JP2006002041A - 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 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, (B) a hardener expressed by general formula (I) (wherein, n is 0 or a positive integer; and a hydrogen on the benzene ring may be substituted with a hydrocarbon group) and (C) an inorganic filler. Component (C) accounts for ≥70 wt.% and ≤88 wt.% of the total weight of the molding material. At least one component of the component (C) has a specific surface area of ≤2.0 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 have more stringent reliability than so-called consumer applications such as personal computers and home appliances in terms of reliability such as cold and heat cycle resistance. In order to improve the cold heat cycle resistance, a technique such as bringing the coefficient of thermal expansion between the semiconductor internal member and the epoxy resin molding material for sealing close to each other can be used.
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 a method 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 adding a metal hydroxide (for example, a patent) (See Document 2). However, especially in the case of copper lead frame packages, if the linear expansion coefficient of the epoxy resin molding material for sealing is to be close to that of the lead frame in order to improve the thermal cycle resistance, the flame retardancy is reduced due to the decrease in the amount of inorganic filler material. It becomes difficult to ensure, and it becomes necessary to add a large amount of these flame retardants. Addition of a large amount of flame retardant causes problems such as adverse effects on heat resistance, moldability, etc., and at present, no sufficient solution has been found.
JP 9-235449 A Japanese Patent Laid-Open No. 9-241383

  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 adverse effects on heat resistance and moldability.

  The present invention has been made in view of such a situation, and realizes high flame retardancy without substantially using a flame retardant such as a halogenated resin, an antimony compound, or an organic phosphorus flame retardant or a metal hydroxide, An object of the present invention is to provide an epoxy resin molding material for sealing excellent in reliability such as heat resistance and cold-heat cycle resistance, and an electronic component device including an element sealed thereby.

  As a result of intensive studies to solve the above problems, the inventors add a curing agent having a specific structure and an inorganic filler having a specific specific surface area to the epoxy resin molding material for sealing. Thus, the inventors have found that the above object can be achieved, and have completed the present invention.

（一般式（I）で、ｎは０又は正の整数を表す。ベンゼン環の水素は炭化水素基で置換されていても良い。）
（２）(Ｃ)成分のうち、比表面積が２．０ｍ²／ｇ以下である成分が結晶シリカ、溶融シリカ、及び合成シリカの内の少なくとも一つを含む前記（１）に記載の封止用エポキシ樹脂成形材料、
（３）（Ｃ）成分のうち、比表面積が２．０ｍ²／ｇ以下である成分が、（Ｃ）成分全体の３０重量％以上である前記（２）に記載の封止用エポキシ樹脂成形材料、
（４）臭素系難燃剤及びアンチモン系難燃剤を含有しない前記（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）（Ｄ）硬化促進剤を含み、該硬化促進剤に有機リン系化合物を含有する前記（１）〜（４）のいずれかに記載の封止用エポキシ樹脂成形材料、
（６）前記（１）〜（５）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 comprises (1) (A) an epoxy resin, (B) a curing agent containing a compound represented by the following general formula (I), (C) an inorganic filler, and (C) component is the entire molding material An epoxy resin molding material for sealing wherein the specific surface area of at least one component is 2.0 m ² / g or less.

(In general formula (I), n represents 0 or a positive integer. The hydrogen of the benzene ring may be substituted with a hydrocarbon group.)
(2) Among the components (C), the component having a specific surface area of 2.0 m ² / g or less contains at least one of crystalline silica, fused silica, and synthetic silica. Epoxy resin molding material,
(3) Among the components (C), the component having a specific surface area of 2.0 m ² / g or less is 30% by weight or more of the entire component (C). material,
(4) The epoxy resin molding material for sealing according to any one of (1) to (3), which does not contain a brominated flame retardant and an antimony flame retardant,
(5) The epoxy resin molding material for sealing according to any one of the above (1) to (4), comprising (D) a curing accelerator and containing an organophosphorus compound in the curing accelerator,
(6) An electronic component device including an element sealed with the sealing epoxy resin molding material according to any one of (1) to (5),
About.

