JP2004146620A - Film adhesive and semiconductor adhesive tape - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a heat-resistant film adhesive of high reliability which has good heat resistance, adhesiveness and wettability, and prevents substrates and chips from suffering from thermal damages at the time of assembling by lowering the adhesive temperature. <P>SOLUTION: The film adhesive consists of a combination of a thermoplastic polyimide resin and a thermosetting resin, and is used for an adhesive member for adhering a semiconductor chip and a lead frame in a process of assembling a semiconductor package. The peak top curing exothermic temperature of its adhesive components obtained by a differential scanning calorimeter is permitted to fall between 100°C to 200°C. As a result, the film adhesive enables adhesion at the temperature between 100°C to 200°C for such members that require low-temperature adhesion. With the provision of heat history such as heat treatment, the film adhesive that includes curing components turns out to be an optimum film adhesive for electronics materials or the like that require high reliability and heat resistance after adhesion. <P>COPYRIGHT: (C)2004,JPO

Description

【化６】

【化７】

（式中、Ｒ１，Ｒ２，Ｒ７，Ｒ８，Ｒ９，Ｒ１０，Ｒ１１，及びＲ１２は炭素数１〜４で二価の脂肪族基または芳香族基、Ｒ３，Ｒ４，Ｒ５，およびＲ６は一価の脂肪族基または芳香族基を表し、ｋは１〜１００の整数である。）
（４）硬化性化合物が、１分子中に少なくとも２個以上のエポキシ基を有するエポキシ化合物、及び１分子中に少なくとも２個以上のシアネート基を有するシアネート化合物の中から選ばれる少なくとも１つの化合物である（２）又は（３）記載のフィルム接着剤、
（５）硬化剤が、分子中に少なくとも１個のイミダゾール環を含む化合物、及びフェノールノボラック構造を有する化合物の中から選ばれる少なくとも１つの化合物である（２）〜（４）いずれか記載のフィルム状接着剤、
（６）（１）〜（５）いずれか記載のフィルム状接着剤の接着剤組成物成分、及び溶媒として一般式（５）で表されるフェニルエーテルを含有する溶液を支持体の片面または両面に流延塗布し、加熱乾燥させた後に、残存溶媒量が５００ｐｐｍ以下であることを特徴とする半導体接着テープ、
【化８】

（式中、Ｒ１３は水素原子または炭素原子数１〜６の１価の炭化水素基であり、Ｒ１４は炭素原子数１〜６の１価の炭化水素基を表す。）
（７）（６）記載の半導体接着テープが貼り付いてなることを特徴とするリードフレーム、
（８）（７）記載のリードフレームを用いてなる半導体装置、
である。
【００１３】
【発明の実施の形態】
本発明に用いる一般式（１）で表されるジアミノポリシロキサンとしては、１，３−ビス（３−アミノプロピル）テトラメチルシロキサンやα，ω−ビス（３−アミノプロピル）ポリジメチルシロキサン等が挙げられる。これらは一般式（４）で表されるフェニルエーテルに溶解するものが好ましい。
【００１４】
本発明に用いる芳香族もしくは脂肪族ジアミンとしては、３，３‘−ジメチル−４，４‘−ジアミノビフェニル、４，６−ジメチル−ｍ−フェニレンジアミン、２，５−ジメチル−ｐ−フェニレンジアミン、２，４−ジアミノメシチレン、４，４‘−メチレンジ−ｏ−トルイジン、４，４‘−メチレンジアミン−２，６−キシリジン、４，４‘−メチレン−２，６−ジエチルアニリン、２，４−トルエンジアミン、ｍ−フェニレンジアミン、ｐ−フェニレンジアミン、４，４‘−ジアミノジフェニルプロパン、３，３‘−ジアミノジフェニルプロパン、４，４‘−ジアミノジフェニルエタン、３，３‘−ジアミノジフェニルエタン、４，４‘−ジアミノジフェニルメタン、３，３‘−ジアミノジフェニルメタン、４，４‘−ジアミノジフェニルスルフィド、３，３‘−ジアミノジフェニルスルフィド、４，４‘−ジアミノジフェニルスルフォン、３，３‘−ジアミノジフェニルスルフォン、４，４‘−ジアミノジフェニルエ−テル、３，３‘−ジアミノジフェニルエ−テル、ベンジジン、３，３‘−ジアミノビフェニル、３，３‘−ジメチル−４，４‘−ジアミノビフェニル、３，３‘−ジメトキシベンジジン、ビス（ｐ−アミノシクロヘキシル）メタン、ビス（ｐ−β−アミノ−ｔ−ブチルフェニル）エ−テル、ビス（ｐ−β−メチル−δ−アミノペンチル）ベンゼン、ｐ−ビス（２−メチル−４−アミノペンチル）ベンゼン、１，５−ジアミノナフタレン、２，６−ジアミノナフタレン、２，４−ビス（β−アミノ−ｔ−ブチル）トルエン、２，４−ジアミノトルエン、ｍ−キシレン−２，５−ジアミン、ｐ−キシレン−２，５−ジアミン、ｍ−キシリレンジアミン、ｐ−キシリレンジアミン、２，６−ジアミノピリジン、２，５−ジアミノピリジン、２，５−ジアミノ−１，３，４−オキサジアゾ−ル、１，４−ジアミノシクロヘキサン、ピペラジン、メチレンジアミン、エチレンジアミン、テトラメチレンジアミン、ペンタメチレンジアミン、ヘキサメチレンジアミン、２，５−ジメチルヘキサメチレンジアミン、３−メトキシヘキサメチレンジアミン、ヘプタメチレンジアミン、２，５−ジメチルヘプタメチレンジアミン、３−メチルヘプタメチレンジアミン、４，４−ジメチルヘプタメチレンジアミン、オクタメチレンジアミン、ノナメチレンジアミン、５−メチルノナメチレンジアミン、デカメチレンジアミン、１，３−ビス（３−アミノフェノキシ）ベンゼン、２，２−ビス［４−（４−アミノフェノキシ）フェニル］プロパン、１，３−ビス（４−アミノフェノキシ）ベンゼン、ビス−４−（４−アミノフェノキシ）フェニルスルフォン、ビス−４−（３−アミノフェノキシ）フェニルスルフォンなどを挙げることができる。中でも、２，２−ビス［４−（４−アミノフェノキシ）フェニル］プロパン、１，３−ビス（３−アミノフェノキシ）ベンゼン、または２，５（２，６）−ビス（アミノメチル）ビシクロ［２．２．１］ヘプタン、３（４），８（９）−ビス（アミノメチル）−トリシクロ−５，２，１，０（２．６）デカン、３，９−ビス（３−アミノプロピル）−２，４，８，１０テトラオキサスピロ［５．５］ウンデカンなど分子中にノルボルネン環やスピロアセタール環などの脂環構造を含むジアミンが、フェニルエーテルへの溶解性に関して好ましい。上記のジアミンは、単独で用いても良く、２種類以上を組み合わせて用いても良い。
【００１５】
上記ジアミノポリシロキサンと芳香族もしくは脂肪族ジアミンとの反応比率は、ポリイミド樹脂のガラス転移点が９０℃〜２００℃の範囲にある限りは特に規定しないが、ジアミノポリシロキサンの反応比率がジアミノポリシロキサンと芳香族もしくは脂肪族ジアミンの総モル数に対し、好ましくは５〜９５モル％である。５モル％未満であると、得られるポリイミド樹脂のフェニルエーテルへの溶解性が低下し、作業上問題が生じる可能性がある。９５モル％を超えるとフィルムのガラス転移温度が著しく低下し、フィルムとしての強度が保てない可能性がある。
【００１６】
本発明に用いる芳香族テトラカルボン酸二無水物としては、３，３’，４，４’−ビフェニルテトラカルボン酸二無水物、３，３’，４，４’−ベンゾフェノンテトラカルボン酸二無水物、ピロメリット酸二無水物、４，４’−オキシジフタル酸二無水物、エチレングリコールビストリメリット酸二無水物、４，４‘−（４，４’−イソプロピデンジフェノキシ）フタル酸二無水物などが挙げられる。中でも、４，４’−オキシジフタル酸二無水物、４，４‘−（４，４’−イソプロピデンジフェノキシ）フタル酸二無水物が、得られるポリイミド樹脂のフェニルエーテルへの溶解性に関して好ましい。上記の芳香族テトラカルボン酸二無水物は、単独で用いても良く、２種類以上を組み合わせて用いても良い。
【００１７】
上記ジアミノシロキサン、ジアミン化合物、芳香族テトラカルボン酸無水物を反応させてなるポリイミド樹脂はガラス転移温度が９０℃から２００℃の範囲にあることが必要である。９０℃未満ではポリイミド樹脂自体の耐熱性が低下し、ワイヤーボンディングが行なわれる温度域（１８０〜２３０℃）における弾性率が低く、ワイヤーボンディング時にテープと被着体との間で剥離が生じる恐れがある。逆に２００℃を越える場合ポリイミド樹脂のフェニルエーテルへの溶解性が低くなり、フェニルエーテル溶液の状態でポリイミド樹脂が析出する恐れがある。
【００１８】
本発明の耐熱性接着剤に用いられるポリイミド樹脂組成物の重縮合反応における酸成分とアミン成分の当量比は、得られるポリイミド樹脂の分子量を決定する重要な因子である。また、ポリマーの分子量と物性、特に数平均分子量と機械的性質の間に相関があることは良く知られている。数平均分子量が大きいほど機械的性質が優れている。従って、実用的に優れた強度を得るためには、ある程度高分子量であることが必要である。
【００１９】
本発明に用いるポリイミド樹脂の製造では、酸成分とアミン成分の当量比ｒが
０．９００　≦　ｒ　≦　１．０６
さらには、
０．９７５　≦　ｒ　≦　１．０２５
の範囲にあることが、機械的強度および耐熱性の両面から好ましい。ただし、ｒ＝［全酸成分の当量数］／［全アミン成分の当量数］である。ｒが０．９００未満では、分子量が低くてフィルムとした場合脆くなる。また１．０６を越えると、未反応のカルボン酸が加熱時に脱炭酸して、ガス発生や発泡の原因となり好ましくないことがある。ポリイミド樹脂の分子量制御のために、ジカルボン酸無水物あるいはモノアミンを添加することは、上述の酸／アミンモル比ｒの範囲内であれば、特にこれを妨げない。
【００２０】
本発明に用いる反応溶媒は、Ｎ−メチル−２−ピロリドン又は式（５）で表されるフェニルエーテルである事が好ましい。
【００２１】
ここで、式（５）で表されるフェニルエーテルの代表的なものとして、アニソール、フェネトール、メトキシトルエン等が挙げられるが、より低温の熱処理でポリイミド樹脂フィルムが得られることから、アニソールが最も好ましい。
【００２２】
この時、共沸用溶媒として上記のフェニルエーテルと相溶性のある非極性溶媒を混合して使用しても良い。前記非極性溶媒としては、トルエン、キシレン、ソルベントナフサなどの芳香族炭化水素が好ましい。混合溶媒における非極性溶媒の割合は、５０重量％以下であることが好ましい。これは非極性溶媒が５０重量％を越える場合は、溶媒の溶解力が低下し、原料であるジアミノポリシロキサンと芳香族もしくは脂肪族ジアミン、脂環式ジアミン又はポリイミド樹脂が析出する恐れがあるためである。
【００２３】
上述した成分、配合比によりポリイミド樹脂を合成する場合、上記成分のジアミノポリシロキサンと芳香族もしくは脂肪族ジアミンとを、フェニルエーテルを主とする反応溶媒中に仕込み、７０〜８０℃程度に加熱し、ジアミノポリシロキサンと芳香族もしくは脂肪族ジアミンを溶解させる（Ａ液）。さらに、別の反応器に上記成分のテトラカルボン酸二無水物を、フェニルエーテルを主とする溶媒中に仕込み、還流が起きるまで加熱昇温を行う（Ｂ液）。引き続き、前記Ａ液を、還流中のＢ液内に添加して、ポリアミド化と脱水閉環反応を短時間で進行させ、一般式（６）で表される繰り返し単位と一般式（７）で表される繰り返し単位とを有するポリイミド樹脂の溶液が得られる。イミド化反応によって生じた水は閉環反応を妨害するため、ディーン・スターク（Ｄｅａｎ−Ｓｔａｒｋ）管などの装置を使用して系外に排出する。
【００２４】
【化９】

