JP2006188573A - Liquid epoxy resin composition, electronic component device using the composition and method for producing the same - Google Patents

Liquid epoxy resin composition, electronic component device using the composition and method for producing the same Download PDF

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JP2006188573A
JP2006188573A JP2005000267A JP2005000267A JP2006188573A JP 2006188573 A JP2006188573 A JP 2006188573A JP 2005000267 A JP2005000267 A JP 2005000267A JP 2005000267 A JP2005000267 A JP 2005000267A JP 2006188573 A JP2006188573 A JP 2006188573A
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epoxy resin
resin composition
liquid epoxy
dbu
bisphenol
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Satoru Tsuchida
悟 土田
Michitoshi Arata
道俊 荒田
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Showa Denko Materials Co Ltd
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Hitachi Chemical Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/10—Bump connectors; Manufacturing methods related thereto
    • H01L2224/15—Structure, shape, material or disposition of the bump connectors after the connecting process
    • H01L2224/16—Structure, shape, material or disposition of the bump connectors after the connecting process of an individual bump connector
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/73—Means for bonding being of different types provided for in two or more of groups H01L2224/10, H01L2224/18, H01L2224/26, H01L2224/34, H01L2224/42, H01L2224/50, H01L2224/63, H01L2224/71
    • H01L2224/732—Location after the connecting process
    • H01L2224/73201—Location after the connecting process on the same surface
    • H01L2224/73203—Bump and layer connectors
    • H01L2224/73204—Bump and layer connectors the bump connector being embedded into the layer connector
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
    • H01L2224/83—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a layer connector
    • H01L2224/8319—Arrangement of the layer connectors prior to mounting
    • H01L2224/83192—Arrangement of the layer connectors prior to mounting wherein the layer connectors are disposed only on another item or body to be connected to the semiconductor or solid-state body
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/10—Details of semiconductor or other solid state devices to be connected
    • H01L2924/11—Device type
    • H01L2924/13—Discrete devices, e.g. 3 terminal devices
    • H01L2924/1301—Thyristor

Abstract

<P>PROBLEM TO BE SOLVED: To provide an epoxy resin molding compound with no defects such as voids, excellent in solder jointability, and having good reliability such as reflow resistance, temperature cycle resistance and humidity resistance, and to provide a semiconductor device comprising an element sealed with the epoxy resin molding compound for sealing. <P>SOLUTION: A solvent-free liquid epoxy resin composition comprises an epoxy resin (A), a curing agent (B), and an accelerator (C) composed of at least one compound selected from DBU, a salt of DBU, DBN and a salt of DBN, wherein the curing agent (B) is an aromatic amine, and the weight ratio of the sum of DBU and DBN to the total amount of the epoxy resin (A) and the accelerator (C) is 0.02-0.10. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

本発明は、液状エポキシ樹脂組成物、それを用いた半導体装置等の電子部品装置及びその製造方法に関する。   The present invention relates to a liquid epoxy resin composition, an electronic component device such as a semiconductor device using the same, and a method for manufacturing the same.

半導体は素子を外部環境から保護して各種信頼性を確保すると同時に基板への実装を容易にするためパッケージが必要である。パッケージには種々の形態があるが、一般的には金属製リードフレームに形成されたタブに素子を固着し、素子表面の電極とインナーリード間を金ワイヤで電気的に接続し、素子、金ワイヤ及びリードフレームの一部をエポキシ樹脂組成物を用い低圧トランスファ成形法で封止したパッケージが広く実用に供されている。このような樹脂封止型半導体装置は、素子サイズに比べてパッケージの外形がかなり大きく、高密度実装の観点からは極めて非効率的である。そのため、パッケージ形態はピン挿入型から表面実装型に移行するとともに小型・薄型化が積極的に行われた。しかし、金属製リードフレームに素子を搭載し、ワイヤボンディングしたものを樹脂封止する構造を採用する以上、実装効率を高めるには限界があった。そこで、ＣＯＢ（Chip on Board）、ハイブリッドＩＣ、モジュール、カードなどの分野では、一部の素子を高密度実装するためベアチップをバンプを介して基板にフェースダウンで実装するいわゆるフリップチップ実装を採用してきた。最近は素子の高集積化、高機能化、多ピン化、システム化、高速化、低コスト化などに対応するためＣＳＰ（Chip Size/Scale Package）と呼ばれる種々の小型パッケージが開発され、パッケージ用基板に素子を搭載する方法として、実装効率のほか電気特性、多ピン化対応に優れるフリップチップ実装の採用が増えている。また、最近の表面実装型パッケージやＣＳＰは、端子がエリアアレイ状に配置されたものが多く、この種のパッケージの実装形態はフリップチップ実装と同じである。   A semiconductor needs a package in order to protect the element from the external environment and ensure various reliability, and at the same time facilitate mounting on a substrate. There are various types of packages, but in general, an element is fixed to a tab formed on a metal lead frame, and an electrode on the element surface and an inner lead are electrically connected by a gold wire, and the element, gold A package in which a part of a wire and a lead frame is sealed by a low-pressure transfer molding method using an epoxy resin composition is widely used. Such a resin-encapsulated semiconductor device has a considerably larger package outer shape than the element size, and is extremely inefficient from the viewpoint of high-density mounting. For this reason, the package form has shifted from the pin insertion type to the surface mount type, and has been actively reduced in size and thickness. However, as long as a structure in which an element is mounted on a metal lead frame and a wire-bonded structure is resin-sealed is adopted, there is a limit to increasing the mounting efficiency. Therefore, in the fields of COB (Chip on Board), hybrid ICs, modules, cards, etc., so-called flip chip mounting has been adopted in which a bare chip is mounted face-down on a substrate via bumps in order to mount some elements at high density. It was. Recently, various small packages called CSP (Chip Size / Scale Package) have been developed to cope with high integration, high functionality, high pin count, systemization, high speed, and low cost of devices. As a method for mounting an element on a substrate, flip chip mounting which is excellent in mounting efficiency, electrical characteristics, and high pin count is increasing. Also, many recent surface mount packages and CSPs have terminals arranged in an area array, and the mounting form of this type of package is the same as flip chip mounting.

