JP2004292506A - Flame-retardant epoxy resin composition, semiconductor sealing medium using the same and semiconductor device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a flame-retardant epoxy resin composition which imparts excellent flame retardance and can give good curability and flowability, and to provide a semiconductor device excellent in moisture-resistant reliability and soldering crack resistance as well. <P>SOLUTION: The flame-retardant epoxy resin composition has a biphenyl type epoxy resin (A) represented by formula (1) (wherein R<SP>1</SP>to R<SP>7</SP>and R<SP>8</SP>are each one kind selected from hydrogen, methyl group, ethyl group, propyl group, butyl group, and phenyl group and may be the same or different from one another; and (a) is an integer of ≥1), a biphenyl type phenolic resin (B) represented by formula (2), and an aromatic compound (C) having an ethynyl group as the essential components. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

［式中、Ｒ^１〜Ｒ^７、およびＲ^８は、それぞれ、水素原子、メチル基、エチル基、プロピル基、ブチル基、フェニル基から選択される１種を表し、互いに同一であっても異なっていてもよい。ただしａは１以上の整数である。］
【００１１】
【化４】

［式中、Ｒ^９〜Ｒ^１５、およびＲ^１６は、それぞれ、水素原子、メチル基、エチル基、プロピル基、ブチル基、フェニル基から選択される１種を表し、互いに同一であっても異なっていてもよい。ただし、ｂは、１以上の整数である。］
さらに、前記一般式（１）および一般式（２）におけるａ、ｂは、それぞれ１〜１０であることが好ましい。
【００１２】
前記エチニル基を有する芳香族化合物（Ｃ）は、ｐ−エチニルフェノール、ｍ−エチニルフェノール、ｏ−エチニルフェノール、１，２−ジエチニルベンゼン、１，３−ジエチニルベンゼン、１，４−ジエチニルベンゼン、１，３，５−トリエチニルベンゼン、１，２，４−トリエチニルベンゼン、１，２，４，５−テトラエチニルベンゼン、ヘキサエチニルベンゼン、ペンタエチニルフェノール、または３，３’，５，５’−テトラエチニルビフェニルが好ましい。
【００１３】
【発明の実施の形態】
本発明の難燃性エポキシ樹脂組成物、及びそれを用いた半導体封止材料は、ハロゲン化エポキシ樹脂などのハロゲン系化合物や、金属水酸化物を使用せず、特定構造のビフェニル型エポキシ樹脂と特定構造のビフェニル型フェノール樹脂に炭素−炭素三重結合を少なくとも１個以上含有する化合物（Ｃ）の添加によって、優れた難燃性、良好な硬化性、流動性を付与し、該エポキシ樹脂組成物より得られる半導体装置は耐半田クラック性に優れることを見出した。
【００１４】
本発明に用いる一般式（１）で表されるビフェニル型エポキシ樹脂の置換基Ｒ_１〜Ｒ_８は、水素原子、炭素数１〜４のアルキル基、およびハロゲン原子から選択される１種を表し、これらは、互いに同一であっても異なっていてもよい。
これらの置換基Ｒ^１〜Ｒ^８の具体例としては、それぞれ、例えば、水素原子、メチル基、エチル基、プロピル基、ブチル基、およびフェニル基などが挙げられるが、これらの中でも、特に、水素原子またはメチル基であるビス（メトキシメチル）ビフェニル・フェノール重縮合物型エポキシ化合物が好ましい。
【００１５】
本発明に用いる一般式（２）で表されるビフェニル型フェノール樹脂（Ｂ）の置換基Ｒ^９〜Ｒ^１５は、水素原子、炭素数１〜４のアルキル基、およびハロゲン原子から選択される１種を表し、これらは、互いに同一であっても異なっていてもよい。
これらの置換基Ｒ^９〜Ｒ^１５の具体例としては、それぞれ、例えば、水素原子、メチル基、エチル基、プロピル基、ブチル基、およびフェニル基などが挙げられるが、これらの中でも、特に、水素原子またはメチル基であるビス（メトキシメチル）ビフェニル・フェノール重縮合物が好ましい。
【００１６】
これらの樹脂を用いることにより、エポキシ樹脂組成物の成形時（例えば半導体装置の製造時等）の流動性が向上するとともに、得られた半導体装置の耐半田クラック性および耐湿信頼性が、より向上する。
【００１７】
本発明において、一般式（１）で表されるビフェニル型エポキシ樹脂（Ａ）と一般式（２）で表されるビフェニル型フェノール樹脂（Ｂ）の配合割合は、エポキシ樹脂（Ａ）のエポキシ当量に対する化合物（Ｂ）の水酸基当量の割合が、０．５〜２．０の範囲で配合することが好ましい。
【００１８】
本発明に用いるエチニル基を有する芳香族化合物（Ｃ）としては、ｐ−エチニルフェノール、ｍ−エチニルフェノール、ｏ−エチニルフェノール、１，２−ジエチニルベンゼン、１，３−ジエチニルベンゼン、１，４−ジエチニルベンゼン、１，３，５−トリエチニルベンゼン、１，２，４−トリエチニルベンゼン、１，２，４，５−テトラエチニルベンゼン、ヘキサエチニルベンゼン、ペンタエチニルフェノール、および３，３’，５，５’−テトラエチニルビフェニルなどが挙げられる。これらは、単独で用いてもよく、複数を混合しても良い。