【化１０】

（式中、Ｒ１，Ｒ２，Ｒ１７は炭素数１〜４で二価の脂肪族基または芳香族基、Ｒ３，Ｒ４，Ｒ５，およびＲ６は一価の脂肪族基または芳香族基、Ｒ１５，Ｒ１６は四価の脂肪族基または芳香族基を表し、ｋは１〜１００の整数である。ｍ、ｎの割合は各成分合計１００モル％中、ｍが５〜９５モル％、ｎが５〜９５モル％である。）
【００２５】
本発明に用いる硬化性化合物は、１分子中に少なくとも２個以上のエポキシ基を有するエポキシ化合物、及び１分子中に少なくとも２個以上のシアネート基を有するシアネート化合物の中から選ばれる少なくとも１つの化合物である事が好ましい。
本発明に用いるエポキシ化合物（Ｄ）は、少なくとも１分子中に２個のエポキシ基を有し、ポリイミド樹脂（Ｃ）との相溶性を有するものであれば、特に限定されるものではないが、ポリイミド樹脂（Ｃ）を合成する際に使用する溶媒への溶解性が良好なものが好ましい。例として、ビスフェノールＡ型のジグリシジルエーテル、ビスフェノールＦ型のジグリシジルエーテル、ビスフェノールＡ−エピクロルヒドリン型エポキシ化合物、ジフェニルエーテル型エポキシ化合物、フェノールノボラック型エポキシ化合物、クレゾールネボラック型エポキシ化合物、ビフェニル型エポキシ化合物、水添ビスフェノールＡ型エポキシ化合物等が挙げられる。
【００２６】
本発明に用いるシアネート化合物（Ｅ）は少なくとも１分子中に２個のシアネート基を有し、ポリイミド樹脂との相溶性を有するものであれば特に限定されるものではない。例として、ビスフェノール−Ａ−ジシアネート４，４‘−イソプロピリデンジフェニルシアネート、４，４’−エチリデンジフェニルジシアネート、４，４‘−メチレンビス（２，６−ジメチルフェニルシアネート）、オリゴ（３−メチレン−１，５−フェニレンシアネート）などが挙げられる。
【００２７】
また、本発明のポリイミド樹脂組成物におけるエポキシ化合物（Ｄ）とシアネート化合物（Ｅ）の総含有量は、ポリイミド樹脂（Ｃ）１００重量部に対して０．０１〜２００重量部が好ましい。含有量が０．０１未満であると、高温時のフィルム強度が低下し、接着力が低下する。含有量が２００重量部を超えるとエポキシ化合物やシアネート化合物の樹脂特性の影響を受け、ポリイミド樹脂の特性である耐熱性や機械強度が損なわれる。
【００２８】
本発明に用いられる硬化剤（Ｆ）はエポキシ化合物（Ｄ）またはシアネート化合物（Ｅ）などの硬化性化合物と反応し、ＤＳＣ測定（試料重量１０ｍｇ，昇温速度１０℃／分）において１００℃から２００℃の間に硬化発熱反応ピークトップが存在するようなものでなければならない。従来硬化性樹脂はその硬化反応時に溶融粘度が極小値を有するもので、この温度間にピークトップが存在することで加熱貼り付け時の基材への濡れ性が確保できる。ピークトップ温度が１００℃未満だと接着剤の保存性を著しく低下させ、２００℃を超えると１００℃〜２００℃の低温加熱貼り付け時に未硬化物の存在による樹脂成分からの分解や過流動による発泡が生じる。またポリイミド樹脂（Ｃ）やエポキシ化合物（Ｄ）との相溶性や、ポリイミド樹脂（Ｃ）を合成する際に使用する溶媒への溶解性が良好なものが好ましい。例として１−ベンジル−２−メチルイミダゾール、１−ベンジル−２−フェニルイミダゾール、１−シアノエチル−２−エチル−４−メチルイミダゾール、２−フェニル−４−メチルイミダゾールなどのイミダゾール化合物などが挙げられる。
【００２９】
本発明のポリイミド樹脂組成物における硬化剤（Ｆ）の含有量は、エポキシ化合物（Ｄ）、及びシアネート化合物（Ｅ）の硬化性化合物の合計１００重量部に対して０．０１〜５０重量部以下が好ましい。０．０１未満であると、十分な硬化特性が得られない。５０重量部を越えると硬化時に未反応の硬化剤が残存し、フィルム状接着剤にした際、熱圧着した時に未反応成分が溶出し、信頼性に悪影響を及ぼすこととなる。
【００３０】
本発明に用いるシランカップリング剤（Ｇ）は、ポリイミド樹脂（Ｃ）やエポキシ化合物（Ｄ）、シアネート化合物（Ｅ）、硬化剤（Ｆ）との相溶性や、ポリイミド樹脂（Ｃ）を合成する際に使用する溶媒への溶解性が良好なものが好ましい。例として、ビニルトリクロルシラン、ビニルトリエトキシシラン、γ−メタクリロキシプロピルトリメトキシシラン、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、Ｎ−β（アミノエチル）γ−アミノプロピルトリメトキシシラン、Ｎ−β（アミノエチル）γ−アミノプロピルメチルジメトキシシラン、γ−アミノプロピルトリエトキシシラン、Ｎ−フェニル−γ−アミノプロピルトリメトキシシラン等が挙げられ、Ｎ−フェニル−γ−アミノプロピルトリメトキシシランが接着性の面で好ましい。
【００３１】
本発明のポリイミド樹脂組成物におけるシランカップリング剤（Ｇ）の含有量は、ポリイミド樹脂（Ｃ）１００重量部に対して０．０１〜５０重量部が好ましい。０．０１未満であると、十分な接着特性が得られない。５０重量部を越えると、ポリイミド樹脂同士の架橋が起きやすくなり、ポリイミド樹脂組成物溶液を調製した際、溶液がゲル化しやすく、またフィルム状接着剤にした際、熱圧着した時、被着体に対する濡れ性が低下し、接着力が低下する。
【００３２】
本発明のポリイミド樹脂組成物は、ポリイミド樹脂（Ｃ）にエポキシ化合物（Ｄ）、シアネート化合物（Ｅ）、硬化剤（Ｆ）及びシランカップリング剤（Ｇ）を添加し混合することにより得られる。本発明のポリイミド樹脂組成物には、上記成分の他に、表面平滑性を出すための平滑剤、レベリング剤、脱泡剤などの各種添加剤を必要に応じて添加することができる。また、ポリイミド樹脂溶液中の溶剤の蒸発速度を調節するために、均一に溶解する範囲で芳香族炭化水素系溶剤を使用することができる。
【００３３】
本発明においてポリイミド樹脂組成物は、接着剤として用いられ、これを用いて、フィルム状接着剤とするには、上記で得られたポリイミド樹脂溶液を、例えば、ロールや金属シート、又は、ポリエステルシートなどの離型シートの上に、フローコーター、ロールコーターなどにより、流延あるいは塗布して、樹脂層からなるフィルムを形成させ、加熱乾燥後、剥離してポリイミド樹脂フィルムとすることができる。この際の加熱処理は、通常５０〜１５０℃、より好ましくは５０〜１２０℃で行われ、エポキシ樹脂等、硬化成分が架橋することなくフィルム状接着剤を製造することが可能である。熱処理時間については、通常０．１〜１時間程度で良く、低温短時間で完全に溶剤を除去することが可能であり、フィルム状接着剤を熱圧着した際、残存溶剤による発泡を抑制することができる。残存溶媒の量としては５００ｐｐｍ以下であることが好ましい。
【００３４】
上記の方法で得られたフィルム接着剤は、未処理の状態でガラス転移点が４０℃から１５０℃、より好ましくは５０から１００℃の範囲にあることが好ましい。これは、リードフレームへの貼付およびダイマウントに要する貼付温度を２５０℃以下にするために必要な、接着剤の濡れ性を確保する為である。
【００３５】
上記の方法で得られたフィルム接着剤をリードフレームおよび半導体素子に接着させた後、熱処理することで耐熱性に優れたフィルムを得ることができるが、その熱処理条件は１００〜２００℃で５秒から１時間であることが好ましく、より好ましくは１００〜１５０℃で５秒から３０分である。これは、２００℃を越える熱処理温度はリードフレームおよび半導体素子への熱損傷を深刻にし、１００℃未満の熱処理温度では封止する際に未硬化成分の残存成分が揮発成分となって、リードフレームへや半導体素子の汚染の原因となる恐れがある。１時間を越える熱処理時間は生産性の低下を引き起こし、５秒未満の熱処理時間では低温熱処理の場合と同様、未硬化成分の残存成分が揮発成分となって、リードフレームへや半導体素子の汚染の原因となる恐れがある。
【００３６】
本発明で得られるフィルム接着剤は吸水率が３重量％以下であることが好ましい。これはフィルム接着剤を用いて半導体装置を組み立てる場合、フィルム接着剤の吸水性が半導体装置の信頼性に影響を及ぼす場合があるためである。
【００３７】
本発明のフィルム接着剤は、低温度短時間の熱処理で硬化したフィルムの２１０℃における弾性率が１０から１００ＭＰａ、好ましくは３０から１００ＭＰａの範囲にあることが好ましい。この弾性率の範囲にあれば、ワイヤーボンディングを問題無く行なうことができる。
【００３８】
また本発明のフィルム接着剤を半導体装置の組立に用いたとき、低吸水性・高温時の接着性に優れていることから高信頼性の半導体装置を提供することが可能となる。
【００３９】