ところで、フリップチップ実装を行う場合、素子と基板あるいはＣＳＰはそれぞれ熱膨張係数が異なるため接合部に熱応力が発生し接続信頼性の確保が重要な課題である。また、ベアチップは回路形成面が充分に保護されていないため、水分やイオン性不純物が浸入し易く耐湿信頼性の確保も重要な課題である。その対策として、通常素子と基板の間隙にアンダーフィル材と呼ばれるエポキシ樹脂組成物を介在させ、接合部の補強及び素子の保護を行っている。樹脂組成物を介在させる方式として、一般的には液状のエポキシ樹脂組成物を素子の周辺に滴下し、毛細管現象により素子と基板の隙間にしみ込ませる方法が採用されている。しかしながらこの方式ではフリップチップや基板のはんだ酸化皮膜を除去するためのフラックス塗付工程、パッケージ組み立て工程、フラックス残渣洗浄工程、アンダーフィル材注入工程、アンダーフィル材硬化工程等、時間やプロセスが長くなるという欠点があった。
そこで、この問題を解決するために回路基板に先に樹脂を塗布し、はんだバンプを有したチップをその上から搭載しバンプ接合と樹脂封止を同時に行う方法が提案されている（特許文献１参照。）。この場合、樹脂にははんだの酸化皮膜を除去する機能が必要なため一般的には樹脂に酸性度の強いカルボン酸系化合物が添加される。
しかし、カルボン酸系化合物は樹脂のイオン性不純物や電気伝導度を悪化させるため絶縁不良を招いたり、またＰＣＴやＨＡＳＴ処理による吸湿の際に接着力を低下させるため耐湿信頼性を悪化させる恐れがあった。
特開平4-80443号公報（特許第2589239号） By the way, when flip chip mounting is performed, the thermal expansion coefficient is different between the element and the substrate or the CSP, so that thermal stress is generated at the joint and it is important to ensure connection reliability. In addition, since the circuit forming surface of the bare chip is not sufficiently protected, moisture and ionic impurities are liable to enter, and ensuring moisture resistance reliability is also an important issue. As a countermeasure, an epoxy resin composition called an underfill material is usually interposed between the element and the substrate to reinforce the joint and protect the element. As a method of interposing the resin composition, generally, a method is adopted in which a liquid epoxy resin composition is dropped around the element and soaked into the gap between the element and the substrate by a capillary phenomenon. However, this method requires a long time and process such as a flux coating process, a package assembly process, a flux residue cleaning process, an underfill material injection process, and an underfill material curing process for removing the solder oxide film on the flip chip and the substrate. There was a drawback.
In order to solve this problem, a method has been proposed in which a resin is first applied to a circuit board, a chip having solder bumps is mounted thereon, and bump bonding and resin sealing are simultaneously performed (Patent Document 1). reference.). In this case, since the resin needs to have a function of removing the oxide film of the solder, a carboxylic acid compound having a strong acidity is generally added to the resin.
However, carboxylic acid compounds may deteriorate the ionic impurities and electrical conductivity of the resin, leading to poor insulation, and may deteriorate the moisture resistance reliability due to a decrease in adhesive strength during moisture absorption by PCT or HAST treatment. there were.
Japanese Patent Laid-Open No. 4-80443 (Patent No. 2589239)

本発明は酸性度の高い添加剤を含有せずに、フリップチップパッケージの接合と封止を同時に行うことができ、高信頼性を有する液状エポキシ樹脂組成物及び電子部品装置を提供しようとするものである。   The present invention is intended to provide a liquid epoxy resin composition and an electronic component device that can perform bonding and sealing of a flip chip package at the same time without containing a highly acidic additive, and have high reliability. It is.

本発明者らは上記の課題を解決するために鋭意検討した結果、エポキシ樹脂、硬化剤、及び硬化促進剤を含有する液状エポキシ樹脂組成物において、硬化促進剤として強塩基化合物及び/又はその塩を用いるとはんだ酸化皮膜の除去が可能であること、吸湿処理による信頼性を低下しないこと等を見出し、さらに検討を重ねて本発明を完成するに至った。   As a result of intensive studies to solve the above-mentioned problems, the present inventors have determined that, in a liquid epoxy resin composition containing an epoxy resin, a curing agent, and a curing accelerator, a strong base compound and / or a salt thereof as a curing accelerator As a result, it has been found that the solder oxide film can be removed and the reliability of the moisture absorption treatment is not lowered, and the present invention has been completed through further studies.

本発明は、
（１）（Ａ）エポキシ樹脂、（Ｂ）硬化剤、（Ｃ）DBU、DBUの塩、DBN及びDBNの塩の内の少なくとも一種類からなる硬化促進剤を含有する無溶剤型液状エポキシ樹脂組成物であって、（Ｂ）硬化剤が芳香族アミンであり、（Ａ）エポキシ樹脂と（Ｃ）硬化促進剤との合計量におけるDBU及びDBNの和の重量比率が0.02〜0.10の範囲にあることを特徴とする液状エポキシ樹脂組成物、
（２）（Ａ）エポキシ樹脂が、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＡ／Ｄ型エポキシ樹脂、ビスフェノールＳ型エポキシ樹脂、水添ビスフェノールＡ型エポキシ樹脂、ナフタレンジオール型エポキシ樹脂、アミノグリシジルエーテル型エポキシ樹脂から選ばれる少なくとも１種類の液状エポキシ樹脂を含む前記（１）の液状エポキシ樹脂組成物、
（３）無機または有機基板の回路形成面の素子を搭載する位置に上記（１）または（２）の液状エポキシ樹脂組成物を塗布した後、素子の電極と基板の回路をバンプを介して接合すると同時に前記エポキシ樹脂組成物の硬化を行うかまたはその後の加熱処理により前記エポキシ樹脂組成物の硬化を行うことを特徴とする電子部品装置の製造方法、
（４）無機または有機基板の回路上に前記（１）または（２）記載の液状エポキシ樹脂組成物により封止された素子を備えたことを特徴とする電子部品装置
に関する。 The present invention
(1) (A) epoxy resin, (B) curing agent, (C) DBU, DBU salt, DBN and DBN salt, a solvent-free liquid epoxy resin composition containing at least one curing accelerator (B) the curing agent is an aromatic amine, and the weight ratio of the sum of DBU and DBN in the total amount of (A) epoxy resin and (C) curing accelerator is in the range of 0.02 to 0.10. A liquid epoxy resin composition characterized by
(2) (A) The epoxy resin is bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol A / D type epoxy resin, bisphenol S type epoxy resin, hydrogenated bisphenol A type epoxy resin, naphthalenediol type epoxy resin, The liquid epoxy resin composition according to (1), comprising at least one liquid epoxy resin selected from aminoglycidyl ether type epoxy resins;
(3) After applying the liquid epoxy resin composition of (1) or (2) above to the position where the element is mounted on the circuit forming surface of the inorganic or organic substrate, the electrode of the element and the circuit of the substrate are bonded via bumps. And simultaneously curing the epoxy resin composition or curing the epoxy resin composition by a subsequent heat treatment,
(4) The present invention relates to an electronic component device comprising an element sealed with a liquid epoxy resin composition as described in (1) or (2) above on an inorganic or organic circuit.

本発明の液状エポキシ樹脂組成物はボイドなどの欠陥が無く、はんだ接合性に優れ、また信頼性も良好である。   The liquid epoxy resin composition of the present invention has no defects such as voids, is excellent in solder jointability, and has good reliability.

