JP4534280B2 - Epoxy resin molding material for sealing and electronic component device - Google Patents

Description

（ここで、ｍは２〜１０の整数、ｎは５〜３０の整数を示す。）
（３）（Ｃ）成分の数平均分子量が８００〜１５００で、かつエポキシ当量が２００〜２４０である上記（１）又は（２）記載の封止用エポキシ樹脂成形材料、及び
（４）液状芳香族アミン系硬化剤（Ｂ）が３，３’−ジエチル−４，４’−ジアミノジフェニルメタン及び／又はジエチルトルエンジアミンを含有してなる上記（１）〜（３）のいずれかに記載の封止用エポキシ樹脂成形材料、並びに
（５）上記（１）〜（４）記載のいずれか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る電子部品装置
に関する。
【０００７】
【発明の実施の形態】
本発明において用いられる（Ａ）成分の液状エポキシ樹脂は、一分子中に１個以上のエポキシ基を有し、常温で液状であれば特に制限はなく、封止用成形材料で一般に使用されている液状エポキシ樹脂を用いることができる。また、封止用エポキシ樹脂成形材料が液状であれば固形エポキシ樹脂を併用することもできるが、併用する固形エポキシ樹脂はエポキシ樹脂全量に対して２０重量％以下とすることが好ましい。本発明で使用できるエポキシ樹脂としては、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、水添ビスフェノールＡ等のジグリシジルエーテル、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グリシジルアミン型エポキシ樹脂、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。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であることが好ましい。
【０００８】
本発明において用いられる（Ｂ）成分の液状芳香族アミン系硬化剤は、常温で液状の芳香族炭化水素のアミン誘導体であれば特に制限はないが、例えば、市販品として、エピキュアＷ、エピキュアＺ（油化シェルエポキシ株式会社製商品名）、カヤハードＡ−Ａ、カヤハードＡ−Ｂ、カヤハードＡ−Ｓ（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（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（三井化学株式会社製商品名）、ＤＥＴＤＡ８０（Ｌｏｎｚａ社製商品名）等が入手可能で、これらを単独で用いても２種類以上を組み合わせて用いてもよい。保存安定性の観点からは、３，３’−ジエチル−４，４’−ジアミノジフェニルメタン及び／又はジエチルトルエンジアミンを主成分とする液状芳香族アミン系硬化剤が好ましい。
また、（Ｂ）成分の液状芳香族アミン系硬化剤以外に、フェノール性硬化剤、酸無水物等の封止用成形材料で一般に使用されている硬化剤を併用することができ、封止用エポキシ樹脂成形材料が液状であれば固形硬化剤も併用することもできる。他の硬化剤を併用する場合、（Ｂ）成分の液状芳香族アミン系硬化剤の配合量は、その性能を発揮するために硬化剤全量に対して６０重量％以上とすることが好ましい。
【０００９】
（Ａ）成分を含むエポキシ樹脂と（Ｂ）成分を含む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抑えるために、エポキシ樹脂に対して硬化剤を０．７〜１．６当量の範囲に設定することが好ましく、０．８〜１．４当量がより好ましく、０．９〜１．２当量がさらに好ましい。０．７．〜１．６当量の範囲からはずれた場合、硬化反応が不充分となり信頼性が低下する傾向がある。
【００１０】
本発明において用いられる（Ｃ）成分のエポキシ化ポリブタジエン化合物としては、エポキシ基を有するポリブタジエン化合物であれば特に制限はないが、例えば、下記一般式（Ｉ）で示される化合物が好ましいものとして挙げられる。接着性の観点からは、数平均分子量が８００〜１５００で、かつエポキシ当量が２００〜２４０である化合物が好ましい。
【化３】

上記式（Ｉ）中のｍは２〜１０の整数、ｎは５〜３０の整数を示し、接着性の観点からは、ｍ＝３〜８、ｎ＝８〜２５が好ましく、ｍ＝３〜６、ｎ＝１０〜２１がより好ましい。
【００１１】
上記式（Ｉ）で示される化合物としては、骨格中に下記のｍ個の成分（ｃ１）とｎ個の成分（ｃ２）をランダムに含むもの、交互に含むもの、ブロック状に含むものが挙げられ、これらの１種を単独で用いても２種以上を組み合わせて用いてもよい。
【化４】

【００１２】
上記式（Ｉ）のｍが５で、ｎが１２である１，２−ポリブタジエンが、市販品ＢＦ−１０００（日本曹達株式会社製商品名）として入手可能である。ＢＦ−１０００の数平均分子量は１０００、エポキシ当量は２０６である。
【００１３】
（Ｃ）成分のエポキシ化ポリブタジエン化合物の配合量は、本発明の効果を達成するために、（Ａ）成分、（Ｂ）成分及び（Ｃ）成分の合計量に対して１２〜３４重量％であることが必要で、１４〜２８重量％が好ましい。
【００１４】