【実施例】
以下、実施例により本発明を更に詳細に説明するが、本発明は、何らこれらに限定されるものではない。
なお、実施例における略号は以下の通りである。
ＰＩ：ポリイミド
ＢＰＤＡ：３，３’，４，４’−ビフェニルテトラカルボン酸二無水物
ＢＰＡＤＡ：ビスフェノールＡ酸無水物
ＯＤＰＡ：４，４‘−オキシジフタル酸二無水物
ＢＡＰＰ：２，２−ビス［４−（４−アミノフェノキシ）フェニル］プロパン
ＡＰＢ：　１，３−ビス（３−アミノフェノキシ）ベンゼン
ＴＣＤＤ：３（４），８（９）−ビス（アミノメチル）−トリシクロ−５，２，１，０（２．６）デカン
ＮＢＤＡ：２，５（２，６）−ビス（アミノメチル）ビシクロ［２．２．１］ヘプタン
ＡＴＵ：３，９−ビス（３−アミノプロピル）−２，４，８，１０テトラオキサスピロ［５．５］ウンデカン
ＡＰＰＳ−１：α，ω−ビス（３−アミノプロピル）ポリジメチルシロキサン（平均分子量２４９）（式（１）においてｋ＝１）
ＡＰＰＳ−９：α，ω−ビス（３−アミノプロピル）ポリジメチルシロキサン（平均分子量８３７）（式（１）においてｋ＝９）
ＮＭＰ：Ｎ−メチル−２−ピロリドン
ＫＢＭ５７３：アミノシランカップリング剤（信越化学工業（株）製、商品名ＫＢＭ−５７３
）
Ｅｐ−１：クレゾールノボラック型エポキシ樹脂（日本化薬（株）製、商品名ＥＯＣＮ−１０２０−８０、エポキシ当量２００）
Ｅｐ−２：ビフェニル型エポキシ樹脂（油化シェル（株）製、商品名ＹＸ−４０００ＨＫ、エポキシ当量１９５）
Ｃｙｎ−１：ビスフェノールＡ型ジイソシアネート樹脂（ロンザ（株）製、商品名ＡｒｏｃｙＬ１０）
Ｃｕ−１：１−ベンジル−２−メチルイミダゾール（四国化成（株）製、商品名１Ｂ２ＭＺ）
Ｃｕ−２：１−（２−シアノエチル）−２−エチル−４−メチルイミダゾール（四国化成（株）製、商品名２Ｅ４ＭＺ−ＣＮ）
Ｓｉ−１：アミノシランカップリング剤（信越化学工業（株）製、商品名ＫＢＭ−５７３）
Ｓｉ−２：エポキシシランカップリング剤（信越化学工業（株）製、商品名ＫＢＭ４０３Ｅ）
【００４０】
（ＰＩ−１の合成）
三角フラスコに、アニソール２６．０ｇを入れ、さらに２，２−ビス［４−（４−アミノフェノキシ）フェニル］プロパン８６．２ｇ（０．２１モル）、２，５（２，６）−ビス（アミノメチル）ビシクロ［２．２．１］ヘプタン４．６３ｇ（０．０３モル）とα，ω−ビス（３−アミノプロピル）ポリジメチルシロキサン（平均分子量８３７）（式（１）においてｋ＝９）５０．２２ｇ（０．０６モル）を投入し、７０℃に加熱し、溶解するまで撹拌を行った（Ａ液）。
【００４１】
次に、乾燥窒素ガス導入管、冷却器、温度計、滴下ロート、攪拌機を備えた三口フラスコに、アニソール５２４．２ｇ、トルエン１３７．０ｇを入れ、窒素ガスを流した。次に、酸成分である３，３’，４，４’−ビフェニルテトラカルボン酸二無水物８８．３ｇ（０．３モル）を投入し、トルエンを満たしたディーン・スターク管をフラスコに装着し、油浴にて系を還流が発生するまで加熱した。次に、前記Ａ液を滴下ロートに投入し、フラスコ内に１時間かけて滴下した。その間に発生する水は、ディーン・スターク管を用いて系外に除いた。３時間加熱した後、冷却し、目的とするポリイミド樹脂の溶液を得た。得られたポリイミド樹脂は、東ソー株式会社製ＧＰＣ測定装置を用いて、ポリスチレン換算で測定のところ、Ｍｗ＝３８２００であった。
【００４２】
（ＰＩ−２の合成）
乾燥窒素ガス導入管、冷却器、温度計、攪拌機を備えた三口フラスコに、アニソール５９２．８ｇ、トルエン１４８．１９ｇを入れ、窒素ガスを流した。次に、アミン成分である２，２−ビス［４−（４−アミノフェノキシ）フェニル］プロパン９０．３１ｇ（０．２２モル）とα，ω−ビス（３−アミノプロピル）ポリジメチルシロキサン（平均分子量８３７）（式（１）においてｋ＝９）１３．６７ｇ（０．０５５モル）、そして酸成分であるビスフェノールＡ酸無水物１４３．００ｇ（０．２７５モル）を投入し、トルエンを満たしたディーン・スターク管をフラスコに装着し、油浴にて系を還流が発生するまで加熱した。その間に発生する水は、ディーン・スターク管を用いて系外に除いた。１時間加熱した後、冷却し、目的とするポリイミド樹脂の溶液を得た。得られたポリイミド樹脂は、東ソー株式会社製ＧＰＣ測定装置を用いて、ポリスチレン換算で測定のところ、Ｍｗ＝３８０００であった。
【００４３】
（ＰＩ−３の合成）
三角フラスコに、アニソール４６５．２５ｇを入れ、さらに２，２−ビス［４−（４−アミノフェノキシ）フェニル］プロパン８２．１ｇ（０．２０モル）、３（４），８（９）−ビス（アミノメチル）−トリシクロ−５，２，１，０（２．６）デカン１５．５４ｇ（０．０８モル）、α，ω−ビス（３−アミノプロピル）ポリジメチルシロキサン（平均分子量２４９）（式（１）においてｋ＝１）６．１７ｇ（０．０４モル）、２，５（２，６）−ビス（アミノメチル）ビシクロ［２．２．１］ヘプタン１０．９６ｇ（０．０４モル）、３，９−ビス（３−アミノプロピル）−２，４，８，１０テトラオキサスピロ［５．５］ウンデカン９．９４ｇ（０．０４モル）を投入し、７０℃に加熱し、溶解するまで撹拌を行った（Ａ液）。
【００４４】
次に、乾燥窒素ガス導入管、冷却器、温度計、滴下ロート、攪拌機を備えた三口フラスコにアニソール１３１．８８ｇ、トルエン１４９．２８ｇを入れ、窒素ガスを流した。次に、酸成分である４，４’−オキシジフタル酸二無水物１２４．１ｇ（０．４モル）を投入し、トルエンを満たしたディーン・スターク管をフラスコに装着し、油浴にて系を還流が発生するまで加熱した。次に、前記Ａ液を滴下ロートに投入し、フラスコ内に１時間かけて滴下した。その間に発生する水は、ディーン・スターク管を用いて系外に除いた。３時間加熱した後、冷却し、目的とするポリイミド樹脂の溶液を得た。得られたポリイミド樹脂は、東ソー株式会社製ＧＰＣ測定装置を用いて、ポリスチレン換算で測定のところ、Ｍｗ＝５２０００であった。
【００４５】
（ＰＩ−４の合成）
三角フラスコに、アニソール４３８．５０ｇを入れ、さらに１，３−ビス（３−アミノフェノキシ）ベンゼン４３．８５ｇ（０．１５モル）とα，ω−ビス（３−アミノプロピル）ポリジメチルシロキサン（平均分子量８３７）（式（１）においてｋ＝９）１２５．５５ｇ（０．１５モル）を投入し、７０℃に加熱し、溶解するまで撹拌を行った（Ａ液）。
【００４６】
次に、乾燥窒素ガス導入管、冷却器、温度計、滴下ロート、攪拌機を備えた三口フラスコに、アニソール３４８．９０ｇを入れ、窒素ガスを流した。次に、酸成分である４，４’−オキシジフタル酸二無水物９３．０７ｇ（０．３０モル）を投入し、ディーン・スターク管をフラスコに装着し、油浴にて系を還流が発生するまで加熱した。次に、前記Ａ液を滴下ロートに投入し、フラスコ内に１時間かけて滴下した。その間に発生する水は、ディーン・スターク管を用いて系外に除いた。３時間加熱した後、冷却し、目的とするポリイミド樹脂の溶液を得た。得られたポリイミド樹脂は、東ソー株式会社製ＧＰＣ測定装置を用いて、ポリスチレン換算で測定のところ、Ｍｗ＝５５４００であった。
【００４７】
（ＰＩ−５の合成）
乾燥窒素ガス導入管、冷却器、温度計、攪拌機を備えた三口フラスコにＮＭＰ５９４．６３ｇを入れ、窒素ガスを流した。次にアミン成分である３，９−ビス（３−アミノプロピル）−２，４，８，１０テトラオキサスピロ［５．５］ウンデカン２９．１５ｇ（０．１５モル）とＡＰＰＳ−９　１２５．６ｇ（０．１５０モル）を投入し、均一になるまで撹拌した。均一に溶解後、系を氷水浴で２０℃に保ちながら、酸成分であるＯＤＰＡ　９３．０７ｇ（０．３０モル）を粉末状のまま１０分間かけて添加し、その後２時間撹拌を続けポリアミド酸溶液を得た。この間フラスコは２０℃を保った。
その後、窒素ガス導入管と冷却器を外し、トルエンを満たしたディーン・スターク管をフラスコに装着し、系にトルエン　１４８．７０ｇを添加した。氷水浴から油浴に替えて系を加熱し発生する水を系外に除いた。３時間加熱した後冷却し、ポリイミド溶液ＰＩ−５を得た。
【００４８】
上記で得たポリイミドＰＩ−１〜５の配合表を表１に示す。表中の配合数値はモル比を表わす。これらポリイミド溶液をシリコン離型処理二軸延伸ポリエステルフィルムにロールコーターで、厚みが２５μｍになるように塗布し、８０℃で２分、１３０℃で２分、１８０℃で２分乾燥を行い、ポリイミド樹脂フィルムを得た。このフィルムのガラス転移点を熱機械分析装置（ＴＭＡ，セイコーインスツルメンツ社製，ＳＳ−６０００）を用いて測定した結果を併せて表１に示す。
【００４９】
【表１】