【００１９】
本発明におけるエチニル基を有する芳香族化合物（Ｃ）の配合量としては、ビフェニル型エポキシ樹脂（Ａ）とビフェニル型フェノール樹脂（Ｂ）との合計１００重量部に対して、１〜５０重量部が好ましいが、１０〜３０重量部の範囲とするのが、より好ましい。前記下限値未満では難燃性の効果が小さくなる恐れがあり、一方、前記上限値を越えると硬化性が低下する恐れがある。
【００２０】
本発明に用いる充填剤としては、溶融シリカおよび結晶シリカ等のシリカ、アルミナ、タルク、炭酸カルシウム、クレー、マイカなどが挙げられる。これらに内、好ましくは溶融シリカであり、さらに好ましくは、粒子形状が球状をなしており、平均粒径は、１〜１００μｍの球状シリカである。
【００２１】
本発明における充填剤の配合量としては、ビフェニル型エポキシ樹脂（Ａ）と、ビフェニル型フェノール樹脂（Ｂ）との合計量１００重量部あたり、２００〜２４００重量部であることが好ましい。
【００２２】
また、本発明の難燃性エポキシ樹脂組成物および半導体封止材料中には、前記成分の他に、必要に応じて、例えば、γ−グリシドキシプロピルトリメトキシシラン等のカップリング剤、カーボンブラック等の着色剤、シリコーンオイル、シリコーンゴム等の低応力成分、天然ワックス、合成ワックス、高級脂肪酸またはその金属塩類、パラフィン等の離型剤、酸化防止剤等の各種添加剤を添加することができる。
【００２３】
本発明の難燃性エポキシ樹脂組成物は、前記成分（Ａ）、成分（Ｂ）および成分（Ｃ）を、必要に応じて、その他の各種添加剤を、ミキサーを用いて、常温混合し、半導体封止材料は、これに充填剤を加えて、前記同様に混合し、更にこれらの混合物を、熱ロールおよび加熱ニーダー等の混練機を用いて、加熱混練後、冷却、粉砕することにより得られる。
【００２４】
本発明の半導体装置は、上記で得られた半導体封止材料を、モールド樹脂として用いて、トランスファーモールド、コンプレッションモールド、インジェクションモールド等の成形方法で、硬化成形することにより、半導体素子を封止して、得られる。
このようにして得られた本発明の半導体装置は、耐湿信頼性はもちろん耐半田クラック性が特に優れ、樹脂組成物は優れた難燃性を示し、硬化性、流動性は良好である。
【００２５】
以上、本発明の難燃性エポキシ樹脂組成物および半導体装置の好適実施形態について説明したが、本発明は、これに限定されるものではない。
【００２６】
【実施例】
以下、実施例により本発明を詳しく説明するが、本発明はこれによって何ら限定されるものではない。
【００２７】
［エチニル基を有する芳香族化合物（Ｃ）の合成例］
化合物（Ｃ）の合成は、Ｍａｃｒｏｍｏｌｅｃｕｌｅｓ（２００２，Ｖｏｌ．３５，ｐｐ１１８０−１１８９）Ｐｏｌｙｍｅｒ（１９９５， Ｖｏｌ３６ Ｎｏ．１ ｐｐ１８７−１９２），Ｃｈｅｍ．Ｒｅｖ（１９９９，Ｖｏｌ．９，ｐｐ１７４７−１７８５）に順じ合成した。以下に合成例を示すが、必ずしも文献の方法、反応温度、反応時間に限定されるものではない。
【００２８】
（ｐ−エチニルフェノールの合成）
窒素置換、及び真空が可能で、冷却管および撹拌装置付きの２Ｌのセパラブルフラスコに、ｐ−ヨードフェノール２０ｇ（９０．８ｍｍｏｌ）、２−メチル−３−ブチニル−２−オール１８．３６ｇ（２１８．４ｍｍｏｌ）、トリエチルアミン６００ｍｌを入れ、窒素を流し攪拌する。その後、ジクロロビス（トリフェニルホスフィン）パラジウム（ＩＩ）０．６４ｇ（６．４ｍｍｏｌ）、ヨウ化銅０．８８ｇ（４．４ｍｍｏｌ）、トリフェニルホスフィン１．６８ｇ（６．４ｍｍｏｌ）を素早入れ、攪拌した。その後、オイルバスに入れ、７０℃に加温し１２時間放置した。その後、トリエチルアミンを減圧蒸留し、イソプロパノールで抽出した。メタノールで再結晶し、４−（３−ヒドロキシ−３−メチル−１−ブチニル）フェノールを２０ｇ得た。
真空が可能で冷却管および撹拌装置付きの１Ｌのセパラブルフラスコに、４−（３−ヒドロキシ−３−メチル−１−ブチニル）フェノール１０ｇ、１，４−ジオキサン２００ｍｌ、水酸化カルウム（粒状）４．２ｇを入れ、１３０℃のオイルバスで１０時間加熱した。その後、冷却し、６ｍｏｌ／Ｌ塩酸２００ｍｌを敵下し、イソプロパノールで抽出し、ｐ−エチニルフェノール（Ｃ−１）を６ｇ得た。
【００２９】
（ｍ−エチニルフェノール（Ｃ−２）、ｏ−エチニルフェノール（Ｃ−３）の合成）
ｐ−ヨードフェノールに代え、ｍ−ヨードフェノール、ｏ−ヨードフェノールを用いた以外はＣ−１を得たときと同様の方法で、それぞれ、Ｃ−２を６ｇ、Ｃ−３を６ｇ得た。
【００３０】
（１，２−エチニルベンゼン（Ｃ−４）の合成）
窒素置換、及び真空が可能で、冷却管および撹拌装置付きの１Ｌのセパラブルフラスコに、１，２−ジブロモベンゼン１２．５ｇ（５３ｍｍｏｌ）、２−メチル−３−ブチニル−２−オール９．２５ｇ（１１０ｍｍｏｌ）、トリエチルアミン２２１ｍｌ（１．１ｍｏｌ）、ピリジン１４６ｍｌ（１．８１ｍｏｌ）を入れ、窒素を流し攪拌した。その後、ジクロロビス（トリフェニルホスフィン）パラジウム（ＩＩ）１．１１ｇ（１．５９ｍｍｏｌ）、ヨウ化銅１．０１ｇ（５．２８ｍｍｏｌ）、トリフェニルホスフィン２．２２ｇ（８．４６ｍｍｏｌ）を素早入れ、攪拌した。その後、セパラブルフラスコを、オイルバスに入れ、８５℃に加温し１２時間放置した。その後、ピリジン、トリエチルアミンを減圧蒸留し、イソプロパノールで抽出した。メタノールで再結晶し、１，２−ビス（３−ヒドロキシ−３−メチル−１−ブチニル）ベンゼンを１５ｇ得た。
真空が可能で冷却管および撹拌装置付きの１Ｌのセパラブルフラスコに、１，２−ビス（３−ヒドロキシ−３−メチル−１−ブチニル）ベンゼン１０ｇ、１，４−ジオキサン２００ｍｌ、水酸化カルウム（粒状）４．２ｇを入れ、１３０℃のオイルバスで１０時間加熱した。その後、冷却し、６ｍｏｌ／Ｌ塩酸２００ｍｌを敵下し、イソプロパノールで抽出し、１，２−ジエチニルベンゼン（Ｃ−４）を６ｇ得た。
【００３１】
（１，３−エチニルベンゼン（Ｃ−５）、１，４−エチニルベンゼン（Ｃ−６）の合成）
１，２−ジブロモベンゼンに代え、１，３−ジブロモベンゼン、１，４−ジブロモベンゼンを用いた以外はＣ−１を得たときと同様の方法で、それぞれ、Ｃ−５を６ｇ、Ｃ−６を６ｇ得た。