  The epoxy resin molding material for sealing according to the present invention is excellent in reliability such as flame retardancy, heat resistance, and cold cycle resistance, and electronic components such as ICs, LSIs and the like are made using this epoxy resin molding material for sealing. If sealed, an electronic component device having excellent reliability such as flame retardancy, heat resistance, and thermal cycle resistance can be obtained, and its industrial value is great.

  In the present invention, it is possible to use an epoxy resin that is generally used as an epoxy resin molding material for sealing as the component (A) without any particular limitation. For example, phenol novolac type epoxy resin, orthocresol novolac type epoxy resin and other phenols, cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol F and other phenols and / or α-naphthol, β-naphthol, Epoxidized novolak resin obtained by condensation or cocondensation of naphthols such as dihydroxynaphthalene and a compound having an aldehyde group such as formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, salicylaldehyde under an acidic catalyst, bisphenol A, Biglycidyl ethers such as bisphenol F, bisphenol S, bisphenol A / D, and diglycidyl ethers of alkyl-substituted or unsubstituted biphenols Phenyl type epoxy resins, phenol / aralkyl resins synthesized from phenols and / or naphthols and dimethoxyparaxylene or bis (methoxymethyl) biphenyl, naphthol / aralkyl resins, epoxidized biphenyl / aralkyl resins, stilbene type epoxy resins, Hydroquinone type epoxy resins, glycidyl ester type epoxy resins obtained by the reaction of polybasic acids such as phthalic acid and dimer acid and epichlorohydrin, glycidyl amine type epoxy resins obtained by the reaction of polyamines such as diaminodiphenylmethane and isocyanuric acid and epichlorohydrin, cyclohexane Dicyclopentadiene type epoxy resin, epoxidized product of co-condensation resin of pentadiene and phenol, epoxy resin having naphthalene ring, triphenol Type epoxy resin, trimethylolpropane type epoxy resin, terpene modified epoxy resin, linear aliphatic epoxy resin obtained by oxidizing olefinic bond with peracid such as peracetic acid, alicyclic epoxy resin, and these epoxy resins And epoxy resin modified with silicone, acrylonitrile, butadiene, isoprene-based rubber, polyamide-based resin and the like.

（一般式（I）で、ｎは０又は正の整数を表す。ベンゼン環の水素は炭化水素基で置換されていても良い。）
本発明の効果である高い難燃性を実現する為には、一般式（I）で表される硬化剤を（Ｂ）成分の５０重量％以上とすることが好ましく、６０重量％以上がより好ましく、７０重量％以上が特に好ましい。一般式（I）で表される硬化剤としては、ｎ＝１〜１０程度で、ベンゼン環の側鎖がすべて水素であるＭＥＨ-７８５１（明和化成株式会社製商品名）が市場で入手可能である。
本発明では（Ｂ）成分として、一般式（I）で表される硬化剤の他に、封止用エポキシ樹脂成形材料に一般に使用されている硬化剤を、その発明の効果を失わない範囲において併用することができる。例えば、フェノール、クレゾール、レゾルシン、カテコール、ビスフェノールＡ、ビスフェノールＦ、フェニルフェノール、アミノフェノール等のフェノール類及び／又はα−ナフトール、β−ナフトール、ジヒドロキシナフタレン等のナフトール類とホルムアルデヒド、ベンズアルデヒド、サリチルアルデヒド等のアルデヒド基を有する化合物とを酸性触媒下で縮合又は共縮合させて得られるノボラック型フェノール樹脂、ジシクロペンタジエン型フェノール樹脂、テルペン変性フェノール樹脂、トリフェノールメタン型フェノール樹脂等が挙げられ、信頼性や難燃性の点からは、下記一般式（II）〜（IV）で表されるフェノール・アラルキル樹脂、ナフトール・アラルキル樹脂等を併用することが好ましい。