本発明に用いる（Ａ）液状エポキシ樹脂は、特に制限はなく、例えば、ビスフェノールＡ、ビスフェノールＦ、ビスフェノールＡＤ、ビスフェノールＳ、ナフタレンジオール、水添ビスフェノールＡ等とエピクロルヒドリンの反応により得られるグリシジルエーテル型エポキシ樹脂、オルソクレゾールノボラック型エポキシ樹脂をはじめとするフェノール類とアルデヒド類とを縮合又は共縮合させて得られるノボラック樹脂をエポキシ化したもの、フタル酸、ダイマー酸等の多塩基酸とエピクロルヒドリンの反応により得られるグリシジルエステル型エポキシ樹脂、ジアミノジフェニルメタン、イソシアヌル酸等のポリアミンとエピクロルヒドリンの反応により得られるアミノグリシジルエーテル型エポキシ樹脂、オレフィン結合を過酢酸等の過酸で酸化して得られる線状脂肪族エポキシ樹脂、及び脂環族エポキシ樹脂などを用いることができる。特に、本発明では、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＡＤ型エポキシ樹脂、ビスフェノールＳ型エポキシ樹脂、水添ビスフェノールＡ型エポキシ樹脂、ナフタレンジオール型エポキシ樹脂、アミノグリシジルエーテル型エポキシ樹脂から選ばれる少なくとも１種を用いることが望ましく、これらは単独で用いても２種以上を組み合わせて用いてもよい。
また、発明の目的を損なわない範囲であれば固形のエポキシ樹脂を併用しても良い。さらには粘度調整のためエポキシ基を有する反応性希釈剤を混合しても良い。エポキシ基を有する反応性希釈剤としては例えばｎ−ブチルグリシジルエーテル、バーサティック酸グリシジルエーテル、スチレンオキサイド、エチルヘキシルグリシジルエーテル、フェニルグリシジルエーテル、ブチルフェニルグリシジルエーテル、１,６−ヘキサンジオールジグリシジルエーテル、ネオペンチルグリコールジグリシジルエーテル、ジエチレングリコールジグリシジルエーテル、トリメチロールプロパントリグリシジルエーテルがあり、これらの内の１種類あるいは複数種と併用しても良い。
これらのエポキシ樹脂は、十分に精製されたもので、イオン性不純物が少ないものが好ましい。例えば、遊離Ｎａイオン、遊離Ｃｌイオンは５００ｐｐｍ以下であることが好ましい。 The (A) liquid epoxy resin used in the present invention is not particularly limited. For example, glycidyl ether type epoxy obtained by reaction of bisphenol A, bisphenol F, bisphenol AD, bisphenol S, naphthalene diol, hydrogenated bisphenol A and the like with epichlorohydrin. Resin, epoxidized novolak resin obtained by condensation or cocondensation of phenols and aldehydes, including orthocresol novolac type epoxy resin, by reaction of polybasic acids such as phthalic acid and dimer acid with epichlorohydrin Obtained glycidyl ester type epoxy resin, aminoglycidyl ether type epoxy resin obtained by reaction of polyamine such as diaminodiphenylmethane, isocyanuric acid and epichlorohydrin, olefin bond with peracetic acid, etc. Linear aliphatic epoxy resins obtained by oxidation with peracetic acid, and alicyclic epoxy resins. In particular, in the present invention, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, bisphenol S type epoxy resin, hydrogenated bisphenol A type epoxy resin, naphthalenediol type epoxy resin, aminoglycidyl ether type epoxy resin It is desirable to use at least one selected from the above, and these may be used alone or in combination of two or more.
Further, a solid epoxy resin may be used in combination as long as the object of the invention is not impaired. Furthermore, you may mix the reactive diluent which has an epoxy group for viscosity adjustment. Examples of the reactive diluent having an epoxy group include n-butyl glycidyl ether, versatic acid glycidyl ether, styrene oxide, ethylhexyl glycidyl ether, phenyl glycidyl ether, butylphenyl glycidyl ether, 1,6-hexanediol diglycidyl ether, neodymium There are pentyl glycol diglycidyl ether, diethylene glycol diglycidyl ether, and trimethylolpropane triglycidyl ether, and one or more of them may be used in combination.
These epoxy resins are sufficiently purified and preferably have little ionic impurities. For example, free Na ions and free Cl ions are preferably 500 ppm or less.

本発明に用いる（Ｂ）硬化剤は、芳香族アミンであれば特に制限はなく、組成物が液状であれば硬化剤は固形の芳香族アミンを使用しても良いし、液状及び固形の芳香族アミンを併用しても良い。
芳香族アミンとしては、例えば、エピキュアＷ、エピキュアＺ（いずれもジャパンエポキシレジン株式会社製商品名）、カヤハードＡ−Ａ、カヤハードＡ−Ｂ、カヤハードＡ−Ｓ（いずれも日本化薬株式会社製商品名）、トートアミンＨＭ−２０５（東都化成株式会社製商品名）、アデカハードナーＥＨ−１０１、アデカハードナーＥＨ-Ｍ３２（いずれも旭電化工業株式会社製商品名）、エポミックＱ−６４０、エポミックＱ−６４３（いずれも三井化学株式会社製商品名）、ＤＥＴＤＡ８０（Ｌｏｎｚａ社製商品名）等が挙げられ、これらを単独で用いても２種以上を組み合わせて用いてもよい。
（Ａ）エポキシ樹脂と（Ｂ）硬化剤との当量比は特に制限はないが、それぞれの未反応分を少なくするため、エポキシ樹脂に対して硬化剤を０．６〜１．６当量の範囲に設定することが好ましく、０．７〜１．４当量がより好ましく、０．８〜１．２当量がさらに好ましい。０．６．〜１．６当量の範囲からはずれた場合、未反応分が多くなり信頼性が低下する傾向がある。
ここで、芳香族アミンの当量はエポキシ基１個に対しアミノ基の活性水素１個が反応するものとして計算される。 The (B) curing agent used in the present invention is not particularly limited as long as it is an aromatic amine. If the composition is liquid, the curing agent may be a solid aromatic amine, or a liquid and solid aroma. A group amine may be used in combination.
As an aromatic amine, for example, EpiCure W, EpiCure Z (all trade names manufactured by Japan Epoxy Resin Co., Ltd.), Kayahard A-A, Kayahard AB, Kayahard AS (all manufactured by Nippon Kayaku Co., Ltd.) Name), Totoamine HM-205 (trade name, manufactured by Toto Kasei Co., Ltd.), Adeka Hardener EH-101, Adeka Hardner EH-M32 (all trade names manufactured by Asahi Denka Kogyo Co., Ltd.), Epomic Q-640, Epomic Q- 643 (both trade names manufactured by Mitsui Chemicals, Inc.), DETDA80 (trade names manufactured by Lonza) and the like may be used, and these may be used alone or in combination of two or more.
The equivalent ratio of (A) epoxy resin and (B) curing agent is not particularly limited, but in order to reduce each unreacted component, the curing agent is in the range of 0.6 to 1.6 equivalents relative to the epoxy resin. Is preferably set to 0.7 to 1.4 equivalents, and more preferably 0.8 to 1.2 equivalents. 0.6. When deviating from the range of ˜1.6 equivalents, there is a tendency that unreacted components increase and reliability decreases.
Here, the equivalent of an aromatic amine is calculated on the assumption that one active hydrogen of an amino group reacts with one epoxy group.