本発明において用いられる（Ｄ）成分の無機充填剤は、吸湿性、熱膨張係数低減、熱伝導性向上及び強度向上のために成形材料に配合されるものであり、例えば、溶融シリカ、結晶シリカ、アルミナ、ジルコン、珪酸カルシウム、炭酸カルシウム、チタン酸カリウム、炭化珪素、窒化珪素、窒化アルミ、窒化ホウ素、ベリリア、ジルコニア、ジルコン、フォステライト、ステアタイト、スピネル、ムライト、チタニア等の粉体、又はこれらを球形化したビーズ、ガラス繊維などが挙げられる。さらに、難燃効果のある無機充填剤としては水酸化アルミニウム、水酸化マグネシウム、硼酸亜鉛、モリブデン酸亜鉛等が挙げられる。これらの無機充填剤は単独で用いても２種類以上を組み合わせて用いてもよい。上記の無機充填剤の中で、熱膨張係数低減の観点からはシリカが、高熱伝導性の観点からはアルミナが好ましい。無機充填剤の粒子形状は、微細間隙への流動性、浸透性の観点から球形が好ましい。また、平均粒径は１〜２０μｍが好ましく、２〜１０μｍがより好ましい。平均粒径が１μｍ未満では、液状樹脂への分散性が劣ったり、液状の封止用成形材料にチキソトロピック性が付与され流動性が劣ったりする傾向があり、２０μｍを超えるとフィラ沈降が起きやすくなったり、微細間隙への流動性、浸透性が劣ったりする傾向がある。
【００１５】
（Ｄ）成分の無機充填剤の配合量は、封止用エポキシ樹脂成形材料全体に対して２０〜９０重量％が好ましく、３０〜８５重量％の範囲がより好ましく、４０〜８０重量％がさらに好ましい。配合量が２０重量％未満では熱膨張係数低減効果が小さい傾向があり、９０重量％を超えると封止用エポキシ樹脂成形材料の粘度が上昇し、流動性、浸透性、ディスペンス性が低下する傾向がある。
【００１６】
本発明の封止用成形材料には、シクロアミジン化合物、３級アミン類、イミダゾール類、有機ホスフィン類、リン化合物、テトラフェニルボロン塩及びこれらの誘導体などの封止用成形材料に一般に使用されている硬化促進剤を、単独で又は２種以上を組み合わせて、必要に応じて配合することができる。
硬化促進剤の配合量は、硬化促進効果が達成される量であれば特に限定されるものではないが、封止用成形材料全体に対して０．００５〜２重量％が好ましく、より好ましくは０．０１〜１重量％、さらに好ましくは０．０５〜０．５重量％である。０．００５重量％未満では短時間での硬化性に劣る傾向があり、２重量％を超えると硬化速度が速すぎて良好な成形品を得ることが困難になる傾向がある。
【００１７】
本発明の封止用成形材料には、エポキシシラン、アミノシラン、ウレイドシラン、ビニルシラン、アルキルシラン、有機チタネート、アルミニウムアルコレート等のカップリング剤を、単独で又は２種以上を組み合わせて、必要に応じて配合することができる。また、赤燐、リン酸エステル、メラミン、メラミン誘導体、トリアジン環を有する化合物、シアヌル酸誘導体、イソシアヌル酸誘導体等の窒素含有化合物、シクロホスファゼン等の燐窒素含有化合物、酸化亜鉛、酸化鉄、酸化モリブデン、フェロセン等の金属化合物、三酸化アンチモン、四酸化アンチモン、五酸化アンチモン等の酸化アンチモン、ブロム化エポキシ樹脂などの従来公知の難燃剤を、単独で又は２種以上を組み合わせて、必要に応じて配合することができる。
本発明の封止用成形材料には、ＩＣ等の半導体素子の耐湿性、高温放置特性を向上させる観点から、イオントラップ剤を配合することもできる。イオントラップ剤としては特に制限はなく、従来公知のものを用いることができるが、例えば、ハイドロタルサイト類、マグネシウム、アルミニウム、チタン、ジルコニウム、ビスマス等の元素の含水酸化物などが挙げられ、これらを単独で又は２種類以上を組み合わせて用いることができる。
【００１８】
さらに、本発明の封止用成形材料には、その他の添加剤として、高級脂肪酸、高級脂肪酸金属塩、エステル系ワックス、ポリオレフィン系ワックス、ポリエチレン、酸化ポリエチレン等の離型剤、シリコーンオイルやシリコーンゴム粉末等の応力緩和剤、染料、カーボンブラック等の着色剤、希釈剤、レベリング剤、消泡剤などを必要に応じて配合することができる。
【００１９】
本発明の封止用エポキシ樹脂成形材料は、上記各種成分を均一に分散混合できるのであれば、いかなる手法を用いても調製できるが、一般的な手法として、所定の配合量の成分を秤量し、三本ロール、らいかい機等によって分散混練を行う方法を挙げることができる。
【００２０】
本発明で得られる封止用エポキシ樹脂成形材料により素子を封止して得られる電子部品装置としては、リードフレーム、配線済みのテープキャリア、配線板、ガラス、シリコンウエハ等の支持部材に、半導体チップ、トランジスタ、ダイオード、サイリスタ等の能動素子、コンデンサ、抵抗体、抵抗アレイ、コイル、スイッチ等の受動素子などの素子を搭載し、必要な部分を本発明の封止用エポキシ樹脂成形材料で封止して得られる電子部品装置などが挙げられる。このような電子部品装置としては、例えば、リードフレーム上に半導体素子を固定し、ボンディングパッド等の素子の端子部とリード部をワイヤボンディングやバンプで接続した後、本発明の封止用エポキシ樹脂成形材料を用いてディスペンス方式等により封止してなる、ＰＬＣＣ（Plastic Leaded Chip Carrier）、ＱＦＰ（Quad Flat Package）、ＳＯＰ（Small Outline Package）、ＳＯＪ（Small Outline J-leaded package）、ＴＳＯＰ（Thin Small Outline Package）、ＴＱＦＰ（Thin Quad Flat Package）等の一般的な樹脂封止型ＩＣ、テープキャリアにバンプで接続した半導体チップを、本発明の封止用エポキシ樹脂成形材料で封止したＴＣＰ（Tape Carrier Package）、配線板やガラス上に形成した配線に、ワイヤーボンディング、フリップチップボンディング、はんだ等で接続した半導体チップ、トランジスタ、ダイオード、サイリスタ等の能動素子及び／又はコンデンサ、抵抗体、コイル等の受動素子を、本発明の封止用エポキシ樹脂成形材料で封止したＣＯＢ（Chip On Boad）モジュール、ハイブリッドＩＣ、マルチチップモジュール、裏面に配線板接続用の端子を形成した有機基板の表面に素子を搭載し、バンプまたはワイヤボンディングにより素子と有機基板に形成された配線を接続した後、本発明の封止用エポキシ樹脂成形材料で素子を封止したＢＧＡ（Ball Grid Array）、ＣＳＰ（Chip Size Package）などが挙げられる。また、プリント回路板にも本発明の封止用エポキシ樹脂成形材料は有効に使用できる。
