl resin represented by (V) can be mentioned, and from the viewpoint of flame retardancy, it is preferable to use the biphenyl aralkyl resin represented by the general formula (III) alone or in combination. It is more preferable to set it as 40 weight% or more of the whole B) component, and it is especially preferable to set it as 50 weight% or more.

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

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

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

(In general formula (V), n represents 0 or an integer of 1 to 10.)
As a phenol aralkyl resin represented by the above general formula (II), 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 above general formula (III), Meiwa Kasei Co., Ltd. product name MEH-7851 is mentioned. Moreover, as a naphthol aralkyl resin shown by the said general formula (IV), Nippon Steel Chemical Co., Ltd. brand name SN-170 is mentioned as a commercial item, The naphthol aralkyl resin shown by the said general formula (V) is mentioned. As a commercial item, Nippon Steel Chemical Co., Ltd. product name SN-475 is mentioned. In addition, in the compounds represented by the general formulas (II) to (V), 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 (I). include.

  In the present invention, as the component (B), in addition to the curing agent represented by the general formula (I), a curing agent generally used for an epoxy resin molding material for sealing can be used in combination without any particular limitation. Examples of curing agents that can be used in combination include phenols such as phenol, cresol, resorcin, catechol, bisphenol A, bisphenol F, phenylphenol, aminophenol, and / or naphthols such as α-naphthol, β-naphthol, dihydroxynaphthalene, and formaldehyde. , Novolak-type phenolic resin, dicyclopentadiene-type phenolic resin, terpene-modified phenolic resin, triphenolmethane-type phenolic resin, etc. obtained by condensation or cocondensation with compounds having an aldehyde group such as benzaldehyde, salicylaldehyde, etc. under an acidic catalyst Is mentioned.

  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 an epoxy resin molding material for sealing which is excellent in moldability and reliability, it is more preferable to set in the range of 0.8 to 1.2.

The (C) inorganic filler of the present invention is a component necessary for ensuring high flame retardance in addition to 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 formed by spheroidizing these, and glass fibers. These may be used alone or in combination of two or more. Furthermore, you may add metal hydroxide type inorganic fillers, such as aluminum hydroxide and magnesium hydroxide with a flame-retardant effect, in the range which does not lose the effect of this invention. From the viewpoint of reducing fluidity and linear expansion coefficient, it is preferable to use crystalline silica or fused silica, more preferably fused silica, and particularly preferably spherical fused silica.
The blending amount of the inorganic filler is preferably 70% by weight or more and 88% by weight or less of the entire molding material, particularly from the viewpoint of cold heat cycle resistance in the copper lead frame package, and is 75% by weight or more and 85% by weight or less. The following is particularly preferable. When the amount is less than 70% by weight or more than 88% by weight, the mismatch of the linear expansion coefficient between the epoxy resin molding material for sealing and the lead frame tends to be remarkable, which is disadvantageous for the thermal cycle resistance.

In order to obtain high flame retardancy, which is one of the effects of the present invention, an inorganic filler having an average particle size of 15 μm or more and a specific surface area of at least one of 4.5 m ² / g or less is used. It is more preferable to use an inorganic filler having an average particle size of 18 μm or more and / or a specific surface area of 4.0 m ² / g or less, and an average particle size of 20 μm or more and / or a specific surface area of 3.5 m. It is particularly preferable to use an inorganic filler that is ² / g or less. In addition, an average particle diameter and a specific surface area point out the value measured with the following method here.
(1) Average particle size measuring device: Laser diffraction / scattering particle size distribution measuring device LA-920 manufactured by Horiba, Ltd.
Dispersion medium: sodium hexametaphosphate 0.2 wt / vol% aqueous solution relative refractive index: 1.10
Transmittance: 70-90%
Circulation speed: 7
Ultrasonic time: 3 minutes Ultrasonic intensity: 7
(2) Specific surface area measuring device: Flow method BET single point method specific surface area measuring device manufactured by Yuasa Ionics Co., Ltd. Monosorb Carrier gas: Nitrogen / helium mixed gas 1.5 kg / cm ² , Nitrogen gas 0.7 kg / cm ²
Sample degassing condition: 200 ° C./30 minutes When two or more kinds of inorganic fillers having different properties are used in combination, it is preferable to perform selection so that the properties after sufficiently mixing each are within the above range. An inorganic filler having an average particle size and / or a specific surface area in the above range gives a thick surface expansion layer having a relatively large heat insulating effect when burning an epoxy resin molding material for sealing, thereby providing high flame retardancy. It is thought to give.