本発明に用いる（Ｃ）硬化促進剤は、1,8−ジアザビシクロ（5,4,0）ウンデセン−7（以下、ＤＢＵという。）及び/又は1,5−ジアザビシクロ（4,3,0）ノネン−5（以下、ＤＢＮという。）及び/又はＤＢＵの塩及び/又はＤＢＮの塩であれば特に制限がなく、一種類でまたは二種類以上を組み合わせて使用される。特に本発明では半導体装置の信頼性の点からＤＢＵ及び／又はその塩を用いるのが好ましい。
ＤＢＵ及びその塩の例として、たとえばＤＢＵ、Ｕ−ＣＡＴ ＳＡ１（ＤＢＵ−フェノール塩）、Ｕ−ＣＡＴ ＳＡ１０２（ＤＢＵ−オクチル酸塩）、Ｕ−ＣＡＴ ＳＡ５０６（ＤＢＵ−ｐ−トルエンスルホン酸塩）、Ｕ−ＣＡＴ ＳＡ６０３（ＤＢＵ−蟻酸塩）、Ｕ−ＣＡＴ ＳＡ８１０（ＤＢＵ−オルソフタル塩）、Ｕ−ＣＡＴ ＳＡ８４１（ＤＢＵ−フェノールノボラック樹脂塩）（いずれもサンアプロ株式会社製商品名）、ＴＯＹＯＣＡＴ ＡＣ−７１０（ＤＢＵ−トリメリット酸塩）、ＴＯＹＯＣＡＴ ＡＣ−７２２（ＤＢＵ−テレフタル酸塩）、ＴＯＹＯＣＡＴ ＡＣ-７４０（ＤＢＵ-シアヌル酸塩）（いずれも東ソー株式会社製商品名）を挙げることができる。
（Ａ）エポキシ樹脂と（Ｃ）硬化促進剤との合計量に対する、（Ｃ）硬化促進剤内のDBU及びDBNの和の重量比率は、0.02〜0.10の範囲にある必要があり、好ましくは0.04〜0.08の範囲である。前記重量比率が下限値を下回ると硬化性やはんだの酸化皮膜除去性が悪化し、逆に上限値を超えると組成物の常温での粘度が上昇するためボイドや接合性が悪化し、またTgが低下し各種信頼性が悪化するため好ましくない。ここで、（Ｃ）硬化促進剤にDBUの塩及び／又はDBNの塩を含む場合、「合計量」の算出には塩の重量を直接使用し、「（Ｃ）硬化促進剤内のDBU及びDBNの和」には、前記塩の重量をDBU及び／又はDBNの重量に換算した値を使用する。 The (C) curing accelerator used in the present invention is 1,8-diazabicyclo (5,4,0) undecene-7 (hereinafter referred to as DBU) and / or 1,5-diazabicyclo (4,3,0) nonene. -5 (hereinafter referred to as DBN) and / or DBU salt and / or DBN salt are not particularly limited and may be used singly or in combination of two or more. In particular, in the present invention, it is preferable to use DBU and / or a salt thereof from the viewpoint of reliability of the semiconductor device.
Examples of DBU and salts thereof include, for example, DBU, U-CAT SA1 (DBU-phenol salt), U-CAT SA102 (DBU-octylate), U-CAT SA506 (DBU-p-toluenesulfonate), U -CAT SA603 (DBU-formate), U-CAT SA810 (DBU-orthophthalic salt), U-CAT SA841 (DBU-phenol novolac resin salt) (all are trade names manufactured by San Apro Co., Ltd.), TOYOCAT AC-710 (DBU) -Trimellitic acid salt), TOYOCAT AC-722 (DBU-terephthalic acid salt), TOYOCAT AC-740 (DBU-cyanuric acid salt) (all are trade names manufactured by Tosoh Corporation).
The weight ratio of the sum of DBU and DBN in (C) cure accelerator to the total amount of (A) epoxy resin and (C) cure accelerator must be in the range of 0.02 to 0.10, preferably 0.04 It is in the range of ~ 0.08. If the weight ratio is lower than the lower limit, curability and solder oxide film removability deteriorate, and conversely if the upper limit is exceeded, the viscosity at room temperature of the composition increases, so voids and bondability deteriorate, and Tg Decreases and various reliability deteriorates, which is not preferable. Here, when (C) the curing accelerator includes a DBU salt and / or a DBN salt, the weight of the salt is directly used for calculating the “total amount”, and “(C) DBU in the curing accelerator and For “sum of DBN”, a value obtained by converting the weight of the salt into the weight of DBU and / or DBN is used.

本発明には必要に応じて、無機充填剤、カップリング剤、可撓化剤、着色剤などを用いることができる。無機充填剤は、エポキシ樹脂組成物の低熱膨張化、剛性、熱伝導性の付与などを目的に配合するものであり、通常溶融シリカ、結晶性シリカ、アルミナ、窒化けい素、窒化ボロン、炭化けい素などを用いることができるが、特に、本発明においてはシリカ粉末をその融点以上の温度に加熱、焼成して製造される実質的に球状溶融シリカが好ましい。チップのバンプと回路基板の隙間でのアンダーフィル材の噛み込みによる接合不良を防止するには、最大粒径が５μｍ以下の球状溶融シリカが好ましく、配合量としてはアンダーフィル材の熱膨張係数低下を目的に樹脂中の４０ｗｔ％以上配合するのが良い。
カップリング剤は無機充填材と樹脂の濡れ、被着体との接着性改善効果があり、具体的には、γ−（２−アミノエチル）アミノプロピルトリメトキシシラン、γ−（２−アミノエチル）アミノプロピルジメトキシシラン、γ−グリシドキシプロピルトリメトキシシラン、γ−メルカプトプロピルトリメトキシシラン、γ−アニリノプロピルトリメトキシシラン、γ−ウレイドトリメトキシシラン、γ−ジブチルアミノプロピルトリメトキシシラン、イミダゾールシランなどを用いることができる。可撓化剤としてはシリコーン、アクリル及びポリオレフィン系エラストマーあるいはその粉末、着色剤としてはカーボンブラック、有機染料、有機顔料、酸化チタン、鉛丹、ベンガラなどを用いることができる。 In the present invention, an inorganic filler, a coupling agent, a flexing agent, a colorant and the like can be used as necessary. Inorganic fillers are blended for the purpose of lowering the thermal expansion, imparting rigidity and thermal conductivity of the epoxy resin composition, and are usually fused silica, crystalline silica, alumina, silicon nitride, boron nitride, silicon carbide. In particular, in the present invention, substantially spherical fused silica produced by heating and baking silica powder to a temperature equal to or higher than its melting point is preferred in the present invention. Spherical fused silica with a maximum particle size of 5 μm or less is preferable to prevent poor bonding due to the biting of the underfill material in the gap between the chip bump and the circuit board, and the compounding amount is reduced in the thermal expansion coefficient of the underfill material For this purpose, it is preferable to blend 40 wt% or more of the resin.
The coupling agent has the effect of improving the adhesion between the inorganic filler and the resin and the adherend. Specifically, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) ) Aminopropyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-anilinopropyltrimethoxysilane, γ-ureidotrimethoxysilane, γ-dibutylaminopropyltrimethoxysilane, imidazole Silane or the like can be used. Silicone, acrylic and polyolefin elastomers or powders can be used as the flexibilizing agent, and carbon black, organic dyes, organic pigments, titanium oxide, red lead, bengara, etc. can be used as the colorant.

本発明の液状エポキシ樹脂組成物の製造方法は特に限定されないが、上記各種成分を均一に分散混合できる方法であれば良い。一般的な方法としては、三本ロール、らいかい機、プラネタリミキサー等による分散混練を挙げることができる。本発明の液状エポキシ樹脂組成物による半導体素子の樹脂封止は通常ディスペンス方式によって行われる。   Although the manufacturing method of the liquid epoxy resin composition of this invention is not specifically limited, What is necessary is just the method which can disperse-mix the said various components uniformly. As a general method, dispersion kneading with a three-roll, a raking machine, a planetary mixer or the like can be mentioned. Resin sealing of a semiconductor element with the liquid epoxy resin composition of the present invention is usually performed by a dispensing method.