【００５０】
実施例１〜６及び比較例１〜４
上記で得たポリイミド溶液と各成分について表２に示す配合により混合して、実施例１〜６、及び比較例１〜４の接着剤溶液を調合した。表中の配合の数値は重量部を表わす。
【００５１】
次に、得られたフィルムを表２に示した乾燥条件で乾燥し、フィルム状接着剤を得た。フィルム状接着剤のガラス転移点、ＤＳＣピーク温度、及び残存溶媒量を測定した結果を表２に示す。フィルム状接着剤を更に表２に示した熱処理条件で硬化させ、硬化したフィルムのガラス転移点、弾性率、吸水率、及び接着強度の測定を行った結果を表２に示す。
【００５２】
硬化発熱ピークトップ測定方法：
サンプル１０ｍｇをアルミパン内に入れて、示差走査熱量計（ＤＳＣ，セイコーインスツルメンツ社製，ＤＳＣ６２００）を用いて昇温速度１０℃／分の条件で測定を行なった。得られたＤＳＣカーブのピークトップを読み取り，硬化発熱ピークトップ温度とした。
【００５３】
ガラス転移点測定方法：
サンプルを厚み２５μｍ，幅３ｍｍの矩形に切り出し，熱機械分析装置（ＴＭＡ，セイコーインスツルメンツ社製，ＳＳ−６０００）を用いて昇温速度５℃／分，荷重２５ｍＮの条件で測定を行なった。ＴＭＡ曲線の外挿点をガラス転移点とした。
【００５４】
弾性率測定方法：
断面積の既知な幅１ｃｍのフィルムサンプルを，動的粘弾性測定装置（ＤＭＳ，セイコーインスツルメンツ社製，ＤＭＳ２１０）を用いて，周波数１０Ｈｚ，昇温速度３℃／分で測定を行なった。得られた貯蔵弾性率Ｅ′の値を弾性率とする。
【００５５】
吸水率測定方法：
厚み２５μｍ，５ｃｍ×５ｃｍの正方形に切り出したフィルムを５０℃乾燥機中にて２４時間乾燥し，このときの重量をｗとする。次いで２５℃の純水中に２４時間フィルムを浸漬し，取り出し後重量を測定してその重量をＷとする。フィルムの吸水率は次の式で表される。
吸水率（％）＝（Ｗ−ｗ）／ｗ×１００
【００５６】
残存溶媒量測定方法：
試料約５０ｍｇをパージ＆トラップの試料管に入れ、流速５０ｍＬ／分のヘリウムガスで揮発分を追い出しながら、２５０℃×１５分の加熱条件で試料を加熱する。この時発生した揮発分を−８０℃でトラップし、試料加熱終了後トラップした成分を急速加熱してＧＣ／ＭＳ計に導入する。各発生ガス成分の定量については、既知濃度のｎ−デカンのトルエン希釈溶液を用いて、試料と同じ加熱条件にてパージ＆トラップ−ＧＣ／ＭＳ法測定を行い、各発生ガス成分のピーク面積値を比較することによって各標準試料に対する換算定量値を、試料重量に対する重量分率として算出する。
【００５７】
接着強度測定方法：
接着フィルムサンプルを４２アロイのプレートに熱圧着して試験片を作成し、圧力を開放後３００℃で３０秒間アニ−ルした。接着面にかかる圧力はゲージ圧力と接着面積から計算の結果４ｋｇｆ／ｃｍ^２であった。この試験片について１８０℃ピール強度の測定を行なった。
【００５８】
【表２】