（一般式（II）で、ｎは０又は１〜１０の整数を表す。ベンゼン環の水素は炭化水素基で置換されていても良い。）

（一般式（III）で、ｎは０又は正の整数を表す。ベンゼン環、ナフタレン環の水素は炭化水素基で置換されていても良い。）

（一般式（IV）で、ｎは０又は正の整数を表す。ベンゼン環、ナフタレン環の水素は炭化水素基で置換されていても良い。）
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三井化学株式会社製商品名ＸＬＣ等が、上記一般式（III）で示されるナフトール・アラルキル樹脂としては新日鐵化学株式会社製商品名ＳＮ−４７５等が、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新日鐵化学株式会社製商品名ＳＮ−１７０等が、それぞれ市場で入手可能である。 In the curing agent (B) of the present invention, it is necessary to use a compound represented by the following general formula (I) alone or in combination, particularly from the viewpoint of flame retardancy.

(In general formula (I), n represents 0 or a positive integer. The hydrogen of the benzene ring may be substituted with a hydrocarbon group.)
In order to achieve the high flame retardancy that is the effect of the present invention, the curing agent represented by the general formula (I) is preferably 50% by weight or more of the component (B), more preferably 60% by weight or more. Preferably, 70% by weight or more is particularly preferable. As the curing agent represented by the general formula (I), MEH-7851 (trade name, manufactured by Meiwa Kasei Co., Ltd.) in which n = 1 to 10 and all side chains of the benzene ring are hydrogen is available on the market. is there.
In the present invention, as the component (B), in addition to the curing agent represented by the general formula (I), the curing agent generally used in the epoxy resin molding material for sealing is within a range not losing the effect of the invention. Can be used together. For example, 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, benzaldehyde, salicylaldehyde, etc. Such as novolak-type phenolic resin, dicyclopentadiene-type phenolic resin, terpene-modified phenolic resin, and triphenolmethane-type phenolic resin obtained by condensation or cocondensation with a compound having an aldehyde group under an acidic catalyst. From the viewpoint of flame retardancy, it is preferable to use a phenol / aralkyl resin, a naphthol / aralkyl resin, or the like represented by the following general formulas (II) to (IV) in combination.

(In the general formula (II), n represents 0 or an integer of 1 to 10. The hydrogen of the benzene ring may be substituted with a hydrocarbon group.)

(In general formula (III), n represents 0 or a positive integer. Hydrogen in the benzene ring and naphthalene ring may be substituted with a hydrocarbon group.)

(In general formula (IV), n represents 0 or a positive integer. Hydrogen in the benzene ring and naphthalene ring may be substituted with a hydrocarbon group.)
The phenolic aralkyl resin represented by the general formula (II) is trade name XLC manufactured by Mitsui Chemicals, and the naphthol aralkyl resin represented by the general formula (III) is trade name manufactured by Nippon Steel Chemical Co., Ltd. As a naphthol-aralkyl resin in which SN-475 and the like are represented by the above general formula (IV), trade name SN-170 manufactured by Nippon Steel Chemical Co., Ltd. is available on the market.

  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.