図１に、本発明の液状エポキシ樹脂組成物により製造される本発明の電子部品装置の一例を縦断面図で示す。図１に示すように、配線回路基板１の片面すなわち回路形成面に、複数の接続用電極部（バンプ）２を介して半導体素子３が搭載された構造をとる。配線回路基板１と半導体素子３との間に本発明の液状エポキシ樹脂組成物の硬化物である封止樹脂層４が形成されている。
なお、上記配線回路基板１の回路と半導体素子３の電極とを電気的に接続する上記複数の接続用電極部２は、予め配線回路基板１面に配設されてもよいし、半導体素子３面に配設されていてもよい。さらには、予め配線回路基板１面及び半導体素子３面の双方にそれぞれ配設されてもよい。
配線回路基板１の材質としては、有機質と無機質のいずれでもよく、特に限定するものではないが、大別して、セラミック基板、プラスチック基板があり、前記プラスチック基板としては、例えば、エポキシ基板、ビスマレイミドトリアジン基板、ポリイミド基板等が挙げられる。本発明の液状エポキシ樹脂組成物は、プラスチック基板と、低融点半田による接続用電極部等の組合せのように耐熱性の問題で接合温度を高温に設定することができないような場合においても、特に限定されることなく、好適に用いられる。
複数の接続用電極部２の材質としては、特に限定するものではないが、例えば半田による低融点、及び高融点バンプ、錫バンプ、銀−錫バンプ、銀−錫−銅バンプ等が挙げられ、また、回路配線基板上の電極部が上記の材質からなるものに対しては、図中の接続用電極部２は金バンプ、銅バンプ等であっても良い。
半導体素子３は、特に限定されず、通常使用されるものが使用できる。例えば、シリコン、ゲルマニウムなどの元素半導体、ガリウムヒ素、インジウムリン等の化合物半導体等の各種半導体が使用される。 In FIG. 1, an example of the electronic component apparatus of this invention manufactured with the liquid epoxy resin composition of this invention is shown with a longitudinal cross-sectional view. As shown in FIG. 1, a structure in which a semiconductor element 3 is mounted on one side of a wired circuit board 1, that is, a circuit forming surface via a plurality of connection electrode portions (bumps) 2 is employed. A sealing resin layer 4 that is a cured product of the liquid epoxy resin composition of the present invention is formed between the printed circuit board 1 and the semiconductor element 3.
The plurality of connection electrode portions 2 that electrically connect the circuit of the wired circuit board 1 and the electrodes of the semiconductor element 3 may be disposed on the surface of the wired circuit board 1 in advance. It may be disposed on the surface. Furthermore, it may be previously arranged on both the printed circuit board 1 surface and the semiconductor element 3 surface.
The material of the printed circuit board 1 may be either organic or inorganic, and is not particularly limited, but is roughly divided into a ceramic substrate and a plastic substrate. Examples of the plastic substrate include an epoxy substrate and a bismaleimide triazine. Examples include a substrate and a polyimide substrate. The liquid epoxy resin composition of the present invention is particularly suitable even when the bonding temperature cannot be set to a high temperature due to heat resistance problems, such as a combination of a plastic substrate and a connecting electrode portion using low melting point solder. It is used suitably, without being limited.
The material of the plurality of connection electrode portions 2 is not particularly limited, and examples thereof include a low melting point by solder and a high melting point bump, a tin bump, a silver-tin bump, a silver-tin-copper bump, and the like. Further, for the electrode part on the circuit wiring board made of the above-mentioned material, the connection electrode part 2 in the figure may be a gold bump, a copper bump or the like.
The semiconductor element 3 is not specifically limited, What is normally used can be used. For example, various semiconductors such as elemental semiconductors such as silicon and germanium, and compound semiconductors such as gallium arsenide and indium phosphide are used.

本発明の液状エポキシ樹脂組成物を用いた電子部品装置の製造方法について、接続用電極部として半田バンプを用いた一例を挙げて図面に基づき順を追って説明する。図２及び図３は、電子部品装置の製造工程の一例を示す概略断面図である。
（１）まず、図２に示すように配線回路基板１上に、本発明の液状エポキシ樹脂組成物７をディスペンス法により塗布する。
（２）ついで、図３に示すように、（１）の基板の液状エポキシ樹脂組成物７の上の所定位置に、基板の回路と電気的接合させるための複数の半田バンプ製接続用電極部（ジョイントボール）２が設けられた半導体素子３を搭載する。
液状エポキシ樹脂組成物７を加熱ステージ上で溶融して溶融状態とし、上記半導体素子３の接続用電極部２が溶融状態の液状エポキシ樹脂組成物７を押しのけ、配線用回路基板１と接続用電極部２が接触することにより仮実装し、かつ半導体素子３と配線回路基板１との間の空隙内に溶融状態の液状エポキシ樹脂組成物７を充填させる。
（３）その後、半田リフローによる金属接合を行うと同時に、液状エポキシ樹脂組成物７を硬化させることにより、空隙を封止して、封止樹脂層４を形成する（図１参照。）。この時、半田を溶融させて半田バンプ付き素子を基板上に電気的に接合させる半田リフロー方式は、リフロー炉を用いた接合方式であっても、ヒータ及び押圧部を備えた装置によりチップ搭載と同時に半田融点以上にヒータ部分を加熱し、半田溶融を行う接合方式であっても良い。また、前記金属接合を行うと同時にエポキシ樹脂組成物７を硬化する方法の他、金属接合の後の加熱処理により該前記エポキシ樹脂組成物の硬化を行う方法も挙げられる。このようにして、図１に示す電子部品装置を製造する。 The manufacturing method of an electronic component device using the liquid epoxy resin composition of the present invention will be described in order with reference to the drawings, taking an example using solder bumps as connection electrode portions. 2 and 3 are schematic cross-sectional views showing an example of the manufacturing process of the electronic component device.
(1) First, as shown in FIG. 2, the liquid epoxy resin composition 7 of the present invention is applied on the printed circuit board 1 by a dispensing method.
(2) Next, as shown in FIG. 3, a plurality of solder bump connection electrode portions for electrical bonding to the circuit of the substrate at a predetermined position on the liquid epoxy resin composition 7 of the substrate of (1). A semiconductor element 3 provided with (joint ball) 2 is mounted.
The liquid epoxy resin composition 7 is melted on the heating stage to be in a molten state, and the connection electrode portion 2 of the semiconductor element 3 pushes away the molten liquid epoxy resin composition 7, so that the circuit board 1 for wiring and the connection electrode The parts 2 are temporarily mounted by contact, and the gap between the semiconductor element 3 and the printed circuit board 1 is filled with the molten liquid epoxy resin composition 7.
(3) Thereafter, metal bonding by solder reflow is performed, and at the same time, the liquid epoxy resin composition 7 is cured, thereby sealing the gap and forming the sealing resin layer 4 (see FIG. 1). At this time, the solder reflow method in which the solder is melted and the solder bumped element is electrically bonded onto the substrate is mounted on the chip by a device having a heater and a pressing portion, even in a bonding method using a reflow furnace. At the same time, a joining method may be employed in which the heater portion is heated to the melting point of the solder or higher to melt the solder. Moreover, the method of hardening | curing the said epoxy resin composition by the heat processing after metal joining other than the method of hardening | curing the epoxy resin composition 7 simultaneously with the said metal joining is mentioned. In this way, the electronic component device shown in FIG. 1 is manufactured.