【００５９】
【発明の効果】
本発明によれば、低温貼付性が要求される部材に対して１００℃〜２００℃の貼付が可能なフィルム状接着材を得ることができる。また貼付後の耐熱性、信頼性については硬化成分を含むことから熱処理などの熱履歴を与えることによって，高信頼性と耐熱性を要求するエレクトロニクス用材料等に最適なフィルム状接着剤を提供することができる。[0001]
[Field of the Invention]
The present invention has both heat resistance and low-temperature processability, and is used in electronic applications, in particular, a film adhesive excellent in adhesive strength to a silicon substrate or metal suitable as a semiconductor mounting material, a method for producing the same, a lead frame using the same, and The present invention relates to a semiconductor device.
[0002]
[Prior art]
2. Description of the Related Art In recent years, the development of high-performance, large-capacity, and lightweight semiconductor elements has been progressing. Substrate materials used for semiconductor devices are also shifting from conventional metal substrates to organic substrates due to the need for lightweight, cost and large capacity designs.
[0003]
Against this background, there is a demand for (1) low-temperature bonding, (2) improvement in wettability, and (3) high reliability in bonding materials used between a substrate and a chip. (1) is that the heat resistance of the substrate is inferior to that of the metal material, so that it is impossible to perform the bonding operation at a high temperature. (2) The step is formed by the formation of the circuit pattern on the substrate, and the substrate is wet when the adhesive is applied. Insufficient properties may cause voids between the substrate and the adhesive layer. For (3), the organic substrate generally has a higher moisture absorption than that of a metal. The reason for this is that reliability is lowered because of the difficulty in performing the above.
[0004]
In addition, low temperature bonding is required not only for substrates but also for semiconductor chips. This is due to the increase in the circuit pattern density and the thinning of the chip for the purpose of increasing the capacity and space of the chip, resulting in thermal damage to the fine circuit and warping of the chip when heat is applied. Therefore, it is necessary to minimize the heat applied during die bonding.
[0005]
As a currently mainstream die bonding method, there is a method using a paste material. Although it is excellent in versatility and reliability, it can be used in place of paste because it is difficult to apply to packages with misalignment and bleed (protruding) during bonding, uneven thickness, and complicated shapes. Adhesives have come to be used. Semiconductor adhesive tapes have been used exclusively for lead-on-chip structures that have been employed in memories and the like for some time.
[0006]
Conventionally, polyimide adhesives are mainly used for conventional semiconductor adhesive tapes, but in the process of mounting a semiconductor chip on a substrate, many of these semiconductor adhesive tapes have a high sticking temperature of 200 ° C. to 300 ° C. or higher, and the substrate and semiconductor There is concern about heat damage to adherends such as chips. Due to this heat, there is a problem that a yield in a production process is reduced due to thermal deformation such as deterioration of a substrate, deterioration of wiring on a semiconductor chip, and warpage of the chip.
[0007]
In order to solve these problems, it is conceivable to lower the glass transition temperature of the adhesive component of the adhesive tape to provide further low-temperature processability. However, simply lowering the glass transition point lowers the heat resistance of the adhesive component and the adhesiveness at high temperatures and high humidity, causing the resin itself to foam due to the heat when attaching the chip, and to high temperatures such as wire bonding. There is a possibility that the assembling operation under the condition where an atmosphere is required becomes difficult due to low elastic modulus retention, and the reliability as a semiconductor device may be impaired.
[0008]
In order to solve these problems, adhesives for semiconductors obtained by mixing a cured resin such as an epoxy resin or the like and a curing agent thereof with a thermoplastic polyimide resin have been developed and put into practical use. Such a configuration of a thermoplastic resin-thermosetting resin hybrid adhesive has been widely used conventionally. The disadvantage of such an adhesive is that the solvent species that dissolves both the polyimide resin and the hardening component is limited to high boiling solvents, and the hardening component contained when the solvent is evaporated to form a film hardens. As a result, there was a problem that the function as an adhesive was lost.
Therefore, the synthesis of a polyimide resin using a low-boiling solvent (see, for example, Patent Document 1) has expanded the range of choices of a polyimide resin and a curing component that can be used for such an adhesive, and has recently made rapid progress. It has become possible to cope with complicated requirements required for an adhesive used for a certain semiconductor element.
The synthesis of a polyimide resin using such a low boiling point solvent is extremely effective in solving the aforementioned low-temperature sticking property and circuit step embedding property. In the design of an adhesive resin for a semiconductor that is adhered to an organic material or the like in a low temperature range of 100 ° C. to 200 ° C. and has good flowability, the curing behavior of the resin plays an extremely important role. This is because the adhesiveness of the thermosetting resin is developed after the curing, and its flowability reaches its maximum value immediately before the curing reaction.
[0009]
[Patent Document 1]
JP 2002-275281 A
[0010]
[Problems to be solved by the invention]
The present invention has been made as a result of intensive studies in view of the above-described problems of the semiconductor device assembling process using an organic material substrate and a large-capacity chip, and uses a heat-resistant adhesive having specific curing characteristics. The present invention provides a highly reliable heat-resistant adhesive which has excellent heat resistance, adhesiveness, and wettability to an organic material substrate, and suppresses heat damage to a substrate and a chip due to heat at the time of assembly due to a decrease in a bonding temperature. .
[0011]
[Means for Solving the Problems]
As a result of intensive studies on the problems required for semiconductor adhesives used between an organic material substrate and a large-capacity chip, the present invention revealed that a polyimide resin having a specific glass transition temperature and a specific curing property were used to solve the problems. Solving by using a three-layer semiconductor adhesive tape obtained by applying an adhesive having a specific curing property to a single layer or both sides of a base material with an adhesive composed of a combination of a curable resin having a curing agent and a curing agent The present inventors have found out what can be done, and have reached the present invention.
[0012]
That is, the present invention:
(1) A film-like adhesive which is used for an adhesive member used for bonding a semiconductor chip and a lead frame in a semiconductor package assembling process and is made of a combination of a thermoplastic polyimide resin and a thermosetting resin. A film adhesive, wherein the temperature of the exothermic peak top obtained by calorimetry is between 100 ° C and 200 ° C,
(2) a polyimide resin containing at least two or more imide rings in one molecule and having a glass transition point of 90 ° C to 200 ° C, a curable compound, a curing agent for the curable compound, and a silane coupling agent. The adhesive according to (1), wherein the cured film has an elastic modulus at 210 ° C. of 10 to 100 MPa and a water absorption of 3% by weight or less,
(3) The polyimide resin contains, as an amine component, a diaminopolysiloxane represented by the general formula (1), an aromatic diamine, an aliphatic diamine, or an alicyclic ring containing a norbornene ring represented by the formula (2) or (3). Reaction of at least one diamine compound selected from the formula diamine and the alicyclic diamine containing a spiroacetal ring represented by formula (4) with an aromatic tetracarboxylic anhydride as an acid component to form an imide The film adhesive according to (1) or (2), wherein a ring-closing and a polyimide resin soluble in an organic solvent is a main component.
Embedded image

Embedded image

Embedded image

(Wherein, R1, R2, R7, R8, R9, R10, R11, and R12 are a divalent aliphatic or aromatic group having 1 to 4 carbon atoms, and R3, R4, R5, and R6 are monovalent. Represents an aliphatic group or an aromatic group, and k is an integer of 1 to 100.)
(4) The curable compound is at least one compound selected from an epoxy compound having at least two or more epoxy groups in one molecule and a cyanate compound having at least two or more cyanate groups in one molecule. A film adhesive according to (2) or (3),
(5) The film according to any one of (2) to (4), wherein the curing agent is at least one compound selected from a compound having at least one imidazole ring in a molecule and a compound having a phenol novolak structure. Glue,
(6) A solution containing the adhesive composition component of the film adhesive according to any one of (1) to (5) and a phenyl ether represented by the general formula (5) as a solvent, on one or both sides of the support. After casting and drying by heating, the amount of residual solvent is 500 ppm or less semiconductor adhesive tape,
Embedded image