【００２１】
本発明の封止用エポキシ樹脂成形材料を用いて素子を封止する方法としては、ディスペンス方式、注型方式、印刷方式等が挙げられる。
【００２２】
【実施例】
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。
【００２３】
実施例１〜６、比較例１〜４
液状エポキシ樹脂としてエポキシ当量１６０のビスフェノールＦ型エポキシ樹脂（東都化成株式会社製商品名ＹＤＦ−８１７０Ｃ）、硬化剤として活性水素当量６３の３，３’−ジエチル−４，４’−ジアミノジフェニルメタン（液状芳香族アミン１、日本化薬株式会社製商品名カヤハードＡ−Ａ）、活性水素当量１１４のエポミックＱ−６４０（液状芳香族アミン２、三井化学株式会社製商品名）、活性水素当量４５のエピキュアＷ（液状芳香族アミン３、油化シェルエポキシ株式会社製商品名）、活性水素当量４８のジエチルトルエンジアミン（液状芳香族アミン４、Ｌｏｎｚａ社製商品名ＤＥＴＤＡ８０）、酸無水物当量１６８のＭＨ−７００（酸無水物、新日本理化株式会社製商品名）、エポキシ化ポリブタジエン化合物としてエポキシ化１，２−ポリブタジエン（日本曹達株式会社製商品名ＢＦ−１０００）、硬化促進剤として２−エチル−４−メチルイミダゾール、無機充填剤として平均粒径４μｍの球状溶融シリカを、それぞれ表１に示す組成で配合し、三本ロールにて混練分散した後、真空脱泡して、実施例１〜６及び比較例１〜４の液状封止用エポキシ樹脂成形材料を作製した。
【００２４】
【表１】

【００２５】
作製した実施例、比較例の封止用エポキシ樹脂成形材料を、１５０℃、３時間の加熱条件でディスペンス方式により成形して、次の各試験により評価した。評価結果を表２に示す。
（１）接着力
３０μｍ厚のアルミ箔又は７５μｍ厚のポリイミドフィルムの片面上に成形した試験片を作製し、オートグラフＡＧＳ−５００Ａ型（株式会社島津製作所製商品名）を用いて、ヘッドスピード３０ｍｍ／分の条件で、１０ｍｍ幅のアルミ箔又はポリイミドフィルムを垂直方向に引き剥がし、その強度（ピール強さ：Ｎ／ｍ）を測定した。この測定は、試験片成形直後、及び１２１℃、２ａｔｍ、１００％ＲＨのＰＣＴ条件で７２ｈ、１６８ｈ、２４０ｈ処理後の計４回行った。
（２）耐湿信頼性
上記成形条件で封止した評価用ＢＧＡパッケージ（チップ：アルミジグザグ配線形成ＴＥＧ）を１２１℃、２ａｔｍ、１００％ＲＨのＰＣＴ条件で２４０ｈ処理後、超音波探傷装置ＡＴ５５００（日立建機株式会社製商品名）を用いて封止用エポキシ樹脂成形材料とチップ及びポリイミドフィルムとの剥離の有無を観察した。また、アルミ配線及びパッドの断線・腐食不良を導通試験及び赤外線顕微鏡により確認し、不良パッケージ数／測定パッケージ数で評価した。
（３）耐熱衝撃性
上記（２）と同様の評価用ＢＧＡパッケージを、−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／測定パッケージ数で評価した。
【００２６】
【表２】

【００２７】
本発明における（Ｃ）成分のエポキシ化ポリブタジエン化合物を含まない比較例１及び２では接着力が低く、耐湿信頼性及び耐熱衝撃性が著しく劣り、（Ｃ）成分を含んでいても本発明の規定量より多い比較例４では相溶性が低く相分離を起こした結果耐湿信頼性及び耐熱衝撃性が低くなった。また、（Ｃ）成分が本発明の規定量より少ない比較例３でも耐湿信頼性及び耐熱衝撃性に劣っていた。さらに、（Ｂ）成分の液状芳香族アミン系硬化剤を含まない比較例１では接着力が著しく低かった。
これに対して、本発明の実施例１〜６は、高温高湿条件下でも接着力が高く、耐湿信頼性及び耐熱衝撃性も優れていた。
【００２８】
【発明の効果】
本発明になる封止用エポキシ樹脂成形材料は、実施例で示したように高温高湿条件下でも接着力が高く、この封止用エポキシ樹脂成形材料を用いて素子を封止すれば耐湿信頼性及び耐熱衝撃性に優れる電子部品装置を得ることができるので、その出荷時の梱包や半導体装置等の電子部品装置の製造工程での吸湿管理等も簡便になり、その工業的価値は大である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an epoxy resin molding material for sealing that is particularly suitable for a semiconductor device that requires high reliability, and an electronic component device including an element sealed with the epoxy resin molding material for sealing.
[0002]
[Prior art]
Conventionally, in the field of element sealing of electronic component devices such as transistors and ICs, resin sealing has been the mainstream in terms of productivity and cost, and epoxy resin molding materials have been widely used. This is because the epoxy resin is balanced in various properties such as workability, moldability, electrical properties, moisture resistance, heat resistance, mechanical properties, and adhesiveness with inserts.