In the present invention, it is necessary to add (C) an inorganic filler for the purpose of reducing the linear expansion coefficient, improving the hygroscopicity and improving the strength, and in particular, from the viewpoint of flame retardancy, the specific surface area is 2.0 m ² / It is necessary to blend at least one component (hereinafter referred to as the component (C1)) of g or less. Examples of the inorganic filler include fused silica, crystalline silica, synthetic silica, alumina, zircon, calcium silicate, calcium carbonate, potassium titanate, silicon carbide, silicon nitride, aluminum nitride, boron nitride, beryllia, zirconia, zircon, phospho Examples thereof include powders such as stellite, steatite, spinel, mullite, and titania, beads formed by spheroidizing these, and glass fibers. 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 a comprehensive viewpoint such as fluidity, linear expansion coefficient, flame retardancy, and reliability, it is preferable that part or all of the component (C) is crystalline silica, fused silica, or synthetic silica, particularly in terms of flame retardancy. More preferably, the components (C1) to (C1) contain at least one of the silica group consisting of crystalline silica fused silica and synthetic silica.
The component (C1) is preferably 30% by weight or more of the total component (C), and more preferably, the component (C1) contains at least one of the above silica group. Setting the component (C1) to 30% by weight or more of the component (C) is effective for ensuring flame retardancy particularly in a region where the amount of the inorganic filler is relatively small. Inorganic fillers with a small specific surface area, especially crystalline silica, fused silica, or synthetic silica, provide a thick surface expansion layer with a relatively large thermal insulation effect during the burning of the epoxy resin molding material for sealing, and thereby high flame resistance It is thought to give.
The crystalline silica, fused silica, or synthetic silica in the present invention is natural silica, natural silica obtained by crushing and then vitrifying through a thermal spraying process, or a silicon compound such as silicon alone or tetrachlorosilane as a starting material. The silica obtained as above (silicon dioxide) is vitrified through a thermal spraying process during or after synthesis. From the viewpoint of fluidity, it is preferable to use so-called spherical silica having a sphericity measured by the following method (1) of 0.70 or more. In addition, the specific surface area in this invention points out the value obtained by following (2).
(1) Sphericality Measuring device: FPIA-2100
Target particle size: 45 μm or more (particles remaining on the sieve with JIS sieve 45 μm)
Number of target particles: 200 Measurement method, etc .:
1) (sample 20 g / pure water 80 ml) + ultrasound 3 minutes.
2) Remove particles of 45 μm or less with a JIS sieve (45 μm).
3) Add 20 ml of a 50% ethylene glycol solution to 1.0 g of the particles on the sieve, and disperse for 3 minutes using ultrasonic waves.
4) Apply to the analyzer and determine the sphericity according to the following formula.
(Sphericity) = (projection area / area of a circle having the same circumference as the projected perimeter of the particle)
(2) Specific surface area measuring device: flow method BET single point method specific surface area measuring device monosorb manufactured by Yuasa Ionics Co., Ltd. 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 The blending amount of the inorganic filler is required to be 70 to 88% by weight of the entire molding material, particularly from the viewpoint of thermal cycle resistance in a copper lead frame package. It is more preferable to set it as -88 weight%, and it is especially preferable to set it as 75-85 weight%. Even if the component (C) is less than 70% by weight or more than 88% by weight, mismatch of the linear expansion coefficient between the epoxy resin molding material for sealing and the lead frame becomes remarkable, which is disadvantageous for the thermal cycle resistance.

In the present invention, it is preferable to further include (D) a curing accelerator. Particularly, when an organic phosphorus compound is used as the curing accelerator, it is effective in terms of flame retardancy and reliability. The organophosphorus compound in the present invention is directly bonded to at least one of an alkyl group, a phenyl group, and a phenyl group derivative in which part or all of the hydrogen atoms of the phenyl group are substituted with an alkyl group or an alkoxy group in the molecule. This compound has an intramolecular polarization formed by adding a compound having a π bond such as maleic anhydride, a quinone compound, diazophenylmethane, or a phenol resin, or a tetraphenylboron salt or a derivative thereof. Also includes compounds.
For example, tributylphosphine, methyldiphenylphosphine, triphenylphosphine, tris (4-methylphenyl) phosphine, diphenylphosphine, phenylphosphine, adduct of triphenylphosphine and p-benzoquinone, tris (4-methylphenyl) phosphine and p- Examples include adducts with benzoquinone, adducts with tributylphosphine and p-benzoquinone, tetraphenylphosphine tetraphenylborate, triphenylphosphinetetraphenylborate, and the like. You may use together.
In addition, 1,8-diaza-bicyclo (5,4,0) undecene-7,1,5-diaza-bicyclo (4,3,0) nonene, 5,6- Cycloamidine compounds such as dibutylamino-1,8-diaza-bicyclo (5,4,0) undecene-7 and these compounds include maleic anhydride, 1,4-benzoquinone, 2,5-toluquinone, 1,4- Naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, phenyl-1,4- Benzyldimethylamine, a compound with intramolecular polarization formed by adding a quinone compound such as benzoquinone, diazophenylmethane, a compound having a π bond such as a phenol resin, etc. Tertiary amine compounds such as triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol, and derivatives thereof, imidazole compounds such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, and the like Derivatives of 2-ethyl-4-methylimidazole tetraphenylborate, tetraphenylboron salts such as N-methylmorpholine tetraphenylborate and nitrogen-based curing accelerators such as these derivatives are used in combination with the organophosphorus curing accelerator. Can also be used.