(In the formula, R13 represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, and R14 represents a monovalent hydrocarbon group having 1 to 6 carbon atoms.)
(7) A lead frame to which the semiconductor adhesive tape according to (6) is attached,
(8) A semiconductor device using the lead frame according to (7),
It is.
[0013]
BEST MODE FOR CARRYING OUT THE INVENTION
Examples of the diaminopolysiloxane represented by the general formula (1) used in the present invention include 1,3-bis (3-aminopropyl) tetramethylsiloxane and α, ω-bis (3-aminopropyl) polydimethylsiloxane. No. These are preferably soluble in the phenyl ether represented by the general formula (4).
[0014]
Examples of the aromatic or aliphatic diamine used in the present invention include 3,3′-dimethyl-4,4′-diaminobiphenyl, 4,6-dimethyl-m-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, 2,4-diaminomesitylene, 4,4′-methylenedi-o-toluidine, 4,4′-methylenediamine-2,6-xylidine, 4,4′-methylene-2,6-diethylaniline, 2,4- Toluenediamine, m-phenylenediamine, p-phenylenediamine, 4,4′-diaminodiphenylpropane, 3,3′-diaminodiphenylpropane, 4,4′-diaminodiphenylethane, 3,3′-diaminodiphenylethane, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfide, 3 3′-diaminodiphenyl sulfide, 4,4′-diaminodiphenyl sulfone, 3,3′-diaminodiphenyl sulfone, 4,4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl ether, benzidine, 3 , 3'-Diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxybenzidine, bis (p-aminocyclohexyl) methane, bis (p-β-amino-t-butyl) Phenyl) ether, bis (p-β-methyl-δ-aminopentyl) benzene, p-bis (2-methyl-4-aminopentyl) benzene, 1,5-diaminonaphthalene, 2,6-diaminonaphthalene, 2,4-bis (β-amino-t-butyl) toluene, 2,4-diaminotoluene, m-xylene-2,5-diamine, p-ki Silene-2,5-diamine, m-xylylenediamine, p-xylylenediamine, 2,6-diaminopyridine, 2,5-diaminopyridine, 2,5-diamino-1,3,4-oxadiazol, 1,4-diaminocyclohexane, piperazine, methylenediamine, ethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, 2,5-dimethylhexamethylenediamine, 3-methoxyhexamethylenediamine, heptamethylenediamine, 2,5- Dimethylheptamethylenediamine, 3-methylheptamethylenediamine, 4,4-dimethylheptamethylenediamine, octamethylenediamine, nonamethylenediamine, 5-methylnonamethylenediamine, decamethylenediamine, 1,3-bis (3-aminophenyl Noxy) benzene, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 1,3-bis (4-aminophenoxy) benzene, bis-4- (4-aminophenoxy) phenylsulfone, bis- 4- (3-aminophenoxy) phenylsulfone and the like can be mentioned. Among them, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 1,3-bis (3-aminophenoxy) benzene, or 2,5 (2,6) -bis (aminomethyl) bicyclo [ 2.2.1] Heptane, 3 (4), 8 (9) -bis (aminomethyl) -tricyclo-5,2,1,0 (2.6) decane, 3,9-bis (3-aminopropyl ) Diamines having an alicyclic structure such as a norbornene ring or a spiroacetal ring in the molecule, such as -2,4,8,10 tetraoxaspiro [5.5] undecane, are preferred in terms of solubility in phenyl ether. The above diamines may be used alone or in combination of two or more.
[0015]
The reaction ratio of the diaminopolysiloxane and the aromatic or aliphatic diamine is not particularly limited as long as the glass transition point of the polyimide resin is in the range of 90 ° C. to 200 ° C., but the reaction ratio of the diaminopolysiloxane is diaminopolysiloxane. And preferably 5 to 95 mol% based on the total number of moles of the aromatic or aliphatic diamine. If the amount is less than 5 mol%, the solubility of the obtained polyimide resin in phenyl ether is reduced, and there is a possibility that a problem occurs in operation. If it exceeds 95 mol%, the glass transition temperature of the film is remarkably lowered, and the strength as a film may not be maintained.
[0016]
The aromatic tetracarboxylic dianhydride used in the present invention includes 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride and 3,3', 4,4'-benzophenonetetracarboxylic dianhydride , Pyromellitic dianhydride, 4,4'-oxydiphthalic dianhydride, ethylene glycol bistrimellitic dianhydride, 4,4 '-(4,4'-isopropylidene diphenoxy) phthalic dianhydride, etc. No. Among them, 4,4'-oxydiphthalic dianhydride and 4,4 '-(4,4'-isopropylidene diphenoxy) phthalic dianhydride are preferable in terms of solubility of the obtained polyimide resin in phenyl ether. The above aromatic tetracarboxylic dianhydrides may be used alone or in combination of two or more.
[0017]
The polyimide resin obtained by reacting the diaminosiloxane, the diamine compound, and the aromatic tetracarboxylic anhydride needs to have a glass transition temperature in the range of 90 ° C to 200 ° C. When the temperature is lower than 90 ° C., the heat resistance of the polyimide resin itself decreases, the elastic modulus in a temperature range where wire bonding is performed (180 to 230 ° C.) is low, and peeling may occur between the tape and the adherend during wire bonding. is there. On the other hand, when the temperature exceeds 200 ° C., the solubility of the polyimide resin in phenyl ether becomes low, and the polyimide resin may be precipitated in a phenyl ether solution state.
[0018]
The equivalent ratio between the acid component and the amine component in the polycondensation reaction of the polyimide resin composition used for the heat-resistant adhesive of the present invention is an important factor that determines the molecular weight of the obtained polyimide resin. It is also well known that there is a correlation between the molecular weight and physical properties of a polymer, particularly the number average molecular weight and mechanical properties. The larger the number average molecular weight, the better the mechanical properties. Therefore, in order to obtain practically excellent strength, it is necessary to have a high molecular weight to some extent.
[0019]
In the production of the polyimide resin used in the present invention, the equivalent ratio r of the acid component and the amine component is
0.900 ≦ r ≦ 1.06
Moreover,
0.975 ≦ r ≦ 1.025
Is preferable in terms of both mechanical strength and heat resistance. Here, r = [equivalent number of all acid components] / [equivalent number of all amine components]. When r is less than 0.900, the film has a low molecular weight and becomes brittle when formed into a film. If it exceeds 1.06, unreacted carboxylic acid will be decarbonated during heating, causing gas generation and foaming, which may be undesirable. The addition of a dicarboxylic anhydride or a monoamine for controlling the molecular weight of the polyimide resin does not particularly hinder the addition of the dicarboxylic acid anhydride or monoamine as long as the acid / amine molar ratio r is within the above-mentioned range.
[0020]
The reaction solvent used in the present invention is preferably N-methyl-2-pyrrolidone or phenyl ether represented by the formula (5).
[0021]
Here, typical examples of the phenyl ether represented by the formula (5) include anisole, phenetole, and methoxytoluene. Anisole is most preferable because a polyimide resin film can be obtained by heat treatment at a lower temperature. .
[0022]
At this time, the above-mentioned non-polar solvent compatible with phenyl ether may be mixed and used as an azeotropic solvent. As the non-polar solvent, aromatic hydrocarbons such as toluene, xylene, and solvent naphtha are preferable. The proportion of the non-polar solvent in the mixed solvent is preferably 50% by weight or less. This is because when the amount of the nonpolar solvent exceeds 50% by weight, the solvent power of the solvent is reduced, and there is a possibility that the raw material diaminopolysiloxane and aromatic or aliphatic diamine, alicyclic diamine or polyimide resin may be precipitated. It is.
[0023]
In the case of synthesizing a polyimide resin according to the above-described components and the mixing ratio, the diaminopolysiloxane and the aromatic or aliphatic diamine of the above components are charged into a reaction solvent mainly containing phenyl ether, and heated to about 70 to 80 ° C. Then, the diaminopolysiloxane and the aromatic or aliphatic diamine are dissolved (Solution A). Further, the tetracarboxylic dianhydride of the above-mentioned component is charged into a separate reactor in a solvent mainly composed of phenyl ether, and heated and heated until reflux occurs (Solution B). Subsequently, the solution A is added to the refluxing solution B to allow the polyamideation and the dehydration ring closure reaction to proceed in a short time, and the repeating unit represented by the general formula (6) and the repeating unit represented by the general formula (7) are expressed. And a polyimide resin solution having the repeating unit to be obtained. The water generated by the imidization reaction is discharged out of the system using a device such as a Dean-Stark tube to prevent the ring closure reaction.
[0024]
Embedded image