【００３２】
（１，３，５−トリスエチニルベンゼン（Ｃ−７）の合成）
窒素置換、及び真空が可能で、冷却管および撹拌装置付きの１Ｌのセパラブルフラスコに、１，３，５−トリスブロモベンゼン１６．７ｇ（５３ｍｍｏｌ）、２−メチル−３−ブチニル−２‐オール１３．８７ｇ（１６５ｍｍｏｌ）、トリエチルアミン２２１ｍｌ（１．５８ｍｏｌ）、ピリジン１４６ｍｌ（１．８１ｍｏｌ）を入れ、窒素を流し攪拌した。その後、ジクロロビス（トリフェニルホスフィン）パラジウム（ＩＩ）１．１１ｇ（１．５９ｍｍｏｌ）、ヨウ化銅１．０１ｇ（５．２８ｍｍｏｌ）、トリフェニルホスフィン２．２２ｇ（８．４６ｍｍｏｌ）を素早入れ、攪拌した。その後、セパラブルフラスコを、オイルバスに入れ、８５℃に加温し１２時間放置した。その後、ピリジン、トリエチルアミンを減圧蒸留し、イソプロパノールで抽出した。メタノールで再結晶し、１，２，３−トリス（３−ヒドロキシ−３−メチル−１−ブチニル）ベンゼンを１４ｇ得た。
真空が可能で冷却管および撹拌装置付きの１Ｌのセパラブルフラスコに、１，２，３−トリス（３−ヒドロキシ−３−メチル−１−ブチニル）ベンゼン１０ｇ、１，４−ジオキサン２００ｍｌ、水酸化カルウム（粒状）４．２ｇを入れ、１３０℃のオイルバスで１０時間加熱した。その後、冷却し、６規定塩酸２００ｍｌを敵下し、イソプロパノールで抽出し、１，３，５−トリエチニルベンゼン（Ｃ−７）を６ｇ得た。
【００３３】
（１，２，４−トリスエチニルベンゼン（Ｃ−８）の合成）
１，３，５−トリスブロモベンゼンに代え、１，２，４−トリスブロモベンゼンを用いた以外はＣ−７を得たときと同様の方法でＣ−８を６ｇ得た。
【００３４】
（１，２，４，５−テトラエチニルベンゼン（Ｃ−９）の合成）
窒素置換、及び真空が可能で冷却管および撹拌装置付きの１Ｌのセパラブルフラスコに、１，２，４，５−テトラブロモベンゼン２０．８７ｇ（５３ｍｍｏｌ）、２−メチル−３−ブチニル−２‐オール１８．５１ｇ（２２０ｍｍｏｌ）、トリエチルアミン２２１ｍｌ（１．５８ｍｏｌ）、ピリジン１４６ｍｌ（１．８１ｍｏｌ）を入れ、窒素を流し攪拌した。その後、ジクロロビス（トリフェニルホスフィン）パラジウム（ＩＩ）１．１１ｇ（１．５９ｍｍｏｌ）、ヨウ化１．０１ｇ（５．２８ｍｍｏｌ）、トリフェニルホスフィン２．２２ｇ（８．４６ｍｍｏｌ）を素早入れ、攪拌した。その後、セパラブルフラスコを、オイルバスに入れ、８５℃に加温し１２時間放置した。その後、ピリジン、トリエチルアミンを減圧蒸留し、イソプロパノールで抽出した。メタノールで再結晶し、１，２，４，５−テトラ（３−ヒドロキシ−３−メチル−１−ブチニル）ベンゼンを１４ｇ得た。
真空が可能で冷却管および撹拌装置付きの１Ｌのセパラブルフラスコに、１，２，４，５−テトラ（３−ヒドロキシ−３−メチル−１−ブチニル）ベンゼン１０ｇ、１，４−ジオキサン２００ｍｌ、水酸化カルウム（粒状）４．２ｇを入れ、１３０℃のオイルバスで１０時間加熱した。その後、冷却し、６ｍｏｌ／Ｌ塩酸２００ｍｌを敵下し、イソプロパノールで抽出し、１，２，４，５−テトラエチニルベンゼン（Ｃ−９）を６ｇ得た。
【００３５】
（ヘキサエチニルベンゼン（Ｃ−１０）の合成）
窒素置換、及び真空が可能で、冷却管および撹拌装置付きの１Ｌのセパラブルフラスコに、ヘキサブロモベンゼン２９．２３ｇ（５３ｍｍｏｌ）、２−メチル−３−ブチニル−２‐オール２７．７６ｇ（３３０ｍｍｏｌ）、トリエチルアミン２２１ｍｌ（１．５８ｍｏｌ）、ピリジン１４６ｍｌ（１．８１ｍｏｌ）を入れ、窒素を流し攪拌した。その後、ジクロロビス（トリフェニルホスフィン）パラジウム（ＩＩ）１．１１ｇ（１．５９ｍｍｏｌ）、ヨウ化銅１．０１ｇ（５．２８ｍｍｏｌ）、トリフェニルホスフィン２．２２ｇ（８．４６ｍｍｏｌ）を素早入れ、攪拌した。その後、セパラブルフラスコを、オイルバスに入れ、８５℃に加温し、１２時間放置した。その後、ピリジン、トリエチルアミンを減圧蒸留し、イソプロパノールで抽出した。メタノールで再結晶し、ヘキサ（３−ヒドロキシ−３−メチル−１−ブチニル）ベンゼンを１１ｇ得た。
真空が可能で冷却管および撹拌装置付きの１Ｌのセパラブルフラスコに、ヘキサ（３−ヒドロキシ−３−メチル−１−ブチニル）ベンゼン１０ｇ、１，４−ジオキサン２００ｍｌ、水酸化カルウム（粒状）４．２ｇを入れ、１３０℃のオイルバスで１０時間加熱した。その後、冷却し、６ｍｏｌ／Ｌ塩酸２００ｍｌを敵下し、イソプロパノールで抽出しヘキサエチニルベンゼン（Ｃ−１０）を６ｇ得た。
【００３６】
（３，３’，５，５’−テトラエチニルビフェニル（Ｃ−１１）の合成）
窒素置換、及び真空が可能で、冷却管および撹拌装置付きの１Ｌのセパラブルフラスコに、３，３’，５，５’−テトラブロモビフェニル２４．９ｇ（５３ｍｍｏｌ）、２−メチル−３−ブチニル−２−オール２７．７６ｇ（３３０ｍｍｏｌ）トリエチルアミン２２１ｍｌ（１．５８ｍｏｌ）、ピリジン１４６ｍｌ（１．８１ｍｏｌ）を入れ、窒素を流し攪拌した。その後、ジクロロビス（トリフェニルホスフィン）パラジウム（ＩＩ）１．１１ｇ（１．５９ｍｍｏｌ）、ヨウ化銅１．０１ｇ（５．２８ｍｍｏｌ）、トリフェニルホスフィン２．２２ｇ（８．４６ｍｍｏｌ）を素早入れ、攪拌した。その後、セパラブルフラスコを、オイルバスに入れ、８５℃に加温し１２時間放置した。その後、ピリジン、トリエチルアミンを減圧蒸留し、イソプロパノールで抽出した。メタノールで再結晶し、３，３’，５，５’−テトラ（３−ヒドロキシ−３−メチル−１−ブチニル）ビフェニルを１１ｇ得た。
真空が可能で冷却管および撹拌装置付きの１Ｌのセパラブルフラスコに、３，３’，５，５’−テトラ（３−ヒドロキシ−３−メチル−１−ブチニル）ビフェニル１０ｇ、１，４−ジオキサン２００ｍｌ、水酸化カルウム（粒状）４．２ｇを入れ、１３０℃のオイルバスで１０時間加熱した。その後、冷却し、６ｍｏｌ／Ｌ塩酸２００ｍｌを敵下し、イソプロパノールで抽出し、３，３’、５，５’−テトラエチニルビフェニル（Ｃ−１１）を６ｇ得た。
【００３７】
（ペンタエチニルフェノール（Ｃ−１２）の合成）