[0003]
In recent years, high-density mounting of electronic components on printed wiring boards has been progressing. In connection with this, the electronic component devices are changed from conventional pin insertion type packages such as DIP (Dual Inline Package) and PPGA (Plastic Pin Grid Aray) to SOJ (Small Outline J-leaded package) and SOP (Small Outline Package). , BGA (Ball Grid Array), CSP (Chip Size Package) and other surface mount type packages are moving to the mainstream, and bare chip mount type is also used. Surface-mount ICs, LSIs, etc. are thin and small packages to increase the mounting density and reduce the mounting height, increasing the area occupied by the device package, and the package thickness is extremely high It has become thinner. Furthermore, these packages are different in mounting method from the conventional pin insertion type. That is, since the pin insertion type package is soldered from the back side of the wiring board after the pins are inserted into the wiring board, the package is not directly exposed to high temperature. However, surface-mount ICs are temporarily attached to the surface of a wiring board and processed by a solder bath or a reflow device, so that they are directly exposed to a soldering temperature (reflow temperature). As a result, when the IC package absorbs moisture, the vapor pressure generated by vaporization of the moisture absorption works as a peeling stress, and if the adhesive strength of the sealing molding material used for the package is weak, inserts such as elements and lead frames Peels between the sealing material and the sealing molding material, which causes package cracks and poor soldering.
As a molding material for sealing used for element sealing of electronic component devices, liquid epoxy resin molding materials that are advantageous for thin and small packages from the viewpoint of moldability are frequently used in place of conventional solid epoxy resin molding materials. As a result, the sealing method has changed from the transfer molding method to the dispensing method or the printing method. In the liquid epoxy resin molding material, an acid anhydride curing agent that is advantageous for reducing the viscosity is usually blended together with the liquid epoxy resin.