Embedded image

(Wherein, R1, R2 and R17 are a divalent aliphatic or aromatic group having 1 to 4 carbon atoms, R3, R4, R5 and R6 are a monovalent aliphatic or aromatic group, R15 and R16 Represents a tetravalent aliphatic group or an aromatic group, and k is an integer of 1 to 100. The proportion of m and n is such that m is 5 to 95 mol%, n is 5 to 5 95 mol%.)
[0025]
The curable compound used in the present invention is at least one compound selected from an epoxy compound having at least two or more epoxy groups in one molecule and a cyanate compound having at least two or more cyanate groups in one molecule. It is preferred that
The epoxy compound (D) used in the present invention is not particularly limited as long as it has at least two epoxy groups in one molecule and has compatibility with the polyimide resin (C). Those having good solubility in the solvent used when synthesizing the polyimide resin (C) are preferable. Examples include diglycidyl ether of bisphenol A type, diglycidyl ether of bisphenol F type, bisphenol A-epichlorohydrin type epoxy compound, diphenyl ether type epoxy compound, phenol novolak type epoxy compound, cresol nevolak type epoxy compound, biphenyl type epoxy compound, And hydrogenated bisphenol A type epoxy compounds.
[0026]
The cyanate compound (E) used in the present invention is not particularly limited as long as it has at least two cyanate groups in one molecule and has compatibility with the polyimide resin. Examples include bisphenol-A-dicyanate 4,4′-isopropylidene diphenyl cyanate, 4,4′-ethylidene diphenyl dicyanate, 4,4′-methylenebis (2,6-dimethylphenyl cyanate), oligo (3-methylene- 1,5-phenylene cyanate) and the like.
[0027]
The total content of the epoxy compound (D) and the cyanate compound (E) in the polyimide resin composition of the present invention is preferably 0.01 to 200 parts by weight based on 100 parts by weight of the polyimide resin (C). If the content is less than 0.01, the film strength at high temperatures decreases, and the adhesive strength decreases. If the content exceeds 200 parts by weight, the resin properties of the epoxy compound and the cyanate compound are affected, and heat resistance and mechanical strength, which are characteristics of the polyimide resin, are impaired.
[0028]
The curing agent (F) used in the present invention reacts with a curable compound such as an epoxy compound (D) or a cyanate compound (E), and is subjected to DSC measurement (sample weight 10 mg, heating rate 10 ° C./min) from 100 ° C. It must be such that there is a peak of the exothermic cure during 200 ° C. Conventionally, the curable resin has a minimum melt viscosity at the time of the curing reaction, and the presence of a peak top at this temperature can ensure the wettability to the substrate at the time of heat bonding. If the peak top temperature is less than 100 ° C., the preservability of the adhesive is significantly reduced, and if it exceeds 200 ° C., the resin component decomposes or flows due to the presence of an uncured material at the time of low-temperature heat bonding at 100 ° C. to 200 ° C. Foaming occurs. Further, those having good compatibility with the polyimide resin (C) and the epoxy compound (D) and solubility in a solvent used when synthesizing the polyimide resin (C) are preferable. Examples thereof include imidazole compounds such as 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, and 2-phenyl-4-methylimidazole.
[0029]
The content of the curing agent (F) in the polyimide resin composition of the present invention is 0.01 to 50 parts by weight or less based on 100 parts by weight of the total of the epoxy compound (D) and the curable compound of the cyanate compound (E). Is preferred. If it is less than 0.01, sufficient curing properties cannot be obtained. If the amount exceeds 50 parts by weight, an unreacted curing agent remains during curing, and when formed into a film adhesive, unreacted components are eluted when thermocompression bonding is performed, which adversely affects reliability.
[0030]
The silane coupling agent (G) used in the present invention is compatible with the polyimide resin (C), the epoxy compound (D), the cyanate compound (E), and the curing agent (F), and synthesizes the polyimide resin (C). Those having good solubility in the solvent used at this time are preferred. Examples include vinyltrichlorosilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyl Trimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane and the like, and N-phenyl-γ-amino Propyltrimethoxysilane is preferred in terms of adhesion.
[0031]
The content of the silane coupling agent (G) in the polyimide resin composition of the present invention is preferably 0.01 to 50 parts by weight based on 100 parts by weight of the polyimide resin (C). If it is less than 0.01, sufficient adhesive properties cannot be obtained. If the amount exceeds 50 parts by weight, crosslinking between the polyimide resins is likely to occur, and when the polyimide resin composition solution is prepared, the solution is easily gelled. The wettability with respect to water and the adhesive strength.
[0032]
The polyimide resin composition of the present invention is obtained by adding and mixing an epoxy compound (D), a cyanate compound (E), a curing agent (F) and a silane coupling agent (G) to a polyimide resin (C). To the polyimide resin composition of the present invention, in addition to the above components, various additives such as a smoothing agent for improving surface smoothness, a leveling agent, and a defoaming agent can be added as necessary. Further, in order to adjust the evaporation rate of the solvent in the polyimide resin solution, an aromatic hydrocarbon-based solvent can be used as long as the solvent is uniformly dissolved.
[0033]
In the present invention, the polyimide resin composition is used as an adhesive, using this, to make a film-like adhesive, the polyimide resin solution obtained above, for example, a roll or a metal sheet, or a polyester sheet On a release sheet such as this, a film composed of a resin layer is formed by casting or coating with a flow coater, a roll coater or the like, and after heating and drying, it can be peeled off to obtain a polyimide resin film. The heat treatment at this time is usually performed at 50 to 150 ° C., more preferably at 50 to 120 ° C., and it is possible to produce a film-like adhesive without crosslinking of a curing component such as an epoxy resin. The heat treatment time is usually about 0.1 to 1 hour. The solvent can be completely removed in a short time at a low temperature, and when the film adhesive is thermocompression-bonded, foaming due to the residual solvent is suppressed. Can be. The amount of the residual solvent is preferably 500 ppm or less.
[0034]
The film adhesive obtained by the above method preferably has an untreated glass transition point in the range of 40 to 150 ° C, more preferably 50 to 100 ° C. This is to ensure the wettability of the adhesive, which is necessary to keep the temperature for sticking to the lead frame and die mounting at 250 ° C. or less.
[0035]
After bonding the film adhesive obtained by the above method to a lead frame and a semiconductor element, a film having excellent heat resistance can be obtained by heat treatment. The heat treatment condition is 100 to 200 ° C. for 5 seconds. To 1 hour, more preferably at 100 to 150 ° C. for 5 seconds to 30 minutes. This is because a heat treatment temperature exceeding 200 ° C. causes serious thermal damage to the lead frame and the semiconductor element, and a heat treatment temperature less than 100 ° C. causes residual components of the uncured component to become volatile components during sealing, resulting in a lead frame. This may cause contamination of the semiconductor element. If the heat treatment time exceeds 1 hour, the productivity is reduced, and if the heat treatment time is less than 5 seconds, the residual component of the uncured component becomes a volatile component as in the case of the low-temperature heat treatment, and contaminates the lead frame and the semiconductor element. It can be a cause.
[0036]
The film adhesive obtained in the present invention preferably has a water absorption of 3% by weight or less. This is because when a semiconductor device is assembled using a film adhesive, the water absorption of the film adhesive may affect the reliability of the semiconductor device.
[0037]
In the film adhesive of the present invention, the elasticity at 210 ° C. of the film cured by the low-temperature short-time heat treatment is preferably in the range of 10 to 100 MPa, and more preferably in the range of 30 to 100 MPa. Within this elastic modulus range, wire bonding can be performed without any problem.
[0038]
Further, when the film adhesive of the present invention is used for assembling a semiconductor device, it is possible to provide a highly reliable semiconductor device because of its low water absorption and excellent adhesiveness at high temperatures.
[0039]
【Example】
Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited thereto.
Abbreviations in the examples are as follows.
PI: Polyimide
BPDA: 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride
BPADA: Bisphenol A anhydride
ODPA: 4,4'-oxydiphthalic dianhydride
BAPP: 2,2-bis [4- (4-aminophenoxy) phenyl] propane
APB: 1,3-bis (3-aminophenoxy) benzene
TCDD: 3 (4), 8 (9) -bis (aminomethyl) -tricyclo-5,2,1,0 (2.6) decane
NBDA: 2,5 (2,6) -bis (aminomethyl) bicyclo [2.2.1] heptane
ATU: 3,9-bis (3-aminopropyl) -2,4,8,10 tetraoxaspiro [5.5] undecane
APPS-1: α, ω-bis (3-aminopropyl) polydimethylsiloxane (average molecular weight: 249) (k = 1 in formula (1))
APPS-9: α, ω-bis (3-aminopropyl) polydimethylsiloxane (average molecular weight 837) (k = 9 in the formula (1))
NMP: N-methyl-2-pyrrolidone
KBM573: aminosilane coupling agent (trade name: KBM-573, manufactured by Shin-Etsu Chemical Co., Ltd.)
)
Ep-1: Cresol novolak type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., trade name: EOCN-1020-80, epoxy equivalent: 200)
Ep-2: Biphenyl type epoxy resin (YY-4000HK, manufactured by Yuka Shell Co., Ltd., epoxy equivalent: 195)
Cyn-1: bisphenol A-type diisocyanate resin (trade name: ArocyL10, manufactured by Lonza Co., Ltd.)
Cu-1: 1-benzyl-2-methylimidazole (trade name 1B2MZ, manufactured by Shikoku Chemicals Co., Ltd.)
Cu-2: 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole (2E4MZ-CN, manufactured by Shikoku Chemicals Co., Ltd.)
Si-1: aminosilane coupling agent (brand name KBM-573, manufactured by Shin-Etsu Chemical Co., Ltd.)
Si-2: epoxy silane coupling agent (brand name KBM403E, manufactured by Shin-Etsu Chemical Co., Ltd.)
[0040]
(Synthesis of PI-1)
In an Erlenmeyer flask, 26.0 g of anisole was added, and 86.2 g (0.21 mol) of 2,2-bis [4- (4-aminophenoxy) phenyl] propane and 2,5 (2,6) -bis ( Aminomethyl) bicyclo [2.2.1] heptane 4.63 g (0.03 mol) and α, ω-bis (3-aminopropyl) polydimethylsiloxane (average molecular weight 837) (k = 9 in the formula (1)) ), 50.22 g (0.06 mol) was added, and the mixture was heated to 70 ° C and stirred until dissolved (Solution A).
[0041]
Next, 524.2 g of anisole and 137.0 g of toluene were put into a three-necked flask equipped with a dry nitrogen gas inlet tube, a cooler, a thermometer, a dropping funnel, and a stirrer, and nitrogen gas was flown. Next, 88.3 g (0.3 mol) of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride as an acid component was charged, and a Dean-Stark tube filled with toluene was attached to the flask. The system was heated in an oil bath until reflux occurred. Next, the solution A was put into a dropping funnel and dropped into the flask over 1 hour. Water generated during this time was removed from the system using a Dean-Stark tube. After heating for 3 hours, the mixture was cooled to obtain a target polyimide resin solution. The obtained polyimide resin was measured using a GPC measuring device manufactured by Tosoh Corporation in terms of polystyrene and found to have Mw = 38200.
[0042]
(Synthesis of PI-2)
592.8 g of anisole and 148.19 g of toluene were placed in a three-necked flask equipped with a dry nitrogen gas inlet tube, a condenser, a thermometer, and a stirrer, and nitrogen gas was flown therein. Next, 90.31 g (0.22 mol) of 2,2-bis [4- (4-aminophenoxy) phenyl] propane as an amine component and α, ω-bis (3-aminopropyl) polydimethylsiloxane (average 13.67 g (0.055 mol) of molecular weight 837) (k = 9 in the formula (1)) and 143.00 g (0.275 mol) of bisphenol A acid anhydride as an acid component were charged and filled with toluene. A Dean-Stark tube was attached to the flask and the system was heated in an oil bath until reflux occurred. Water generated during this time was removed from the system using a Dean-Stark tube. After heating for 1 hour, the solution was cooled to obtain a target polyimide resin solution. The obtained polyimide resin was measured with a GPC measuring device manufactured by Tosoh Corporation in terms of polystyrene, and found to have Mw = 38000.
[0043]
(Synthesis of PI-3)
In an Erlenmeyer flask, put 465.25 g of anisole, and further 82.1 g (0.20 mol) of 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 3 (4), 8 (9) -bis 15.54 g (0.08 mol) of (aminomethyl) -tricyclo-5,2,1,0 (2.6) decane, α, ω-bis (3-aminopropyl) polydimethylsiloxane (average molecular weight 249) ( In formula (1), k = 1) 6.17 g (0.04 mol), 2,5 (2,6) -bis (aminomethyl) bicyclo [2.2.1] heptane 10.96 g (0.04 mol) ), 9.94 g (0.04 mol) of 3,9-bis (3-aminopropyl) -2,4,8,10 tetraoxaspiro [5.5] undecane, and heated to 70 ° C. to dissolve The mixture was stirred until the temperature reached (Solution A).
[0044]
Next, 131.88 g of anisole and 149.28 g of toluene were placed in a three-necked flask equipped with a dry nitrogen gas inlet tube, a cooler, a thermometer, a dropping funnel, and a stirrer, and nitrogen gas was flown. Next, 124.1 g (0.4 mol) of 4,4′-oxydiphthalic dianhydride as an acid component was charged, a Dean-Stark tube filled with toluene was attached to the flask, and the system was placed in an oil bath. Heat until reflux occurs. Next, the solution A was put into a dropping funnel and dropped into the flask over 1 hour. Water generated during this time was removed from the system using a Dean-Stark tube. After heating for 3 hours, the mixture was cooled to obtain a target polyimide resin solution. The obtained polyimide resin was measured using a GPC measuring device manufactured by Tosoh Corporation in terms of polystyrene, and found to have Mw = 52,000.
[0045]
(Synthesis of PI-4)
In an Erlenmeyer flask, 438.50 g of anisole was added, and 43.85 g (0.15 mol) of 1,3-bis (3-aminophenoxy) benzene and α, ω-bis (3-aminopropyl) polydimethylsiloxane (average) 125.55 g (0.15 mol) of (molecular weight: 837) (k = 9 in the formula (1)) was added, the mixture was heated to 70 ° C., and stirred until dissolved (solution A).
[0046]
Next, 348.90 g of anisole was charged into a three-necked flask equipped with a dry nitrogen gas inlet tube, a cooler, a thermometer, a dropping funnel, and a stirrer, and nitrogen gas was flown. Next, 93.07 g (0.30 mol) of 4,4′-oxydiphthalic dianhydride, which is an acid component, was charged, a Dean-Stark tube was attached to the flask, and the system was refluxed in an oil bath. Until heated. Next, the solution A was put into a dropping funnel and dropped into the flask over 1 hour. Water generated during this time was removed from the system using a Dean-Stark tube. After heating for 3 hours, the mixture was cooled to obtain a target polyimide resin solution. The obtained polyimide resin was measured using a GPC measuring device manufactured by Tosoh Corporation in terms of polystyrene and found to have Mw = 55400.
[0047]
(Synthesis of PI-5)
In a three-necked flask equipped with a dry nitrogen gas inlet tube, a cooler, a thermometer, and a stirrer, 594.63 g of NMP was charged, and nitrogen gas was flown. Next, 29.15 g (0.15 mol) of 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5.5] undecane, which is an amine component, and 125.6 g of APPS-9 (0.150 mol) and stirred until uniform. After uniformly dissolving, 93.07 g (0.30 mol) of ODPA, which is an acid component, is added over 10 minutes while keeping the system at 20 ° C. in an ice water bath while stirring, and stirring is continued for 2 hours. A solution was obtained. During this time, the flask was kept at 20 ° C.
Thereafter, the nitrogen gas inlet tube and the condenser were removed, a Dean-Stark tube filled with toluene was attached to the flask, and 148.70 g of toluene was added to the system. The system was heated by replacing the ice water bath with an oil bath, and the generated water was removed from the system. After heating for 3 hours, the mixture was cooled to obtain a polyimide solution PI-5.
[0048]
Table 1 shows a composition table of the polyimides PI-1 to PI-5 obtained above. The blending values in the table represent molar ratios. These polyimide solutions were applied to a silicone release treated biaxially stretched polyester film with a roll coater to a thickness of 25 μm, dried at 80 ° C. for 2 minutes, 130 ° C. for 2 minutes, and dried at 180 ° C. for 2 minutes. A resin film was obtained. Table 1 also shows the results of measuring the glass transition point of this film using a thermomechanical analyzer (TMA, manufactured by Seiko Instruments Inc., SS-6000).
[0049]
[Table 1]