窒素置換、及び真空が可能で、冷却管および撹拌装置付きの１Ｌのセパラブルフラスコに、ペンタブロモフェノール２５．９ｇ（５３ｍｍｏｌ）、２−メチル−３−ブチニル−２‐オール２２．７１ｇ（２７０ｍｍｏｌ）、トリエチルアミン２２１ｍｌ（１．５８ｍｏｌ）、ピリジン１４６ｍｌ（１．８１ｍｏｌ）を入れ、窒素を流し攪拌した。その後、ジクロロビス（トリフェニルホスフィン）パラジウム（ＩＩ）１．１１ｇ（１．５９ｍｍｏｌ）、ヨウ化銅１．０１ｇ（５．２８ｍｍｏｌ）、トリフェニルホスフィン２．２２ｇ（８．４６ｍｍｏｌ）を素早入れ、攪拌した。その後、セパラブルフラスコを、オイルバスに入れ、８５℃に加温し１２時間放置した。その後、ピリジン、トリエチルアミンを減圧蒸留し、イソプロパノールで抽出した。メタノールで再結晶し、ペンタ（３−ヒドロキシ−３−メチル−１−ブチニル） フェノールを１１ｇ得た。
真空が可能で冷却管および撹拌装置付きの１Ｌのセパラブルフラスコに、ペンタ（３−ヒドロキシ−３−メチル−１−ブチニル） フェノール１０ｇ、１，４−ジオキサン２００ｍｌ、水酸化カルウム（粒状）４．２ｇを入れ、１３０℃のオイルバスで１０時間加熱した。その後、冷却し、６ｍｏｌ／Ｌ塩酸２００ｍｌを敵下し、イソプロパノールで抽出し、ペンタエチニルフェノール（Ｃ−１２）を６ｇ得た。
【００３８】
次いで、上記で得たエチニル基を有する芳香族化合物（Ｃ）のそれぞれを用いて、半導体封止材料を作製し、各種特性を評価した。各特性の測定方法および試験方法は、下記の通りとした。
【００３９】
［評価方法］
（１）スパイラルフロー
ＥＭＭＩ−Ｉ−６６に準じたスパイラルフロー測定用の金型を用い、金型温度１７５℃、注入圧力６．８ＭＰａ、硬化時間２分で測定した。スパイラルフローは、流動性のパラメータであり、数値が大きい方が、流動性が良好である。
【００４０】
（２）硬化トルク
キュラストメーター（オリエンテック（株）製、ＪＳＲキュラストメーターＩＶＰＳ型）を用い、１７５℃、４５秒後のトルクを測定した。この値の大きい方が硬化性は良好である。
【００４１】
（３）耐半田クラック性
１００ピンＴＱＦＰ（Ｔｈｉｎ Ｑｕａｄ Ｆｌａｔ Ｐａｃｋａｇｅ）（パッケージサイズは１４×１４ｍｍ、厚み１．４ｍｍ、シリコンチップサイズは８．０×８．０ｍｍ、リードフレームは４２アロイ製）を、金型温度１７５℃、注入圧力７．４ＭＰａ、硬化時間２分の条件で、トランスファー成形機を用いて成形し、１７５℃、８時間で後硬化させた。得られた半導体パッケージを、８５℃、相対湿度８５％の環境下で、１６８時間放置し、その後、２６０℃の半田槽に１０秒間浸漬した。顕微鏡で外部クラックを観察し、クラック発生率［（クラック発生パッケージ数）／（全パッケージ数）×１００］を％で表示した。また、チップと樹脂組成物の硬化物との剥離面積の割合を、超音波探傷装置を用いて測定し、剥離率［（剥離面積）／（チップ面積）×１００］として、５個のパッケージの平均値を求め、％で表示した。クラック数、剥離率が少ないほど、耐半田クラック性は良好である。
【００４２】
（４）耐湿信頼性
金型温度１７５℃、注入圧力６．８ＭＰａ、硬化時間２分の条件で、トランスファー成形機を用いて、１６ｐＤＩＰ（Ｄｕａｌ Ｉｎｌｉｎｅ Ｐａｃｋａｇｅ）を成形し、この成形物を、１７５℃で８時間、後硬化した後、１２５℃、相対湿度１００％の水蒸気中で、２０Ｖの電圧を、１６ｐＤＩＰに印加し、断線不良を調べた。１５個のパッケージのうち、８個以上に不良が出るまでの時間を、不良時間とした。単位は時間。なお、測定時間は、最長で５００時間とし、その時点で不良パッケージ数が８個未満であったものは、不良時間を５００時間以上と示した。不良時間が長いほど、耐湿信頼性に優れる。
【００４３】
（５）ＵＬ９４難燃性
試験片（１２７ｍｍ×１２．７ｍｍ×厚み１．６ｍｍ）を、トランスファー成形機を用いて、金型温度１７５℃、注入圧力６．８６ＭＰａ、硬化時間１２０秒で成形し、１７５℃、８時間で後硬化し、ＵＬ−９４垂直法に準じて測定し、難燃性を判定した。
【００４４】
［半導体封止材料の調整］
（実施例１）
ビフェニルアラルキル型エポキシ樹脂（日本化薬（株）製ＮＣ−３０００Ｐ）を５７重量部、ビフェニ
ルアラルキル型フェノール樹脂（明和化成（株）製ＭＥＨ−７８５１ｓｓ）を４３重量部、上記で得た化
合物Ｃ１を１０重量部のほか、さらに溶融球状シリカ（平均粒径２０μｍ、最大粒径１００μｍ）を７３０重量部、カーボンブラックを２重量部、トリフェニルホスフィン１．５重量部、カルナバワックス２重量部を、まず、室温で混合し、ついで、熱ロールを用いて、１０５℃で８分間混練、冷却粉砕して半導体封止材料を得た。得られた半導体封止材料を、各特性の評価に供した。評価結果は表１に示した通りであった。
【００４５】
（実施例２〜１２、比較例１〜３）
各成分を、表１に従って、配合した以外は、実施例１と同様にして、半導体封止材料を調製し、各特性の評価をした。評価結果は表１に示した通りであった。
【００４６】
【表１】

【００４７】
表１に示した結果から分かるように、実施例１〜１２では、いずれも難燃性はＵＬ９４ Ｖ−０を示し、従来のものに比べて、難燃性だけでなく、良好な流動性、硬化性、耐湿信頼性、耐半田性を示した。
これに対して、比較例１は、難燃性、耐湿信頼性は問題ないものの、耐半田性が低下した。比較例２は、耐半田性、耐湿信頼性は問題ないものの、難燃性がＵＬ９４Ｖ−０未達であった。比較例３は、難燃性は問題ないもののフロー、硬化性、耐湿信頼性、耐半田性が十分でなかった。
【００４８】
【発明の効果】
本発明によれば、ハロゲン系化合物や金属水酸化物を添加することなく高度な難燃性、良好な硬化性、および流動性を有する難燃性エポキシ樹脂組成物が得られ、これを含む半導体封止材料により、耐湿信頼性はもちろん、耐半田クラック性にも優れる半導体装置を提供することができる。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a flame-retardant epoxy resin composition, a semiconductor sealing material using the same, and a semiconductor device.