なお、上記電子部品装置の製造方法では、複数の接続用電極部２が設けられた半導体素子３を用いた場合について述べたが、これに限定するものではなく、例えば予め配線回路基板１に複数の接続用電極部２が配設されたものを用いてもよい。
配線回路基板１上に、液状エポキシ樹脂組成物７を塗布する方法は、ディスペンス法の他、印刷法、転写法などが挙げられる。
また、液状エポキシ樹脂組成物７の厚み及び重量は、上記同様、搭載される半導体素子３の大きさ及び半導体素子に設けられた球状の接続用電極の大きさ、すなわち、半導体素子３と配線回路基板１との空隙を充填し、封止することにより形成される封止樹脂層４の占める容積により、適宜に設定される。
また、上記電子部品装置の製造方法において、上記（２）の仮実装時には、必ずしも液状エポキシ樹脂組成物７を加熱して溶融させなくてもよい。さらに、液状エポキシ樹脂組成物７を加熱して溶融状態にする際の加熱温度としては、半導体素子３及び配線回路基板１の耐熱性、接続用電極部２の融点、並びに液状エポキシ樹脂組成物７の軟化点、耐熱性等を考慮して適宜に設定されるものである。 In the above-described method for manufacturing an electronic component device, the case where the semiconductor element 3 provided with the plurality of connection electrode portions 2 is used has been described. However, the present invention is not limited to this. Those having the connecting electrode portion 2 may be used.
Examples of the method for applying the liquid epoxy resin composition 7 on the printed circuit board 1 include a printing method and a transfer method in addition to the dispensing method.
Further, the thickness and weight of the liquid epoxy resin composition 7 are the same as described above in the size of the semiconductor element 3 to be mounted and the size of the spherical connection electrode provided on the semiconductor element, that is, the semiconductor element 3 and the wiring circuit. It is set appropriately depending on the volume occupied by the sealing resin layer 4 formed by filling the gap with the substrate 1 and sealing.
In the method for manufacturing an electronic component device, the liquid epoxy resin composition 7 does not necessarily have to be heated and melted during the temporary mounting of (2). Furthermore, as the heating temperature when the liquid epoxy resin composition 7 is heated to a molten state, the heat resistance of the semiconductor element 3 and the printed circuit board 1, the melting point of the connection electrode portion 2, and the liquid epoxy resin composition 7 are used. In view of the softening point, heat resistance, etc., the thickness is appropriately set.

本発明で得られる液状エポキシ樹脂組成物は、セラミックス、ガラス/エポキシ、ポリイミドなどの基板に樹脂封止されたLSI、トランジスタ、ダイオード、サイリスタなどの能動素子、コンデンサ、抵抗、コイルなどの受動素子などとともにベアの半導体チップをフリップチップ実装するＣＯＢ（Chip on Board）、モジュール、カードなどのベアチップと基板の隙間を充填する封止材として用いるのが好ましい。また、パッケージレベルでフリップチップ実装を行うＦＣ−ＢＧＡ（Flip chip Ball Grid Array）、ＥＢＧＡ（Enhanced BGA）、ＡＢＧＡ（Advanced BGA）、Stacked−ＢＧＡ、ＳＩＰ（System in Package）などのベアチップと基板の隙間を充填する封止材として用いるのが好ましい。特に、最近はチップサイズの大型化、ギャップの狭間隙化が進んでおり、本発明の液状エポキシ樹脂組成物は、チップサイズ１５×１５ｍｍ以上、ギャップ８０μｍ以下の場合に優れた効果を発揮する。
なお、ＢＧＡ、ＣＳＰ（Chip Size/Scale Package）、ＷＬ-ＣＳＰ（Wafer Level CSP）などの最新のパッケージは、端子がエリアアレイ構造になっており、基板への実装形態はフリップチップ実装と同じである。特に携帯電話のようなモバイル型の電子機器においては接合部の耐衝撃性が厳しく要求されており、接続信頼性を確保するためパッケージと基板の隙間を補強用の樹脂組成物で封止することがある。本発明の液状エポキシ樹脂組成物はこのような用途にも用いることができる。また、従来から液状エポキシ樹脂組成物によって封止が行われていた、キャリアテープにバンプを介して半導体チップを接合したＴＣＰ（Tape Carrier Package）、セラミックス、ガラス/エポキシ、ポリイミド基板などにベアチップをワイヤボンディング法で搭載したＣＯＢ、モジュール、カード、ＢＧＡ、ＣＳＰなどの樹脂封止にも用いることができる。
特に、素子の回路形成面と無機または有機基板の回路形成面とが対向し、前記素子の電極と前記基板の回路とがバンプを介して電気的に接続されているフリップチップ実装型で、前記素子と前記基板との隙間に液状エポキシ樹脂組成物が充填されているものが特に好ましい。
また、プリント回路板にも本発明の液状エポキシ樹脂組成物は有効に使用できる。 The liquid epoxy resin composition obtained by the present invention includes LSIs, transistors, diodes, thyristors, and other active elements resin-sealed with ceramics, glass / epoxy, polyimide and other substrates, capacitors, resistors, passive elements such as coils, etc. At the same time, it is preferably used as a sealing material for filling a gap between the bare chip and the substrate such as a COB (Chip on Board), a module, or a card for flip-chip mounting a bare semiconductor chip. Also, the gap between the bare chip and the substrate such as FC-BGA (Flip chip Ball Grid Array), EBGA (Enhanced BGA), ABGA (Advanced BGA), Stacked-BGA, and SIP (System in Package) that perform flip chip mounting at the package level It is preferable to use it as a sealing material for filling. In particular, the chip size has recently been increased and the gap has been narrowed. The liquid epoxy resin composition of the present invention exhibits excellent effects when the chip size is 15 × 15 mm or more and the gap is 80 μm or less.
The latest packages such as BGA, CSP (Chip Size / Scale Package), and WL-CSP (Wafer Level CSP) have an area array structure, and the mounting form on the substrate is the same as flip chip mounting. is there. Particularly in mobile electronic devices such as mobile phones, the impact resistance of joints is strictly required, and the gap between the package and the substrate is sealed with a reinforcing resin composition to ensure connection reliability. There is. The liquid epoxy resin composition of the present invention can also be used for such applications. In addition, bare chips are wire-bonded to TCP (Tape Carrier Package), ceramics, glass / epoxy, polyimide substrates, etc., which have been conventionally sealed with liquid epoxy resin compositions and bonded to semiconductor tape via bumps. It can also be used for resin sealing of COB, module, card, BGA, CSP and the like mounted by the bonding method.
In particular, the flip chip mounting type in which the circuit forming surface of the element and the circuit forming surface of the inorganic or organic substrate are opposed to each other, and the electrode of the element and the circuit of the substrate are electrically connected via bumps, It is particularly preferred that the liquid epoxy resin composition is filled in the gap between the element and the substrate.
The liquid epoxy resin composition of the present invention can also be used effectively for printed circuit boards.