[Problems to be solved by the invention]
[0004]
However, the liquid epoxy resin molding material using an acid anhydride-based curing agent has low adhesive strength under high-temperature and high-humidity conditions, and due to thermal stress generated by the difference in thermal expansion coefficient of resin / element / organic substrate, Interfacial delamination is likely to occur between inserts. For this reason, an electronic component device such as a semiconductor device having an element sealed with a liquid epoxy resin molding material using an acid anhydride-based curing agent has a drawback of poor moisture resistance reliability and thermal shock resistance. Therefore, in electronic component devices sealed with the current epoxy resin molding material for sealing, measures are taken such as shipping in moisture-proof packaging, or using it after thoroughly drying before mounting on a wiring board. However, these methods are laborious and costly.
The present invention has been made in view of such circumstances, and has a high adhesive strength sealing epoxy even under high-temperature and high-humidity conditions, such as simple packaging and moisture absorption management in the manufacturing process of electronic component devices such as semiconductor devices. An object of the present invention is to provide an electronic component device that is excellent in moisture resistance reliability and thermal shock resistance, comprising a resin molding material and an element sealed thereby.
[0005]
[Means for Solving the Problems]
As a result of intensive studies in order to solve the above-mentioned problems, the inventors compounded an epoxy resin molding material for sealing with a liquid epoxy resin, a liquid aromatic amine-based curing agent, and a specific amount of an epoxidized polybutadiene compound. As a result, the inventors have found that the above object can be achieved, and completed the present invention.
[0006]
That is, the present invention
(1) (A) liquid epoxy resin, (B) liquid aromatic amine-based curing agent, (C) epoxidized polybutadiene compound, and (D) inorganic filler are essential components, and the amount of component (C) is ( An epoxy resin molding material for sealing that is 12 to 34% by weight based on the total amount of the component (A), the component (B) and the component (C),
(2) The epoxy resin molding material for sealing according to the above (1), wherein the epoxidized polybutadiene compound (C) is a compound represented by the following general formula (I):
[Chemical 2]

(Here, m represents an integer of 2 to 10, and n represents an integer of 5 to 30.)
(3) The epoxy resin molding material for sealing according to (1) or (2) above, wherein the number average molecular weight of component (C) is 800 to 1500 and the epoxy equivalent is 200 to 240, and (4) liquid aroma The sealing according to any one of (1) to (3) above, wherein the group amine curing agent (B) contains 3,3′-diethyl-4,4′-diaminodiphenylmethane and / or diethyltoluenediamine. The present invention relates to an epoxy resin molding material for use, and (5) an electronic component device including an element sealed with the sealing epoxy resin molding material described in any one of (1) to (4) above.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
The liquid epoxy resin of component (A) used in the present invention is not particularly limited as long as it has one or more epoxy groups in one molecule and is liquid at room temperature, and is generally used in molding materials for sealing. A liquid epoxy resin can be used. Moreover, if the epoxy resin molding material for sealing is liquid, a solid epoxy resin can be used in combination, but the solid epoxy resin used in combination is preferably 20% by weight or less based on the total amount of the epoxy resin. Examples of the epoxy resin that can be used in the present invention include phenols and aldehydes such as diglycidyl ethers such as bisphenol A, bisphenol F, bisphenol AD, bisphenol S, hydrogenated bisphenol A, and orthocresol novolac type epoxy resins. Epoxy of novolak resin obtained by condensation or co-condensation of glycidyl ester type epoxy resin obtained by reaction of polybasic acid such as phthalic acid and dimer acid and epichlorohydrin, polyamine such as diaminodiphenylmethane, isocyanuric acid and epichlorohydrin Glycidylamine-type epoxy resin obtained by the above reaction, linear aliphatic epoxy resin obtained by oxidizing olefinic bonds with peracid such as peracetic acid, and alicyclic epoxy resin. May be used in combination or two or more of them may be used in Germany. 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.
[0008]
The liquid aromatic amine curing agent (B) used in the present invention is not particularly limited as long as it is an amine derivative of an aromatic hydrocarbon that is liquid at room temperature. For example, EpiCure W and EpiCure Z are commercially available products. (Trade name manufactured by Yuka Shell Epoxy Co., Ltd.), Kayahard A-A, Kayahard AB, Kayahard AS (trade name manufactured by Nippon Kayaku Co., Ltd.), Totoamine HM-205 (trade name manufactured by Toto Kasei Co., Ltd.) ), Adeka Hardener EH-101 (trade name, manufactured by Asahi Denka Kogyo Co., Ltd.), Epomic Q-640, Epomic Q-643 (trade name, Mitsui Chemicals Co., Ltd.), DETDA 80 (trade name, manufactured by Lonza) are available. These may be used alone or in combination of two or more. From the viewpoint of storage stability, a liquid aromatic amine-based curing agent mainly composed of 3,3′-diethyl-4,4′-diaminodiphenylmethane and / or diethyltoluenediamine is preferable.