  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 addition to the components (A) to (D), if necessary, silane coupling agents such as epoxy silane, mercapto silane, amino silane, alkyl silane, ureido silane, vinyl silane, aluminate coupling agent, Known coupling agents conventionally used in sealing epoxy resin molding materials such as titanate coupling agents can be added.
When a coupling agent is added, the addition amount is set to 0% of the entire molding material in order to ensure reliability and particularly flame retardance in a region (70 wt% to 85 wt%) where the inorganic filler is relatively small. It is preferable that the content be 5% by weight or less.

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.
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, A conventionally known release agent used for an epoxy resin molding material for sealing, such as polyethylene wax, can be used.

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. Of these, hydrotalcite and bismuth hydrous oxide represented by the following general formula (V) are preferable.
(Chemical formula 6)
Mg _1-X Al _X (OH) ₂ (CO ₃ ) _{X / 2} · mH ₂ O (V)
(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.

  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.

（一般式（I）で、ｎは０又は正の整数を表す。ベンゼン環の水素は炭化水素基で置換されていても良い。） Examples 1-9 and Comparative Examples 1-8
As the epoxy resin of component (A), an ortho-cresol novolak type epoxy resin having an epoxy equivalent of 200 and a softening point of 60 ° C. (epoxy resin 1, trade name EPICLON N500P-1 manufactured by Dainippon Ink and Chemicals, Inc.), an epoxy equivalent of 196, a melting point 106 ° C. biphenyl type epoxy resin (epoxy resin 2, Japan Epoxy Resin Co., Ltd. trade name Epicoat YX-4000H),
As a curing agent for component (B), a biphenyl aralkyl type phenolic resin (curing agent 1, curing agent Meiwa Kasei Co., Ltd.) having a hydroxyl group equivalent of 200, a softening point of 65 ° C., and the side chain of the benzene ring is all hydrogen in the following general formula (I) Company product name MEH-7851), hydroxyl group equivalent 175, softening point 70 ° C phenol aralkyl resin (comparative curing agent 1, Mitsui Chemicals product name Millex XL-225), hydroxyl group equivalent 185, softening point 67 ° C β-naphthol / aralkyl resin (comparative curing agent 2, Nippon Steel Chemical Co., Ltd., trade name SN-170L),
As component (C), fused 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, an average particle size of 20 μm and a specific surface area of 3.3 m ² / g 5 / of fused spherical silica (trade name S-COX31 manufactured by Micron Co., Ltd.) and synthetic spherical silica (trade name SO-25R, manufactured by Admatex Co., Ltd.) having an average particle size of 0.5 μm and a specific surface area of 6.5 m ² / g. 4/1 (weight ratio) mixture (silica 1),
Similarly 2/7/1 mixed product (silica 2),
Fused spherical silica (trade name MSR-2212 manufactured by Tatsumori Co., Ltd.) having a mean particle size of 20 μm and a specific surface area of 3.5 m ² / g, and a 5/4/1 mixture of the SO-25R (silica) 3),
Similarly 2/7/1 mixed product (silica 4),
7/2/1 mixing of FB-950 with crushed silica (trade name F-205, manufactured by Fukushima Ceramics Co., Ltd.) having an average particle size of 5.0 μm and a specific surface area of 6.0 m ² / g, and SO-25R Product (silica 5),
Spherical silica having an average particle size of 20 μm and a specific surface area of 1.6 m ² / g (trade name S-125 manufactured by Micron Co., Ltd.), and a 9/1 mixed product with the SO-25R (silica 6),
(C) 9/1 mixed product of S-COX31 and SO-25R (comparative silica 1), 9/1 mixed product of MSR-2212 and SO-25R (comparative silica 2) as comparative components of component (C),
As component (D), triphenylphosphine (curing accelerator 1), adduct of triphenylphosphine and p-benzoquinone (curing accelerator 2), 1,8-diazabicyclo (5,4,0) undecene-7 (DBU, Curing accelerator 3),
Tables 1 and 2 show γ-glycidoxypropyltriethoxysilane as a coupling agent, oxidized polyethylene wax as a release agent, and carbon black (trade name MA-100 manufactured by Mitsubishi Chemical Corporation) as a colorant, respectively. Blended in parts by weight, roll kneading was carried out under conditions of a kneading temperature of 80 ° C. and a kneading time of 10 minutes to produce the epoxy resin molding materials for sealing of Examples and Comparative Examples. The average particle diameter and specific surface area of the component (C) were measured by the following methods.
(1) Average particle diameter 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 monosorb manufactured by Yuasa Ionics Co., Ltd. Carrier gas: nitrogen / helium mixed gas 1.5 kg / cm ² , nitrogen gas 0.7 kg / cm ²
Sample degassing conditions: 200 ° C./30 minutes