次に実施例により本発明を説明するが、本発明の範囲はこれらの実施例に限定されるものではない。なお、液状エポキシ樹脂組成物の諸特性及びボイドの観察、各種信頼性の評価は以下の方法及び条件で行った。信頼性の評価に使用した半導体装置の諸元は、チップサイズ１０．０４×１０．０４×０．７３ｔｍｍ（回路はアルミのジグザグ配線、パッシベーション：ポリイミド膜）、バンプ：はんだボール（Ｓｎ/Ｐｂ：融点３１０℃、φ８０μｍ、１９３６ｐｉｎ、）、バンプピッチ：２００μｍ、基板：ＦＲ−５（５３×３０×０．７ｔｍｍ、Ｓｎ/Ａｇ/Ｃｕ：融点２１７℃受けはんだ）、チップ／基板間のギャップ：４５μｍである。   EXAMPLES Next, although an Example demonstrates this invention, the scope of the present invention is not limited to these Examples. In addition, the various characteristics of a liquid epoxy resin composition, observation of a void, and evaluation of various reliability were performed with the following method and conditions. The specifications of the semiconductor device used for the reliability evaluation are as follows: chip size 10.04 × 10.04 × 0.73 tmm (circuit is aluminum zigzag wiring, passivation: polyimide film), bump: solder ball (Sn / Pb: Melting point 310 ° C., φ80 μm, 1936 pin), bump pitch: 200 μm, substrate: FR-5 (53 × 30 × 0.7 tmm, Sn / Ag / Cu: melting point 217 ° C. receiving solder), chip / substrate gap: 45 μm It is.

（１）粘度及びチキソトロピック指数
Ｅ型粘度計（株式会社東京計器製）を用いて、液状エポキシ樹脂組成物の２５℃の粘度（Ｐａ・ｓ）をロータ回転数 １０ｒｐｍで測定した。チキソトロピック指数はロータ回転数２．５ｒｐｍで測定した粘度と１０ｒｐｍで測定した粘度の比で表した。 (1) Viscosity and thixotropic index Using an E-type viscometer (manufactured by Tokyo Keiki Co., Ltd.), the viscosity (Pa · s) at 25 ° C. of the liquid epoxy resin composition was measured at a rotor rotation speed of 10 rpm. The thixotropic index was expressed as the ratio of the viscosity measured at 2.5 rpm of the rotor and the viscosity measured at 10 rpm.

（２）ボイド観察
液状エポキシ樹脂組成物で封止した半導体装置の内部を超音波探傷装置ＡＴ−５５００（株式会社日立建機製）で観察し、ボイドの有無を調べた。 (2) Void observation The inside of the semiconductor device sealed with the liquid epoxy resin composition was observed with an ultrasonic flaw detector AT-5500 (manufactured by Hitachi Construction Machinery Co., Ltd.) to examine the presence or absence of voids.

（３）はんだ接合性
導通検査により半導体装置の１９３６バンプ全てに導通とれたものを○、それ以外を×で示した。
また、バンプと受けはんだの断面観察を行い、バンプと受けはんだの界面が均一に濡れ接合しているものを○、それ以外を×で示した。 (3) Solder Joinability A continuity test indicated that all the 1936 bumps of the semiconductor device were conductive, and the others were indicated by x.
Further, cross-sectional observation of the bump and the receiving solder was performed, and the case where the interface between the bump and the receiving solder was uniformly wet-joined was indicated by ○, and the others were indicated by ×.

（４）信頼性評価
（1） 耐リフロー性
半導体装置を１２０℃／１２時間加熱乾燥した後、８５℃、６０％ＲＨ下で１６８時間吸湿させ、遠赤外線加熱方式のリフロー炉（２６０℃加熱時間１０秒）中を３回通した後、内部を超音波探傷装置で観察し、液状エポキシ樹脂組成物とチップ及び基板との剥離、エポキシ樹脂組成物のクラックの有無を調べた。
（2） 耐温度サイクル性
半導体装置を−５０℃〜１５０℃、各３０分のヒートサイクルで１０００サイクル処理し、導通試験を行いアルミ配線の断線不良を調べ、不良パッケージ数／評価パッケージ数で評価した。
（3） 耐湿信頼性
半導体装置を１２１℃、２ａｔｍ、１００％ＲＨのＰＣＴ条件で２４０ｈ処理後、アルミ配線及びパッドの断線有無を導通試験より確認し、不良パッケージ数／評価パッケージ数で評価した。 (4) Reliability evaluation (1) Reflow resistance After the semiconductor device was heated and dried at 120 ° C for 12 hours, the semiconductor device was absorbed for 168 hours under 85 ° C and 60% RH, and the far-infrared heating type reflow oven (260 ° C heating time) 10 seconds), the inside was observed with an ultrasonic flaw detector, and the liquid epoxy resin composition was separated from the chip and the substrate, and the presence or absence of cracks in the epoxy resin composition was examined.
(2) Thermal cycle resistance The semiconductor device is processed for 1000 cycles with a heat cycle of -50 ° C to 150 ° C for 30 minutes each, a continuity test is conducted to check for disconnection defects in the aluminum wiring, and evaluation is based on the number of defective packages / number of evaluation packages. did.
(3) Moisture resistance reliability After the semiconductor device was treated for 240 h under PCT conditions of 121 ° C., 2 atm, 100% RH, the presence or absence of disconnection of the aluminum wiring and the pad was confirmed by a continuity test and evaluated by the number of defective packages / number of evaluation packages.

[実施例１〜８]
表１に示す配合割合で計量した各素材を真空擂潰機に入れ、５torrに減圧しながら約２０分間混練して目的とする８種類の液状エポキシ樹脂組成物を得た。次に、ディスペンサーを用いこれらの液状エポキシ樹脂組成物を回路基板上に塗布した。次にチップと回路基板の位置合せをミスズＦＡ株式会社製フリップチップボンダーを用いて行った後、両者を２６０℃で１０秒間圧接した。次いで１６５℃の高温槽中で２時間加熱し樹脂を硬化させて目的とする樹脂封止型半導体装置を得た。得られた液状エポキシ樹脂組成物の特性、成形性、信頼性評価結果を表１に纏めて示す。 [Examples 1 to 8]
Each raw material weighed at the blending ratio shown in Table 1 was put in a vacuum crusher and kneaded for about 20 minutes while reducing the pressure to 5 torr to obtain 8 types of target liquid epoxy resin compositions. Next, these liquid epoxy resin compositions were apply | coated on the circuit board using dispenser. Next, after aligning the chip and the circuit board using a flip chip bonder manufactured by Misuzu FA Co., Ltd., both were pressed at 260 ° C. for 10 seconds. Next, the resin was cured by heating in a high temperature bath at 165 ° C. for 2 hours to obtain the intended resin-encapsulated semiconductor device. The properties, moldability, and reliability evaluation results of the obtained liquid epoxy resin composition are summarized in Table 1.