  In the present invention, in addition to the components (A) to (C), a curing accelerator usually used for an epoxy resin molding material for sealing can be used without any particular limitation. Examples of usable curing accelerators include organic phosphines such as tributylphosphine, methyldiphenylphosphine, triphenylphosphine, tris (4-methylphenyl) phosphine, diphenylphosphine and phenylphosphine, and maleic anhydride to these organic phosphines. 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2 Organic compounds such as compounds having intramolecular polarization formed by adding a quinone compound such as 1,3-dimethoxy-1,4-benzoquinone and phenyl-1,4-benzoquinone, a compound having a π bond such as diazophenylmethane and phenol resin Phosphorus compounds, tetraphenylphosphonium teto Organophosphorus curing accelerators such as tetraphenylboron salts such as phenylborate, triphenylphosphinetetraphenylborate, 2-ethyl-4-methylimidazoletetraphenylborate, N-methylmorpholinetetraphenylborate and derivatives thereof, 8-diaza-bicyclo (5,4,0) undecene-7, 1,5-diaza-bicyclo (4,3,0) nonene, 5,6-dibutylamino-1,8-diaza-bicyclo (5,4 , 0) Amine curing accelerators such as cycloamidine compounds such as undecene-7, imidazole curing accelerators such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, etc. These may be used alone or in combination of two or more. From the viewpoint of moldability, reliability, and flame retardancy, an adduct of an organic phosphine and a quinone compound is preferable.

  The blending amount of the curing accelerator is not particularly limited as long as the curing acceleration effect is achieved, but is preferably 0.1 to 10% by weight, more preferably 1 with respect to the epoxy resin (A). ~ 5% by weight. If it is less than 0.1% by weight, the curability in a short time tends to be inferior. If it exceeds 10% 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.

  In the present invention, in order to ensure smooth releasability from the mold during molding, higher fatty acid waxes such as stearic acid and montanic acid, higher fatty acid ester waxes such as stearic acid ester and montanic acid ester, Conventionally known release agents used for epoxy resin molding materials for sealing, such as polyolefin including polyethylene, can be used alone or 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. Examples thereof include hydrotalcite and hydrated oxides of elements selected from bismuth, zirconium, titanium, tin, magnesium, and aluminum. These may be used alone or in combination of two or more. Among these, hydrotalcite and bismuth hydrous oxide represented by the following general formula (VI) are preferable.
(Chemical formula 7)
Mg _1-X Al _X (OH) ₂ (CO ₃ ) _{X / 2} · mH ₂ O (VI)
(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, an epoxy silane, a mercapto silane, an amino silane, an alkyl silane, a ureido silane, a vinyl silane, etc. are used as necessary in order to improve 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. These may be used alone or in combination of two or more.
The blending 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.

In the molding material of the present invention, particularly from the viewpoint of heat resistance, the content of halogenated flame retardants such as brominated epoxy resins and the content of antimony flame retardants such as antimony trioxide, antimony tetroxide, and antimony pentoxide. Is preferably 0.1% by weight or less of the entire molding material. More preferably, neither halogen-based flame retardant nor antimony-based flame retardant is included.
Furthermore, in the epoxy resin molding material for sealing of the present invention, the colorant such as carbon black, organic dye, organic pigment, titanium oxide, red lead, bengara, imidazole, triazole, as long as the effects of the present invention are not impaired. Adhesion promotion of 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, thiadiazole derivatives, etc. An agent etc. can be mix | blended as needed.