[0050]
Examples 1 to 6 and Comparative Examples 1 to 4
The polyimide solution obtained above and each component were mixed according to the formulations shown in Table 2, and the adhesive solutions of Examples 1 to 6 and Comparative Examples 1 to 4 were prepared. The numerical values of the formulations in the table represent parts by weight.
[0051]
Next, the obtained film was dried under the drying conditions shown in Table 2 to obtain a film adhesive. Table 2 shows the results of measuring the glass transition point, DSC peak temperature, and residual solvent amount of the film adhesive. The film adhesive was further cured under the heat treatment conditions shown in Table 2, and the glass transition point, elastic modulus, water absorption, and adhesive strength of the cured film were measured. The results are shown in Table 2.
[0052]
Curing exothermic peak top measurement method:
A sample (10 mg) was placed in an aluminum pan, and the measurement was performed using a differential scanning calorimeter (DSC, manufactured by Seiko Instruments Inc., DSC6200) at a heating rate of 10 ° C./min. The peak top of the obtained DSC curve was read, and it was set as the peak temperature of the heat generated by curing.
[0053]
Glass transition point measurement method:
The sample was cut into a rectangle having a thickness of 25 μm and a width of 3 mm, and the measurement was performed using a thermomechanical analyzer (TMA, manufactured by Seiko Instruments, SS-6000) under the conditions of a temperature rising rate of 5 ° C./min and a load of 25 mN. The extrapolation point of the TMA curve was defined as the glass transition point.
[0054]
Elastic modulus measurement method:
Using a dynamic viscoelasticity measuring device (DMS, manufactured by Seiko Instruments Inc., DMS210), a film sample having a known cross section of 1 cm in width was measured at a frequency of 10 Hz and a heating rate of 3 ° C./min. The value of the obtained storage elastic modulus E 'is defined as the elastic modulus.
[0055]
Water absorption measurement method:
A film cut into a square having a thickness of 25 μm and 5 cm × 5 cm is dried in a dryer at 50 ° C. for 24 hours, and the weight at this time is defined as w. Then, the film is immersed in pure water at 25 ° C. for 24 hours, taken out, weighed, and designated as W. The water absorption of the film is represented by the following equation.
Water absorption (%) = (W−w) / w × 100
[0056]
Method for measuring residual solvent amount:
About 50 mg of the sample is placed in a sample tube of a purge & trap, and the sample is heated under a heating condition of 250 ° C. × 15 minutes while removing volatile matter with helium gas at a flow rate of 50 mL / min. The volatile matter generated at this time is trapped at -80 ° C, and after the heating of the sample is completed, the trapped component is rapidly heated and introduced into the GC / MS meter. For the quantitative determination of each generated gas component, using a toluene diluted solution of n-decane having a known concentration, a purge & trap-GC / MS measurement was performed under the same heating conditions as the sample, and the peak area value of each generated gas component was measured. Is calculated as a weight fraction relative to the weight of the sample.
[0057]
Adhesive strength measurement method:
The adhesive film sample was thermocompression-bonded to a 42-alloy plate to form a test piece. After releasing the pressure, the sample was annealed at 300 ° C. for 30 seconds. The pressure applied to the bonding surface is 4 kgf / cm as a result of calculation from the gauge pressure and bonding area. ² Met. The test piece was measured for 180 ° C peel strength.
[0058]
[Table 2]

[0059]
【The invention's effect】
ADVANTAGE OF THE INVENTION According to this invention, the film-shaped adhesive material which can be stuck at 100 degreeC-200 degreeC with respect to the member which requires low-temperature sticking property can be obtained. As for the heat resistance and reliability after application, it contains a hardening component, so by providing a heat history such as heat treatment, it provides a film adhesive that is optimal for materials for electronics that require high reliability and heat resistance. be able to.

Claims (8)

A film adhesive made of a combination of a thermoplastic polyimide resin and a thermosetting resin, which is used for an adhesive member used for bonding a semiconductor chip and a lead frame in a semiconductor package assembling process. A film-like adhesive characterized in that the temperature of the peak of the exothermic curing obtained in the measurement with a calorimeter (hereinafter, DSC) is between 100 ° C and 200 ° C. Film containing at least two or more imide rings in one molecule and having a glass transition point of 90 ° C to 200 ° C, a curable compound, a curing agent for the curable compound, and a silane coupling agent The film-like adhesive according to claim 1, wherein the cured film has an elastic modulus at 210C of 10 to 100 MPa and a water absorption of 3% by weight or less. A polyimide resin, as an amine component, a diaminopolysiloxane represented by the general formula (1), an aromatic diamine, an aliphatic diamine, an alicyclic diamine containing a norbornene ring represented by the formula (2) or (3), And reacting at least one diamine compound selected from alicyclic diamines containing a spiroacetal ring represented by the formula (4) with an aromatic tetracarboxylic anhydride as an acid component to form an imide ring, The film adhesive according to claim 1, further comprising a polyimide resin soluble in an organic solvent as a main component.

(Wherein, R1, R2, R7, R8, R9, R10, R11, and R12 are a divalent aliphatic or aromatic group having 1 to 4 carbon atoms, and R3, R4, R5, and R6 are monovalent. Represents an aliphatic group or an aromatic group, and k is an integer of 1 to 100.) The curable compound is at least one compound selected from an epoxy compound having at least two or more epoxy groups in one molecule and a cyanate compound having at least two or more cyanate groups in one molecule. 4. The film adhesive according to 2 or 3. The film adhesive according to any one of claims 2 to 4, wherein the curing agent is at least one compound selected from a compound having at least one imidazole ring in a molecule and a compound having a phenol novolak structure. A solution containing the adhesive composition component of the film-like adhesive according to any one of claims 1 to 5 and a phenyl ether represented by the general formula (5) as a solvent is cast and applied to one or both surfaces of the support. A semiconductor adhesive tape having a residual solvent amount of 500 ppm or less after heating and drying.

(In the formula, R13 represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, and R14 represents a monovalent hydrocarbon group having 1 to 6 carbon atoms.) A lead frame to which the semiconductor adhesive tape according to claim 6 is attached. A semiconductor device using the lead frame according to claim 7.