(In general formula (I), n represents 0 or a positive integer. The hydrogen of the benzene ring may be substituted with a hydrocarbon group.)

Composition

Composition

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) Flammability According to 94UL standard, the test piece thickness after post-curing was tested at 1/8 inch to determine the flammability.
(2) 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.
(3) 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. After sealing with a molding material and post-curing, a thermal cycle test was performed 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.

(B) Comparative Examples 1 to 4 not containing curing agent 1 as a component are inferior in flame retardancy, and Comparative Examples 5 to 8 in which component (C) deviates from the specifications are either flame retardant or cold cycle resistance. Inferior.
On the other hand, Examples 1 to 9 containing the curing agent 1 and the (C1) component as the (B) component are excellent in flame retardancy, heat resistance, cold cycle resistance, and the like. The flame retardancy of Examples 1, 3, 5 and 6 containing 30% by weight or more, and the heat resistance and the like of Examples 1 to 8 using an organophosphorus curing accelerator as the component (D) are particularly excellent. Recognize.

Claims (6)

(A) an epoxy resin, (B) a curing agent containing a compound represented by the following general formula (I), (C) an inorganic filler, and the component (C) is 70% by weight or more of the entire molding material An epoxy resin molding material for sealing which is 88% by weight or less and the specific surface area of at least one component is 2.0 m ² / g or less.

(In general formula (I), n represents 0 or a positive integer. The hydrogen of the benzene ring may be substituted with a hydrocarbon group.) The epoxy resin molding material for sealing according to claim 1, wherein the component having a specific surface area of 2.0 m ² / g or less among the component (C) includes at least one of crystalline silica, fused silica and synthetic silica. . 3. The epoxy resin molding material for sealing according to claim 2, wherein a component having a specific surface area of 2.0 m ² / g or less among the component (C) is 30% by weight or more of the total component (C).   The epoxy resin molding material for sealing according to any one of claims 1 to 3, which does not contain a halogen flame retardant and an antimony flame retardant.   (D) The epoxy resin molding material for sealing according to any one of claims 1 to 4, comprising a curing accelerator, wherein the curing accelerator contains an organic phosphorus compound. The electronic component apparatus provided with the element sealed with the epoxy resin molding material for sealing in any one of Claims 1-5.