[0002]
[Prior art]
As a method for obtaining a semiconductor device by encapsulating a semiconductor element such as an IC or an LSI, transfer molding of an epoxy resin composition is widely used because it is low in cost and suitable for mass production. Further, by improving epoxy resin and phenol resin as a curing agent, the characteristics and reliability of the semiconductor device are improved.
[0003]
On the other hand, flame retardancy of high polymer materials such as epoxy resin has become an important issue, and JIS standards, standards for automotive products, standards for electrical products, UL standards, etc., have been established, and semiconductor encapsulation has been established. Flame retardancy is also required for resin for use.
[0004]
The brominated epoxy resins that have been used to impart flame retardancy are inferior in stability, and are liable to generate bromine compounds such as hydrogen bromide by hydrolysis during moisture absorption or thermal decomposition during solder flow. However, in highly integrated semiconductor devices using an epoxy resin composition containing such a brominated epoxy resin, the moisture resistance reliability may be impaired.
[0005]
Heretofore, as a flame retardant instead of a halogen compound, a technique of decomposing by a dehydration action using a metal hydroxide such as aluminum hydroxide or magnesium hydroxide (for example, see Patent Documents 1 and 2) and carbon- A technology for flame retardation by adding a compound having a carbon triple bond (for example, see Patent Literature 3) has been studied. However, although flame retardancy can be exhibited, there is a drawback that solder crack resistance is significantly reduced.
[0006]
[Patent Document 1]
JP-A-2002-363251 (pages 3 to 10)
[Patent Document 2]
JP-A-11-269349 (pages 2 to 6)
[Patent Document 3]
JP-A-2002-363381 (pages 5 to 7)
[0007]
[Problems to be solved by the invention]
The present invention provides a particularly excellent flame retardancy to the epoxy resin composition, good curability, a flame-retardant epoxy resin composition capable of giving fluidity, and a semiconductor encapsulating material containing the same, and Another object of the present invention is to provide a semiconductor device which is excellent not only in moisture resistance reliability but also in solder crack resistance.
[0008]
[Means for Solving the Problems]
The present inventors have conducted intensive studies in view of the above problems, and as a result, have obtained an excellent flame retardant by using a biphenyl-type epoxy resin, a biphenyl-type phenol resin, and a compound containing at least one carbon-carbon triple bond. The present invention has led to the discovery of an epoxy resin composition exhibiting excellent curability and fluidity, and a semiconductor device having excellent solder crack resistance as well as moisture resistance reliability.
[0009]
That is, the present invention provides a biphenyl type epoxy resin (A) represented by the general formula (1), a biphenyl type phenol resin (B) represented by the general formula (2), and an aromatic compound having an ethynyl group (C A) as an essential component, a flame-retardant epoxy resin composition, and a semiconductor sealing material comprising the flame-retardant epoxy resin composition and a filler. This is a semiconductor device in which a semiconductor element is sealed with a cured product of a semiconductor sealing material.
[0010]
Embedded image

[Wherein, R ^{1 to} R ⁷ and R ⁸ each represent one selected from a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, and a phenyl group; May be. Here, a is an integer of 1 or more. ]
[0011]
Embedded image

[Wherein, R ^{9 to} R ¹⁵ and R ¹⁶ each represent one selected from a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, and a phenyl group. May be. Here, b is an integer of 1 or more. ]
Further, a and b in the general formula (1) and the general formula (2) are each preferably 1 to 10.
[0012]
The aromatic compound (C) having an ethynyl group includes p-ethynylphenol, m-ethynylphenol, o-ethynylphenol, 1,2-diethynylbenzene, 1,3-diethynylbenzene, 1,4-diethynyl Benzene, 1,3,5-triethynylbenzene, 1,2,4-triethynylbenzene, 1,2,4,5-tetraethynylbenzene, hexaethynylbenzene, pentaethynylphenol, or 3,3 ′, 5 5'-tetraethynylbiphenyl is preferred.
[0013]
BEST MODE FOR CARRYING OUT THE INVENTION
The flame-retardant epoxy resin composition of the present invention, and a semiconductor encapsulating material using the same, do not use a halogen-based compound such as a halogenated epoxy resin or a metal hydroxide, and a biphenyl-type epoxy resin having a specific structure. By adding a compound (C) containing at least one carbon-carbon triple bond to a biphenyl-type phenol resin having a specific structure, the epoxy resin composition is imparted with excellent flame retardancy, good curability, and fluidity. It has been found that the resulting semiconductor device has excellent solder crack resistance.
[0014]
The substituents R _{1 to} R ₈ of the biphenyl type epoxy resin represented by the general formula (1) used in the present invention represent one selected from a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and a halogen atom. , May be the same or different from each other.
Specific examples of these substituents R ^{1 to} R ⁸ include, for example, a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a phenyl group and the like. A bis (methoxymethyl) biphenyl phenol polycondensate type epoxy compound which is an atom or a methyl group is preferred.
[0015]
The substituents R ^{9 to} R ¹⁵ of the biphenyl-type phenol resin (B) represented by the general formula (2) used in the present invention are 1 selected from a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and a halogen atom. Represent species, which may be the same or different from each other.
Specific examples of these substituents R ^{9 to} R ¹⁵ include, for example, a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a phenyl group, and the like. Bis (methoxymethyl) biphenyl phenol polycondensates which are atoms or methyl groups are preferred.
[0016]
By using these resins, the fluidity during molding of the epoxy resin composition (for example, during the production of a semiconductor device, etc.) is improved, and the solder crack resistance and moisture resistance reliability of the obtained semiconductor device are further improved. I do.
[0017]
In the present invention, the mixing ratio of the biphenyl type epoxy resin (A) represented by the general formula (1) and the biphenyl type phenol resin (B) represented by the general formula (2) is determined by the epoxy equivalent of the epoxy resin (A). The ratio of the hydroxyl equivalent of the compound (B) to the compound (B) is preferably in the range of 0.5 to 2.0.
[0018]
Examples of the aromatic compound having an ethynyl group (C) used in the present invention include p-ethynylphenol, m-ethynylphenol, o-ethynylphenol, 1,2-diethynylbenzene, 1,3-diethynylbenzene, 4-diethynylbenzene, 1,3,5-triethynylbenzene, 1,2,4-triethynylbenzene, 1,2,4,5-tetraethynylbenzene, hexaethynylbenzene, pentaethynylphenol, and 3,3 ', 5,5'-tetraethynylbiphenyl and the like. These may be used alone or in combination.
[0019]
The amount of the aromatic compound (C) having an ethynyl group in the present invention is 1 to 50 parts by weight based on 100 parts by weight of the total of the biphenyl type epoxy resin (A) and the biphenyl type phenol resin (B). Preferably, it is more preferably in the range of 10 to 30 parts by weight. If it is less than the lower limit, the effect of flame retardancy may be reduced, while if it exceeds the upper limit, curability may be reduced.