Figure 2006188573

＊1：エポキシ当量160
＊2：エポキシ当量95
＊3：活性水素当量45
＊4：1,8−ジアザビシクロ（5,4,0）ウンデセン−7
＊5：1,5−ジアザビシクロ（4,3,0）ノネン−5
＊6：DBU−フェノール塩、DBU濃度62wt%
＊7：DBU−蟻酸塩、DBU濃度75wt%
＊8：DBU−フェノールノボラック樹脂塩、DBU濃度30wt%
＊9：DBU−シアヌル酸塩、DBU濃度54wt%
Figure 2006188573
* 1: Epoxy equivalent 160
* 2: Epoxy equivalent 95
* 3: Active hydrogen equivalent 45
* 4: 1,8-diazabicyclo (5,4,0) undecene-7
* 5: 1,5-diazabicyclo (4,3,0) nonene-5
* 6: DBU-phenol salt, DBU concentration 62wt%
* 7: DBU-formate, DBU concentration 75wt%
* 8: DBU-phenol novolac resin salt, DBU concentration 30 wt%
* 9: DBU-cyanurate, DBU concentration 54 wt%

[比較例１〜５]
表２に示す配合割合で計量した各素材を用い上記同にして５種類の液状エポキシ樹脂組成物を作製し、成形性、半導体装置の各種信頼性を評価した。結果を表２に纏めて示す。 [Comparative Examples 1-5]
Five types of liquid epoxy resin compositions were prepared in the same manner as above using each material weighed at the blending ratio shown in Table 2, and the moldability and various reliability of the semiconductor device were evaluated. The results are summarized in Table 2.

Figure 2006188573
＊1：エポキシ当量160
＊2：エポキシ当量95
＊3：活性水素当量45
＊4：1,8−ジアザビシクロ（5,4,0）ウンデセン−7
＊10：2−エチル−4−メチルイミダゾール
＊11：ベンジルジメチルアミン
＊12：トリスジメチルアミノメチルフェノール
Figure 2006188573
 * 1: Epoxy equivalent 160
* 2: Epoxy equivalent 95
* 3: Active hydrogen equivalent 45
* 4: 1,8-diazabicyclo (5,4,0) undecene-7
* 10: 2-Ethyl-4-methylimidazole * 11: Benzyldimethylamine * 12: Trisdimethylaminomethylphenol

表１及び２から明らかなように、本発明の液状エポキシ樹脂組成物はボイドなどの欠陥が無く、はんだ接合性に優れ、また耐リフロー性、耐温度サイクル性、耐湿性などの信頼性も良好である。   As is clear from Tables 1 and 2, the liquid epoxy resin composition of the present invention has no defects such as voids, is excellent in solder jointability, and has excellent reliability such as reflow resistance, temperature cycle resistance, and moisture resistance. It is.

図１は、電子部品装置の一例を示す概略断面図である。FIG. 1 is a schematic cross-sectional view illustrating an example of an electronic component device. 図２は、電子部品装置の製造工程の一例を示す概略断面図である。FIG. 2 is a schematic cross-sectional view showing an example of the manufacturing process of the electronic component device. 図３は、電子部品装置の製造工程の一例を示す概略断面図である。FIG. 3 is a schematic cross-sectional view showing an example of the manufacturing process of the electronic component device.

符号の説明Explanation of symbols

１ 配線回路基板
２ 接続用電極部
３ 半導体素子
４ 封止樹脂層
７ 液状エポキシ樹脂組成物

DESCRIPTION OF SYMBOLS 1 Wiring circuit board 2 Electrode part for connection 3 Semiconductor element 4 Sealing resin layer 7 Liquid epoxy resin composition

Claims (4)

（Ａ）エポキシ樹脂、（Ｂ）硬化剤、（Ｃ）DBU、DBUの塩、DBN及びDBNの塩の内の少なくとも一種類からなる硬化促進剤を含有する無溶剤型液状エポキシ樹脂組成物であって、（Ｂ）硬化剤が芳香族アミンであり、（Ａ）エポキシ樹脂と（Ｃ）硬化促進剤との合計量におけるDBU及びDBNの和の重量比率が0.02〜0.10の範囲にあることを特徴とする液状エポキシ樹脂組成物。   (A) Epoxy resin, (B) curing agent, (C) DBU, DBU salt, DBN and DBN salt, a solvent-free liquid epoxy resin composition containing a curing accelerator composed of at least one kind. (B) the curing agent is an aromatic amine, and the weight ratio of the sum of DBU and DBN in the total amount of (A) epoxy resin and (C) curing accelerator is in the range of 0.02 to 0.10. A liquid epoxy resin composition. （Ａ）エポキシ樹脂が、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＡＤ型エポキシ樹脂、ビスフェノールＳ型エポキシ樹脂、水添ビスフェノールＡ型エポキシ樹脂、ナフタレンジオール型エポキシ樹脂、アミノグリシジルエーテル型エポキシ樹脂から選ばれる少なくとも１種類の液状エポキシ樹脂を含む請求項１記載の液状エポキシ樹脂組成物。   (A) Epoxy resin is bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, bisphenol S type epoxy resin, hydrogenated bisphenol A type epoxy resin, naphthalenediol type epoxy resin, aminoglycidyl ether type epoxy The liquid epoxy resin composition according to claim 1, comprising at least one liquid epoxy resin selected from resins. 無機または有機基板の回路形成面の素子を搭載する位置に請求項１または２に記載の液状エポキシ樹脂組成物を塗布した後、素子の電極と基板の回路をバンプを介して接合すると同時に前記エポキシ樹脂組成物の硬化を行うかまたはその後の加熱処理により前記エポキシ樹脂組成物の硬化を行うことを特徴とする電子部品装置の製造方法。   3. The liquid epoxy resin composition according to claim 1 or 2 is applied to a position on the circuit forming surface of an inorganic or organic substrate, and then the epoxy of the device is bonded to the circuit of the substrate through a bump at the same time. A method for producing an electronic component device, comprising curing a resin composition or curing the epoxy resin composition by a subsequent heat treatment. 無機または有機基板の回路上に請求項１または２記載の液状エポキシ樹脂組成物により封止された素子を備えたことを特徴とする電子部品装置。
An electronic component device comprising an element sealed with a liquid epoxy resin composition according to claim 1 on a circuit of an inorganic or organic substrate.
JP2005000267A 2005-01-04 2005-01-04 Liquid epoxy resin composition, electronic component device using the composition and method for producing the same Pending JP2006188573A (en)

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JP2008300825A (en) * 2007-05-29 2008-12-11 Samsung Electro Mech Co Ltd Led module for illumination, and manufacturing method thereof
JP2009096886A (en) * 2007-10-17 2009-05-07 Hitachi Chem Co Ltd Liquid sealing resin composition and manufacturing method of semiconductor device using it
JP2010037447A (en) * 2008-08-06 2010-02-18 Sumitomo Bakelite Co Ltd Liquid sealing resin composition and semiconductor device
US8674502B2 (en) 2010-07-16 2014-03-18 Hitachi Chemical Company, Ltd. Semiconductor-encapsulating adhesive, semiconductor-encapsulating film-form adhesive, method for producing semiconductor device, and semiconductor device
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JP2008300825A (en) * 2007-05-29 2008-12-11 Samsung Electro Mech Co Ltd Led module for illumination, and manufacturing method thereof
JP2009096886A (en) * 2007-10-17 2009-05-07 Hitachi Chem Co Ltd Liquid sealing resin composition and manufacturing method of semiconductor device using it
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