  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, and thyristors, and passive elements such as capacitors, resistors, and coils, and encapsulated with the epoxy resin molding material for sealing 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 chips connected to the tape carrier by bumps are molded with epoxy resin for sealing. 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 a wiring board connection terminal is 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 1-7 and Comparative Examples 1-10
As the epoxy resin of component (A), an epoxy resin (epoxy resin 1, epoxy equivalent 168, softening point 70 ° C., trade name HP-manufactured by Dainippon Ink & Chemicals, Inc.) having an epoxidized product of dihydroxynaphthalene dimer as a main component 4701),
As a comparative epoxy resin of component (A), an epoxy equivalent of 196, a biphenyl type epoxy resin having a melting point of 106 ° C. (Comparative epoxy resin 1, trade name Epicoat YX-4000H manufactured by Japan Epoxy Resin Co., Ltd.),
A triphenolmethane type epoxy resin having an epoxy equivalent of 170 and a softening point of 60 ° C. (Comparative Epoxy Resin 2, trade name Epicoat 1032H60 manufactured by Japan Epoxy Resin Co., Ltd.) was prepared.
(B) Biphenyl aralkyl type phenol resin having a hydroxyl equivalent of 200 and a softening point of 65 ° C. as a curing agent for the component (curing agent 1, trade name MEH-7851 manufactured by Meiwa Kasei Co., Ltd.),
Β-naphthol aralkyl resin having a hydroxyl group equivalent of 185 and a softening point of 67 ° C. (curing agent 2, trade name SN-170L manufactured by Nippon Steel Chemical Co., Ltd.), triphenylmethane type phenol resin having a hydroxyl group equivalent of 103 and a softening point of 83 ° C. (comparative curing) Agent 1, Meiwa Kasei Co., Ltd. trade name MEH-7500) was prepared.
(C) Spherical silica having a mean particle size of 25 μm and a specific surface area of 2.5 m ² / g (trade name S30-71, manufactured by Micron Co., Ltd.), spherical silica having a mean particle size of 6 μm and a specific surface area of 4.5 m ² / g (Trade name FB-304, manufactured by Denki Kagaku Kogyo Co., Ltd.) and 7/2 / spherical silica (trade name: SO-25R manufactured by Admatechs Co., Ltd.) having an average particle size of 0.5 μm and a specific surface area of 6.5 m ² / g. Inorganic filler mixed at a weight ratio of 1 (inorganic filler 1. average particle size 22 μm, specific surface area 3.3 m ² / g),
Similarly, an inorganic filler mixed at a weight ratio of 5/4/1 (inorganic filler 2. Average particle size 18 μm, specific surface area 3.8 m ² / g),
Coarse sphere silica (trade name MSR-2507 manufactured by Tatsumori Co., Ltd.) having an average particle size of 22 μm and a specific surface area of 3.0 m ² / g, FB-304, and SO-25R in a weight ratio of 7/2/1. Mixed inorganic filler (inorganic filler 3. Average particle size 20 μm, specific surface area 3.5 m ² / g),
Coarse spherical silica (trade name: S-COX31 manufactured by Micron Co., Ltd.) having an average particle size of 20 μm and a specific surface area of 3.5 m ² / g, FB-304, and SO-25R are mixed at a weight ratio of 7/2/1. Inorganic filler (inorganic filler 4. Average particle size 18 μm, specific surface area 3.4 m ² / g),
Rough spherical silica (trade name FB-950, manufactured by Denki Kagaku Kogyo Co., Ltd.) having an average particle size of 25 μm and a specific surface area of 1.5 m ² / g, and an inorganic filler in which the SO-25R is mixed at a weight ratio of 9/1 ( Inorganic filler 5. Average particle size 24 μm, specific surface area 1.8 m ² / g),
An inorganic filler in which a coarse spherical silica (trade name FB-105X, manufactured by Denki Kagaku Kogyo Co., Ltd.) having an average particle size of 10 μm and a specific surface area of 3.0 m ² / g, and the SO-25R are mixed at a weight ratio of 9/1 ( Inorganic filler 6. Average particle size 16 μm, specific surface area 3.3 m ² / g) and inorganic filling in which S30-71, FB-304, and SO-25R are mixed in a weight ratio of 2/7/1 Agent (Comparative inorganic filler 1. Average particle size 13 μm, specific surface area 4.6 m ² / g),
Spherical silica having an average particle size of 7 μm and a specific surface area of 4.5 μm (trade name FB-105 manufactured by Denki Kagaku Kogyo Co., Ltd.) and an inorganic filler (comparative inorganic filler) in which the SO-25R is mixed at a weight ratio of 9/1. 2. An average particle diameter of 13 μm and a specific surface area of 4.6 m ² / g were prepared.
Addition reaction product of triphenylphosphine and p-benzoquinone as a curing accelerator, oxidized polyethylene as a release agent, γ-glycidoxypropyltrimethoxysilane (epoxysilane) as a coupling agent, and carbon black as a colorant (Mitsubishi) Chemical brand name MA-100) was prepared.
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. .