In addition to the liquid aromatic amine-based curing agent of component (B), a curing agent generally used in sealing molding materials such as phenolic curing agents and acid anhydrides can be used in combination. If the epoxy resin molding material is liquid, a solid curing agent can also be used in combination. When other curing agents are used in combination, the blending amount of the liquid aromatic amine curing agent (B) is preferably 60% by weight or more based on the total amount of the curing agent in order to exhibit its performance.
[0009]
The equivalent ratio of the epoxy resin containing the component (A) and the curing agent containing the component (B) is not particularly limited, but in order to suppress each unreacted component to a small amount, It is preferable to set in the range of -1.6 equivalent, 0.8-1.4 equivalent is more preferable, 0.9-1.2 equivalent is further more preferable. 0.7. When deviating from the range of ˜1.6 equivalents, the curing reaction becomes insufficient and the reliability tends to decrease.
[0010]
The epoxidized polybutadiene compound of the component (C) used in the present invention is not particularly limited as long as it is a polybutadiene compound having an epoxy group, but preferred examples include compounds represented by the following general formula (I). . From the viewpoint of adhesiveness, a compound having a number average molecular weight of 800 to 1500 and an epoxy equivalent of 200 to 240 is preferable.
[Chemical 3]

In the above formula (I), m is an integer of 2 to 10, n is an integer of 5 to 30, and from the viewpoint of adhesiveness, m = 3 to 8 and n = 8 to 25 are preferable, and m = 3 to 3 6, n = 10 to 21 is more preferable.
[0011]
Examples of the compound represented by the formula (I) include those containing the following m components (c1) and n components (c2) in the skeleton at random, those containing them alternately, and those containing them in a block form. These may be used alone or in combination of two or more.
[Formula 4]

[0012]
1,2-polybutadiene in which m in the above formula (I) is 5 and n is 12 is available as a commercial product BF-1000 (trade name, manufactured by Nippon Soda Co., Ltd.). BF-1000 has a number average molecular weight of 1000 and an epoxy equivalent of 206.
[0013]
In order to achieve the effect of the present invention, the blending amount of the (C) component epoxidized polybutadiene compound is 12 to 34% by weight based on the total amount of the (A) component, the (B) component and the (C) component. It is necessary to be 14 to 28% by weight.
[0014]
The inorganic filler of component (D) used in the present invention is blended in a molding material for hygroscopicity, thermal expansion coefficient reduction, thermal conductivity improvement and strength improvement. For example, fused silica, crystalline silica Powder of alumina, zircon, calcium silicate, calcium carbonate, potassium titanate, silicon carbide, silicon nitride, aluminum nitride, boron nitride, beryllia, zirconia, zircon, fosterite, steatite, spinel, mullite, titania, or Examples thereof include spherical beads, glass fibers, and the like. Furthermore, examples of the inorganic filler having a flame retardant effect include aluminum hydroxide, magnesium hydroxide, zinc borate, and zinc molybdate. These inorganic fillers may be used alone or in combination of two or more. Among the above inorganic fillers, silica is preferable from the viewpoint of reducing the thermal expansion coefficient, and alumina is preferable from the viewpoint of high thermal conductivity. The particle shape of the inorganic filler is preferably spherical from the viewpoints of fluidity and penetration into the fine gaps. Moreover, 1-20 micrometers is preferable and, as for an average particle diameter, 2-10 micrometers is more preferable. If the average particle size is less than 1 μm, the dispersibility in the liquid resin tends to be inferior, or the thixotropic property is imparted to the liquid sealing molding material and the fluidity tends to be inferior. It tends to be easy, and the fluidity and permeability to the fine gaps tend to be poor.
[0015]
The blending amount of the inorganic filler of component (D) is preferably 20 to 90% by weight, more preferably 30 to 85% by weight, and further 40 to 80% by weight based on the entire epoxy resin molding material for sealing. preferable. When the blending amount is less than 20% by weight, the effect of reducing the thermal expansion coefficient tends to be small. When the blending amount exceeds 90% by weight, the viscosity of the sealing epoxy resin molding material increases, and the fluidity, permeability, and dispensing property tend to decrease. There is.
[0016]
The sealing molding material of the present invention is generally used for sealing molding materials such as cycloamidine compounds, tertiary amines, imidazoles, organic phosphines, phosphorus compounds, tetraphenylboron salts and derivatives thereof. These curing accelerators can be blended as needed alone or in combination of two or more.