[0020]
Examples of the filler used in the present invention include silica such as fused silica and crystalline silica, alumina, talc, calcium carbonate, clay, and mica. Of these, fused silica is preferred, and more preferred is spherical silica having a spherical particle shape and an average particle size of 1 to 100 μm.
[0021]
The compounding amount of the filler in the present invention is preferably 200 to 2400 parts by weight per 100 parts by weight of the total of the biphenyl type epoxy resin (A) and the biphenyl type phenol resin (B).
[0022]
Further, in the flame-retardant epoxy resin composition and the semiconductor encapsulating material of the present invention, in addition to the above components, if necessary, for example, a coupling agent such as γ-glycidoxypropyltrimethoxysilane, carbon Colorants such as black, low stress components such as silicone oil and silicone rubber, natural wax, synthetic wax, higher fatty acids or metal salts thereof, mold release agents such as paraffin, and various additives such as antioxidants may be added. it can.
[0023]
The flame-retardant epoxy resin composition of the present invention is obtained by mixing the above components (A), (B) and (C) with other various additives, if necessary, at room temperature using a mixer. The semiconductor encapsulating material is obtained by adding a filler thereto, mixing the mixture in the same manner as described above, further kneading the mixture using a kneader such as a hot roll and a heating kneader, heating and kneading, then cooling and pulverizing. Can be
[0024]
The semiconductor device of the present invention uses the semiconductor encapsulant obtained above as a molding resin, and cures and molds the semiconductor element by a molding method such as transfer molding, compression molding, or injection molding, thereby sealing the semiconductor element. And get.
The semiconductor device of the present invention thus obtained has particularly excellent solder crack resistance as well as moisture resistance reliability, the resin composition exhibits excellent flame retardancy, and has good curability and fluidity.
[0025]
The preferred embodiments of the flame-retardant epoxy resin composition and the semiconductor device of the present invention have been described above, but the present invention is not limited to these.
[0026]
【Example】
Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited thereto.
[0027]
[Synthesis example of aromatic compound (C) having ethynyl group]
The synthesis of compound (C) is described in Macromolecules (2002, Vol. 35, pp1180-1189) Polymer (1995, Vol36 No. 1 pp187-192), Chem. Rev (1999, Vol. 9, pp1747-1785). The synthesis examples are shown below, but are not necessarily limited to the methods, reaction temperatures and reaction times in the literature.
[0028]
(Synthesis of p-ethynylphenol)
In a 2 L separable flask equipped with a condenser and a stirrer capable of purging with nitrogen and vacuum, 20 g (90.8 mmol) of p-iodophenol, 18.36 g (218) of 2-methyl-3-butynyl-2-ol .4 mmol) and 600 ml of triethylamine, and nitrogen was flowed in, followed by stirring. Thereafter, 0.64 g (6.4 mmol) of dichlorobis (triphenylphosphine) palladium (II), 0.88 g (4.4 mmol) of copper iodide, and 1.68 g (6.4 mmol) of triphenylphosphine were rapidly added and stirred. . Then, it was put in an oil bath, heated to 70 ° C., and left for 12 hours. Thereafter, triethylamine was distilled under reduced pressure and extracted with isopropanol. Recrystallization from methanol gave 20 g of 4- (3-hydroxy-3-methyl-1-butynyl) phenol.
In a 1 L separable flask equipped with a condenser and a stirrer capable of applying vacuum, 10 g of 4- (3-hydroxy-3-methyl-1-butynyl) phenol, 200 ml of 1,4-dioxane, and calcium hydroxide (granular) 4 Then, the mixture was heated in a 130 ° C. oil bath for 10 hours. Thereafter, the mixture was cooled, and 200 ml of 6 mol / L hydrochloric acid was added thereto, and extracted with isopropanol to obtain 6 g of p-ethynylphenol (C-1).
[0029]
(Synthesis of m-ethynylphenol (C-2) and o-ethynylphenol (C-3))
6 g of C-2 and 6 g of C-3 were obtained in the same manner as when C-1 was obtained, except that m-iodophenol and o-iodophenol were used instead of p-iodophenol.
[0030]
(Synthesis of 1,2-ethynylbenzene (C-4))
12.5 g (53 mmol) of 1,2-dibromobenzene and 9.25 g of 2-methyl-3-butynyl-2-ol were placed in a 1 L separable flask equipped with a condenser tube and a stirrer, which can be replaced with nitrogen and vacuum. (110 mmol), 221 ml (1.1 mol) of triethylamine, and 146 ml (1.81 mol) of pyridine were added, and the mixture was stirred while flowing nitrogen. Thereafter, 1.11 g (1.59 mmol) of dichlorobis (triphenylphosphine) palladium (II), 1.01 g (5.28 mmol) of copper iodide, and 2.22 g (8.46 mmol) of triphenylphosphine were quickly added and stirred. . Thereafter, the separable flask was placed in an oil bath, heated to 85 ° C., and left for 12 hours. Thereafter, pyridine and triethylamine were distilled under reduced pressure and extracted with isopropanol. Recrystallization from methanol gave 15 g of 1,2-bis (3-hydroxy-3-methyl-1-butynyl) benzene.
In a 1 L separable flask equipped with a condenser and a stirrer capable of applying vacuum, 10 g of 1,2-bis (3-hydroxy-3-methyl-1-butynyl) benzene, 200 ml of 1,4-dioxane, and calcium hydroxide ( (Granular) (4.2 g) was added and heated in an oil bath at 130 ° C for 10 hours. Thereafter, the mixture was cooled, and 200 ml of 6 mol / L hydrochloric acid was added thereto, and extracted with isopropanol to obtain 6 g of 1,2-diethynylbenzene (C-4).
[0031]
(Synthesis of 1,3-ethynylbenzene (C-5) and 1,4-ethynylbenzene (C-6))
Except that 1,3-dibromobenzene and 1,4-dibromobenzene were used in place of 1,2-dibromobenzene, 6 g of C-5 and C- 6 g was obtained.
[0032]
(Synthesis of 1,3,5-trisethynylbenzene (C-7))
16.7 g (53 mmol) of 1,3,5-trisbromobenzene, 2-methyl-3-butynyl-2-ol were placed in a 1 L separable flask equipped with a condenser tube and a stirrer, capable of nitrogen replacement and vacuum. 13.87 g (165 mmol), 221 ml (1.58 mol) of triethylamine, and 146 ml (1.81 mol) of pyridine were added thereto, and the mixture was stirred while flowing nitrogen. Thereafter, 1.11 g (1.59 mmol) of dichlorobis (triphenylphosphine) palladium (II), 1.01 g (5.28 mmol) of copper iodide, and 2.22 g (8.46 mmol) of triphenylphosphine were quickly added and stirred. . Thereafter, the separable flask was placed in an oil bath, heated to 85 ° C., and left for 12 hours. Thereafter, pyridine and triethylamine were distilled under reduced pressure and extracted with isopropanol. Recrystallization from methanol gave 14 g of 1,2,3-tris (3-hydroxy-3-methyl-1-butynyl) benzene.