  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.

The epoxy resin molding material for sealing was molded by 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. Further, post-curing was performed at 175 ° C. for 6 hours.
(1) Spiral flow (fluidity index)
The sealing epoxy resin molding material was molded under the above conditions using a spiral flow measurement mold in accordance with EMMI-1-66, and the flow distance (cm) was determined.
(3) Flammability Using the post-cured test piece (test piece thickness 1/8 inch), the flammability was determined according to the 94 UL standard.
(4) Heat resistance TEG-ML1020 chip on SOP-28p (42Alloy lead frame) (Line / Space = 20 μm / 20 μm area 2 locations: 1.90 × 4.20 mm, Line / Space = 10 μm / 10 μm area 2 locations: 1 .90 × 4.20 mm), and the lead frame and the chip were connected by a gold wire of φ20 μm. Then, sealing with the produced molding material was performed, and after post-curing, it was left in an environment of 195 ° C. for 1000 hours.
Of the manufactured packages N = 10 made of each molding material, the presence or absence of electrical continuity after being left was measured, and among the total of 4 wirings, the package having continuity failure even with one wiring was counted as an NG package.
(5) Cold and heat cycle resistance A silicon chip (8 × 10 mm / silicon nitride protective film) was mounted on QFP1420 × 2.0 mmt (EFTEC-64T lead frame / flat island). EN-4065D manufactured by Hitachi Chemical Co., Ltd. was used as the die bond material. The curing condition of the die bond material was 210 ° C./2 minutes. Sealing with a molding material was carried out, and after post-curing, a cooling cycle test was conducted in which the package was alternately immersed in liquid nitrogen (-196 ° C.) and silicone oil (150 ° C.) for 2 minutes each. The package after 50 cycles was observed using SAT manufactured by Hitachi, Ltd., and the presence or absence of chip peeling, lead frame peeling, or package cracking was determined. Of the production packages N = 10 made of each molding material, the packages with defects such as peeling and cracking were counted as NG packages.

  Comparative Examples 1 to 6 in which the component (A) or the component (B) of the present invention deviates from the specifications are all inferior in flame retardancy, and Comparative Examples 5 and 6 are also inferior in cold-heat cycle resistance. Moreover, the comparative examples 7-10 from which (C) component remove | deviates from prescription | regulation are also inferior to a flame retardance.

On the other hand, Examples 1-7 which contain all (A)-(C) component of this invention, and (C) component is an appropriate range are moldability, such as fluidity | liquidity, a flame retardance, and heat resistance. It can be seen that both the heat resistance and the thermal cycle resistance are excellent.

Claims (5)

(A) an epoxy resin containing an epoxy resin obtained by glycidyl etherification of at least one dimer of hydroxynaphthalene and dihydroxynaphthalene, (B) a curing agent containing a compound represented by the following general formula (I), C) An epoxy resin molding material for sealing, containing an inorganic filler, wherein the component (C) is at least one having an average particle size of 15 μm or more and a specific surface area of 4.5 m ² / g or less.

(In general formula (I), n represents 0 or a positive integer, and the hydrogen atom on the benzene ring and naphthalene ring in A and B may be substituted with a hydrocarbon group.)   2. The epoxy resin molding material for sealing according to claim 1, wherein the content of both the halogen-based flame retardant and the antimony-based flame retardant is 0.1% by weight or less of the entire molding material.   The epoxy resin molding material for sealing according to claim 2, which does not contain a halogen flame retardant and an antimony flame retardant.   The epoxy resin molding material for sealing according to any one of claims 1 to 3, wherein the amount of the inorganic filler (C) is 70 wt% or more and 88 wt% or less of the entire molding material. The electronic component apparatus provided with the element sealed with the epoxy resin molding material for sealing in any one of Claims 1-4.