The blending amount of the curing accelerator is not particularly limited as long as the curing acceleration effect is achieved, but is preferably 0.005 to 2% by weight, more preferably based on the whole molding material for sealing. It is 0.01 to 1 weight%, More preferably, it is 0.05 to 0.5 weight%. If it is less than 0.005% by weight, the curability in a short time tends to be inferior, and if it exceeds 2% by weight, the curing rate tends to be too high and it tends to be difficult to obtain a good molded product.
[0017]
In the molding material for sealing of the present invention, a coupling agent such as epoxy silane, amino silane, ureido silane, vinyl silane, alkyl silane, organic titanate, aluminum alcoholate, or a combination of two or more, as required Can be blended. In addition, red phosphorus, phosphate esters, melamine, melamine derivatives, compounds having a triazine ring, nitrogen-containing compounds such as cyanuric acid derivatives and isocyanuric acid derivatives, phosphorus nitrogen-containing compounds such as cyclophosphazene, zinc oxide, iron oxide, molybdenum oxide Conventional flame retardants such as metal compounds such as ferrocene, antimony trioxide, antimony tetroxide, antimony pentoxide and other antimony oxides, brominated epoxy resins, alone or in combination of two or more, as required Can be blended.
From the viewpoint of improving the moisture resistance and high-temperature storage characteristics of a semiconductor element such as an IC, an ion trap agent can also be blended in the sealing molding material of the present invention. The ion trapping agent is not particularly limited and conventionally known ones can be used. Examples thereof include hydrotalcites, hydrous oxides of elements such as magnesium, aluminum, titanium, zirconium, and bismuth. Can be used alone or in combination of two or more.
[0018]
Furthermore, the molding compound for sealing of the present invention includes, as other additives, mold release agents such as higher fatty acids, higher fatty acid metal salts, ester waxes, polyolefin waxes, polyethylenes, polyethylene oxides, silicone oils and silicone rubbers. A stress relaxation agent such as powder, a colorant such as a dye and carbon black, a diluent, a leveling agent, an antifoaming agent, and the like can be blended as necessary.
[0019]
The epoxy resin molding material for sealing of the present invention can be prepared by any method as long as the above-mentioned various components can be uniformly dispersed and mixed, but as a general method, a predetermined amount of components are weighed. And a method of carrying out dispersion kneading with a three-roller, a rough machine or the like.
[0020]
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 Active elements such as chips, transistors, diodes, and thyristors, and passive elements such as capacitors, resistors, resistor arrays, coils, and switches are mounted, and necessary parts are sealed with the sealing epoxy resin molding material of the present invention. An electronic component device obtained by stopping the operation can be used. 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. Sealed by a dispensing method using molding materials, etc., PLCC (Plastic Leaded Chip Carrier), QFP (Quad Flat Package), SOP (Small Outline Package), SOJ (Small Outline J-leaded package), TSOP (Thin Small outline package (TQFP), a general resin-encapsulated IC such as a thin quad flat package (TQFP), and a semiconductor chip that is connected to a tape carrier by a bump (TCP) (encapsulated with the epoxy resin molding material for encapsulation of the present invention) Tape Carrier Package), semiconductors connected to wiring formed on wiring boards and glass by wire bonding, flip chip bonding, solder, etc. COB (Chip On Boad) module, hybrid, in which active elements such as body chips, transistors, diodes, thyristors and / or passive elements such as capacitors, resistors, coils, etc. are sealed with the sealing epoxy resin molding material of the present invention An element is mounted on the surface of an IC, a multichip module, and an organic substrate on which a wiring board connection terminal is formed on the back surface, and the element and the wiring formed on the organic substrate are connected 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 fixing 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.
[0021]
Examples of a method for sealing an element using the epoxy resin molding material for sealing of the present invention include a dispensing method, a casting method, and a printing method.
[0022]
【Example】
EXAMPLES Next, although an Example demonstrates this invention, the scope of the present invention is not limited to these Examples.
[0023]
Examples 1-6, Comparative Examples 1-4
Bisphenol F type epoxy resin having an epoxy equivalent of 160 (trade name YDF-8170C, manufactured by Toto Kasei Co., Ltd.) as a liquid epoxy resin, 3,3′-diethyl-4,4′-diaminodiphenylmethane having an active hydrogen equivalent of 63 as a curing agent (liquid Aromatic amine 1, Nippon Kayaku Co., Ltd. trade name Kayahard A-A), Epoxy Q-640 with active hydrogen equivalent 114 (liquid aromatic amine 2, Mitsui Chemicals trade name), epicure with active hydrogen equivalent 45 W (Liquid aromatic amine 3, product name manufactured by Yuka Shell Epoxy Co., Ltd.), diethyltoluenediamine having an active hydrogen equivalent of 48 (liquid aromatic amine 4, product name DETDA80 manufactured by Lonza), MH- of acid anhydride equivalent 168 700 (acid anhydride, trade name manufactured by Shin Nippon Rika Co., Ltd.), Epoxy as an epoxidized polybutadiene compound 1,2-polybutadiene (trade name BF-1000 manufactured by Nippon Soda Co., Ltd.), 2-ethyl-4-methylimidazole as a curing accelerator, and spherical fused silica having an average particle size of 4 μm as an inorganic filler are shown in Table 1. After blending with the composition shown and kneading and dispersing with three rolls, vacuum defoaming was performed to prepare epoxy resin molding materials for liquid sealing of Examples 1 to 6 and Comparative Examples 1 to 4.