In a 1 L separable flask equipped with a condenser and a stirrer capable of applying a vacuum, 10 g of 1,2,3-tris (3-hydroxy-3-methyl-1-butynyl) benzene, 200 ml of 1,4-dioxane, and hydroxide 4.2 g of calcium (granular) was added and heated in an oil bath at 130 ° C. for 10 hours. Thereafter, the mixture was cooled, 200 ml of 6N hydrochloric acid was added thereto, and the mixture was extracted with isopropanol to obtain 6 g of 1,3,5-triethynylbenzene (C-7).
[0033]
(Synthesis of 1,2,4-trisethynylbenzene (C-8))
6 g of C-8 was obtained in the same manner as when C-7 was obtained, except that 1,2,4-trisbromobenzene was used instead of 1,3,5-trisbromobenzene.
[0034]
(Synthesis of 1,2,4,5-tetraethynylbenzene (C-9))
20.87 g (53 mmol) of 1,2,4,5-tetrabromobenzene, 2-methyl-3-butynyl-2-yl were placed in a 1 L separable flask equipped with a condenser tube and a stirrer capable of nitrogen replacement and vacuum. 18.51 g (220 mmol) of all, 221 ml (1.58 mol) of triethylamine, and 146 ml (1.81 mol) of pyridine were added, and nitrogen was flown thereinto, followed by stirring. Thereafter, 1.11 g (1.59 mmol) of dichlorobis (triphenylphosphine) palladium (II), 1.01 g (5.28 mmol) of iodide, and 2.22 g (8.46 mmol) of triphenylphosphine were quickly added and stirred. Thereafter, the separable flask was placed in an oil bath, heated to 85 ° C., and left for 12 hours. Thereafter, pyridine and triethylamine were distilled under reduced pressure and extracted with isopropanol. Recrystallization from methanol gave 14 g of 1,2,4,5-tetra (3-hydroxy-3-methyl-1-butynyl) benzene.
In a 1 L separable flask equipped with a condenser and a stirrer capable of applying a vacuum, 10 g of 1,2,4,5-tetra (3-hydroxy-3-methyl-1-butynyl) benzene, 200 ml of 1,4-dioxane, 4.2 g of calcium hydroxide (granular) was added and heated in an oil bath at 130 ° C. for 10 hours. Thereafter, the mixture was cooled, and 200 ml of 6 mol / L hydrochloric acid was added thereto, and extracted with isopropanol to obtain 6 g of 1,2,4,5-tetraethynylbenzene (C-9).
[0035]
(Synthesis of hexaethynylbenzene (C-10))
In a 1 L separable flask equipped with a condenser tube and a stirrer capable of purging with nitrogen and vacuum, 29.23 g (53 mmol) of hexabromobenzene, 27.76 g (330 mmol) of 2-methyl-3-butynyl-2-ol were added. , 221 ml (1.58 mol) of triethylamine and 146 ml (1.81 mol) of pyridine were added, and nitrogen was flown thereinto, followed by stirring. Thereafter, 1.11 g (1.59 mmol) of dichlorobis (triphenylphosphine) palladium (II), 1.01 g (5.28 mmol) of copper iodide, and 2.22 g (8.46 mmol) of triphenylphosphine were quickly added and stirred. . Thereafter, the separable flask was placed in an oil bath, heated to 85 ° C., and left for 12 hours. Thereafter, pyridine and triethylamine were distilled under reduced pressure and extracted with isopropanol. Recrystallization from methanol gave 11 g of hexa (3-hydroxy-3-methyl-1-butynyl) benzene.
3. In a 1 L separable flask equipped with a condenser and a stirrer capable of applying a vacuum, 10 g of hexa (3-hydroxy-3-methyl-1-butynyl) benzene, 200 ml of 1,4-dioxane, and calcium hydroxide (granular). 2 g was added and heated in an oil bath at 130 ° C. for 10 hours. Thereafter, the mixture was cooled, and 200 ml of 6 mol / L hydrochloric acid was added thereto, followed by extraction with isopropanol to obtain 6 g of hexaethynylbenzene (C-10).
[0036]
(Synthesis of 3,3 ′, 5,5′-tetraethynylbiphenyl (C-11))
In a 1 L separable flask equipped with a condenser and a stirrer capable of nitrogen substitution and vacuum, 24.9 g (53 mmol) of 3,3 ′, 5,5′-tetrabromobiphenyl, 2-methyl-3-butynyl 27.76 g (330 mmol) of -2-ol, 221 ml (1.58 mol) of triethylamine, and 146 ml (1.81 mol) of pyridine were added, and the mixture was stirred while flowing nitrogen. Thereafter, 1.11 g (1.59 mmol) of dichlorobis (triphenylphosphine) palladium (II), 1.01 g (5.28 mmol) of copper iodide, and 2.22 g (8.46 mmol) of triphenylphosphine were quickly added and stirred. . Thereafter, the separable flask was placed in an oil bath, heated to 85 ° C., and left for 12 hours. Thereafter, pyridine and triethylamine were distilled under reduced pressure and extracted with isopropanol. Recrystallization from methanol gave 11 g of 3,3 ', 5,5'-tetra (3-hydroxy-3-methyl-1-butynyl) biphenyl.
In a 1 L separable flask equipped with a condenser and a stirrer capable of applying a vacuum, 10 g of 3,3 ′, 5,5′-tetra (3-hydroxy-3-methyl-1-butynyl) biphenyl, 1,4-dioxane 200 ml and 4.2 g of calcium hydroxide (granular) were added and heated in a 130 ° C. oil bath for 10 hours. Thereafter, the mixture was cooled, and 200 ml of 6 mol / L hydrochloric acid was added thereto, and extracted with isopropanol to obtain 6 g of 3,3 ′, 5,5′-tetraethynylbiphenyl (C-11).
[0037]
(Synthesis of Pentaethynylphenol (C-12))
25.9 g (53 mmol) of pentabromophenol and 22.71 g (270 mmol) of 2-methyl-3-butynyl-2-ol were placed in a 1 L separable flask equipped with a condenser and a stirrer, which can be replaced with nitrogen and vacuum. , 221 ml (1.58 mol) of triethylamine and 146 ml (1.81 mol) of pyridine were added, and nitrogen was flown thereinto, followed by stirring. Thereafter, 1.11 g (1.59 mmol) of dichlorobis (triphenylphosphine) palladium (II), 1.01 g (5.28 mmol) of copper iodide, and 2.22 g (8.46 mmol) of triphenylphosphine were quickly added and stirred. . Thereafter, the separable flask was placed in an oil bath, heated to 85 ° C., and left for 12 hours. Thereafter, pyridine and triethylamine were distilled under reduced pressure and extracted with isopropanol. The crystals were recrystallized from methanol to obtain 11 g of penta (3-hydroxy-3-methyl-1-butynyl) phenol.