[0024]
[Table 1]

[0025]
The produced epoxy resin molding materials for sealing of Examples and Comparative Examples were molded by a dispensing method under heating conditions of 150 ° C. for 3 hours, and evaluated by the following tests. The evaluation results are shown in Table 2.
(1) A test piece formed on one surface of an aluminum foil having a bonding strength of 30 μm or a polyimide film having a thickness of 75 μm is prepared, and using an autograph AGS-500A type (trade name, manufactured by Shimadzu Corporation), a head speed of 30 mm. The aluminum foil or polyimide film having a width of 10 mm was peeled off in the vertical direction under the conditions of / min, and the strength (peel strength: N / m) was measured. This measurement was performed a total of four times immediately after the test piece molding and after treatment for 72 h, 168 h, and 240 h under PCT conditions of 121 ° C., 2 atm, 100% RH.
(2) Moisture resistance reliability After processing the evaluation BGA package (chip: aluminum zigzag wiring formation TEG) sealed under the above molding conditions under the PCT conditions of 121 ° C., 2 atm and 100% RH for 240 hours, the ultrasonic flaw detector AT5500 (Hitachi) The presence or absence of peeling between the epoxy resin molding material for sealing, the chip, and the polyimide film was observed using a trade name manufactured by Kenki Co., Ltd. In addition, disconnection / corrosion failure of the aluminum wiring and pads was confirmed by a continuity test and an infrared microscope, and evaluated by the number of defective packages / number of measurement packages.
(3) Thermal shock resistance The same evaluation BGA package as in (2) above was processed for 1000 cycles at −50 ° C./150° C. for 30 minutes, and a continuity test was conducted to check for disconnection defects in the aluminum wiring. Evaluation was based on the number of defective packages / number of measurement packages.
[0026]
[Table 2]

[0027]
In Comparative Examples 1 and 2 that do not contain the epoxidized polybutadiene compound of the component (C) in the present invention, the adhesive strength is low, the moisture resistance reliability and the thermal shock resistance are remarkably inferior, and even if the component (C) is included, the definition of the present invention In Comparative Example 4 in which the amount was larger, the compatibility was low and the phase separation was caused. As a result, the moisture resistance reliability and the thermal shock resistance were lowered. Further, even in Comparative Example 3 in which the component (C) was less than the specified amount of the present invention, the moisture resistance reliability and the thermal shock resistance were inferior. Further, in Comparative Example 1 which did not contain the liquid aromatic amine curing agent as the component (B), the adhesive strength was remarkably low.
On the other hand, Examples 1 to 6 of the present invention had high adhesive force even under high temperature and high humidity conditions, and were excellent in moisture resistance reliability and thermal shock resistance.
[0028]
【The invention's effect】
The epoxy resin molding material for sealing according to the present invention has high adhesive force even under high temperature and high humidity conditions as shown in the examples. If the device is sealed using this epoxy resin molding material for sealing, the moisture resistance reliability The electronic component device with excellent heat resistance and thermal shock resistance can be obtained, so the packaging at the time of shipment and the moisture absorption management in the manufacturing process of the electronic component device such as a semiconductor device can be simplified, and its industrial value is great. is there.

Claims (5)

(A) Liquid epoxy resin, (B) Liquid aromatic amine-based curing agent, (C) Epoxidized polybutadiene compound, and (D) Inorganic filler are essential components, and the blending amount of component (C) is component (A) The epoxy resin molding material for sealing which is 12 to 28 % by weight based on the total amount of the components (B) and (C). The epoxy resin molding material for sealing according to claim 1, wherein the epoxidized polybutadiene compound (C) is a compound represented by the following general formula (I).

(Here, m represents an integer of 2 to 10, and n represents an integer of 5 to 30.)   The number average molecular weight of (C) component is 800-1500, and an epoxy equivalent is 200-240, The epoxy resin molding material for sealing of Claim 1 or Claim 2.   The liquid aromatic amine-based curing agent (B) contains 3,3'-diethyl-4,4'-diaminodiphenylmethane and / or diethyltoluenediamine, for sealing according to any one of claims 1 to 3. Epoxy resin 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.