3. In a 1 L separable flask equipped with a condenser and a stirrer capable of applying vacuum, 10 g of penta (3-hydroxy-3-methyl-1-butynyl) phenol, 200 ml of 1,4-dioxane, and calcium hydroxide (granular). 2 g was added and heated in an oil bath at 130 ° C. for 10 hours. Thereafter, the mixture was cooled, dropped in 200 ml of 6 mol / L hydrochloric acid, and extracted with isopropanol to obtain 6 g of pentaethynylphenol (C-12).
[0038]
Next, a semiconductor encapsulating material was prepared using each of the ethynyl group-containing aromatic compounds (C) obtained above, and various characteristics were evaluated. The measuring method and test method of each characteristic were as follows.
[0039]
[Evaluation method]
(1) Spiral flow Using a mold for spiral flow measurement according to EMMI-I-66, the measurement was performed at a mold temperature of 175 ° C, an injection pressure of 6.8 MPa, and a curing time of 2 minutes. Spiral flow is a parameter of fluidity, and the larger the value, the better the fluidity.
[0040]
(2) Curing torque was measured at 175 ° C. for 45 seconds using a curing torque curast meter (manufactured by Orientec Co., Ltd., JSR curast meter IVPS type). The larger the value, the better the curability.
[0041]
(3) Solder crack resistance 100-pin thin quad flat package (TQFP) (package size: 14 × 14 mm, thickness: 1.4 mm, silicon chip size: 8.0 × 8.0 mm, lead frame: 42 alloy) Molding was performed using a transfer molding machine under the conditions of a mold temperature of 175 ° C., an injection pressure of 7.4 MPa, and a curing time of 2 minutes, and post-curing was performed at 175 ° C. for 8 hours. The obtained semiconductor package was left under an environment of 85 ° C. and a relative humidity of 85% for 168 hours, and then immersed in a solder bath at 260 ° C. for 10 seconds. External cracks were observed with a microscope, and the crack occurrence rate [(number of crack occurrence packages) / (total number of packages) × 100] was expressed in%. In addition, the ratio of the peeled area between the chip and the cured product of the resin composition was measured using an ultrasonic flaw detector, and the peeling rate was determined as [(peeled area) / (chip area) × 100]. The average was determined and expressed in%. The smaller the number of cracks and the rate of peeling, the better the solder crack resistance.
[0042]
(4) Moisture resistance reliability Under the conditions of a mold temperature of 175 ° C., an injection pressure of 6.8 MPa, and a curing time of 2 minutes, a transfer molding machine is used to mold 16 pDIP (Dual Inline Package). After curing for 8 hours at 20 ° C., a voltage of 20 V was applied to 16 pDIP in steam at 125 ° C. and 100% relative humidity, and the disconnection failure was examined. Out of the 15 packages, the time until a defect appeared in 8 or more packages was defined as a failure time. The unit is time. The measurement time was 500 hours at the longest, and when the number of defective packages was less than 8 at that time, the defective time was indicated as 500 hours or more. The longer the failure time, the better the moisture resistance reliability.
[0043]
(5) A UL94 flame-retardant test piece (127 mm x 12.7 mm x thickness 1.6 mm) was molded using a transfer molding machine at a mold temperature of 175 ° C, an injection pressure of 6.86 MPa, and a curing time of 120 seconds. Post-curing was performed at 175 ° C for 8 hours, and measured according to the UL-94 vertical method to determine the flame retardancy.
[0044]
[Adjustment of semiconductor sealing material]
(Example 1)
57 parts by weight of biphenyl aralkyl type epoxy resin (NC-3000P manufactured by Nippon Kayaku Co., Ltd.), 43 parts by weight of biphenyl aralkyl type phenol resin (MEH-7851ss manufactured by Meiwa Kasei Co., Ltd.), and compound C1 obtained above were used. In addition to 10 parts by weight, 730 parts by weight of fused spherical silica (average particle size: 20 μm, maximum particle size: 100 μm), 2 parts by weight of carbon black, 1.5 parts by weight of triphenylphosphine, and 2 parts by weight of carnauba wax were first added. Then, the mixture was mixed at room temperature, and then kneaded at 105 ° C. for 8 minutes using a hot roll and cooled and pulverized to obtain a semiconductor sealing material. The obtained semiconductor encapsulating material was subjected to evaluation of each property. The evaluation results were as shown in Table 1.
[0045]
(Examples 2 to 12, Comparative Examples 1 to 3)
A semiconductor encapsulating material was prepared in the same manner as in Example 1 except that each component was blended according to Table 1, and each characteristic was evaluated. The evaluation results were as shown in Table 1.
[0046]
[Table 1]

[0047]
As can be seen from the results shown in Table 1, in each of Examples 1 to 12, the flame retardancy shows UL94 V-0, and compared to the conventional one, not only the flame retardancy but also the good fluidity, It exhibited curability, moisture resistance reliability, and solder resistance.
On the other hand, in Comparative Example 1, although there was no problem in flame retardancy and humidity resistance reliability, solder resistance was reduced. In Comparative Example 2, although the solder resistance and the moisture resistance reliability were not problematic, the flame retardancy was not UL94V-0. In Comparative Example 3, although the flame retardancy was not a problem, the flow, curability, moisture resistance reliability, and solder resistance were not sufficient.
[0048]
【The invention's effect】
According to the present invention, a flame-retardant epoxy resin composition having high flame retardancy, good curability, and fluidity can be obtained without adding a halogen compound or a metal hydroxide, and a semiconductor containing the same. By using the sealing material, a semiconductor device which is excellent not only in moisture resistance reliability but also in solder crack resistance can be provided.

Claims (4)

A biphenyl type epoxy resin (A) represented by the following general formula (1), a biphenyl type phenol resin (B) represented by the following general formula (2), and an aromatic compound (C) having an ethynyl group, A flame-retardant epoxy resin composition characterized as being an essential component.

[Wherein, R ^{1 to} R ⁷ and R ⁸ each represent one selected from a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, and a phenyl group; May also be different. Here, a is an integer of 1 or more. ]

[Wherein, R ^{9 to} R ¹⁵ and R ¹⁶ each represent one selected from a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, and a phenyl group; May also be different. Here, b is an integer of 1 or more. ] When the aromatic compound (C) having an ethynyl group is p-ethynylphenol, m-ethynylphenol, o-ethynylphenol, 1,2-diethynylbenzene, 1,3-diethynylbenzene, 1,4-diethynylbenzene , 1,3,5-triethynylbenzene, 1,2,4-triethynylbenzene, 1,2,4,5-tetraethynylbenzene, hexaethynylbenzene, pentaethynylphenol, or 3,3 ', 5,5 The flame-retardant epoxy resin composition according to claim 1, which is' -tetraethynylbiphenyl. A semiconductor encapsulant comprising: the flame-retardant epoxy resin composition according to claim 1; and a filler. A semiconductor device in which a semiconductor element is sealed with a cured product of the semiconductor sealing material according to claim 4.