JP4411876B2 - Adhesive composition for semiconductor device, adhesive sheet and coverlay film using the same, and copper-clad polyimide film - Google Patents

Description

【００１５】
また、ここで用いられるダイマー酸変性エポキシ樹脂は、全接着剤組成物１００重量部あたり２〜３０重量部添加することが好ましく、２〜２５重量部がより好ましい。３０重量部より多く添加すると硬化物のＴｇが低下し、２重量部未満であると半田耐熱性や寸法安定性が低下する。
【００１６】
ここで使用されるエポキシ樹脂としては、エポキシ基を２個以上含むものであれば特に限定されないが、例えばビスフェノールＡ、ビスフェノールＦ、ビスフェノ−ルＳ、レゾルシノ−ル、ジヒドロキナフタレン、ジシクロペンタジエンジフェノ−ル等のジグリシジルエ−テル、エポキシ化フェノ−ルノボラック、エポキシ化クレゾ−ルノボラック、エポキシ化トリスフェニロ−ルメタン、エポキシ化テトラフェニロ−ルエタン等の脂環式エポキシ樹脂、あるいはビフェノール型エポキシ樹脂あるいはノボラック型エポキシ樹脂とそれらすべての臭素化誘導体などが挙げられる。
【００１７】
また、非ハロゲン難燃化を達成するためには、ハロゲンを含まないエポキシ樹脂、特に非臭素系エポキシ樹脂を選択することができ、例えばリンを含有するエポキシ樹脂等を使用することが出来る。その種類としては特に限定されるものではないが、例えば、９，１０−ジヒドロ−９−オキサ−１０−ホスファフェナントレン−１０−オキシドやその誘導体と、１，４−ベンゾキノン、１，２−ベンゾキノン、トルキノン、１，４−ナフトキノン等が反応して得られる化合物に、エポキシ樹脂を予め反応させたリン含有エポキシ樹脂等が挙げられる。
【００１８】
さらにエポキシ樹脂を含有した接着剤組成物の硬化後のガラス転移温度（Ｔｇ）を高めるために、かさ高い置換基を有するエポキシ樹脂として、ビフェニル、ナフタレン骨格などの芳香環、またはそれらの縮合多環骨格を有するビスフェノール系エポキシ樹脂等を用いてもよい。
【００１９】
また、本発明に用いられる硬化剤は特に限定するものではない。例えば、芳香族ポリアミンである３，３´５，５´−テトラメチル−４，４´−ジアミノジフェニルメタン、３，３´５，５´−テトラエチル−４，４´−ジアミノジフェニルメタン、３，３´−ジメチル−５，５´−ジエチル−４，４´−ジアミノジフェニルメタン、３，３´−ジクロロ−４，４´−ジアミノジフェニルメタン、２，２´３，３´−テトラクロロ−４，４´−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´−ジアミノベンゾフェノン、３，３´−ジアミノジフェニルスルホン、４，４´−ジアミノジフェニルスルホン、３，４´−ジアミノジフェニルスルホン、４，４´−ジアミノベンゾフェノン、３，４，４´−トリアミノジフェニルスルホン等やフェノールノボラック樹脂などを更に用いても良い。また、硬化速度や接着剤膜の適度な柔軟性をコントロールするため、ジシアンジアミド、酸無水物系などの公知の硬化剤を用いることもできる。また、Ｔｇが高い接着剤層の場合には、接着剤層の常温での貯蔵弾性率が高くなる傾向があり、ＦＰＣ材料における銅箔との接着力が低下したり、銅張りポリイミドフィルム（ＣＣＬ）にパターン回路を形成することによってそりやカールが発生するため、それらの問題を軽減するためには、接着性に優れ、柔軟構造を有するジシアンジアミドを用いることが好ましい。
【００２０】
また、本発明で使用されるフェノキシ樹脂は、ビスフェノールＡ型フェノキシ樹脂、多核体を含まないビスフェノールＦからなるビスフェノールＦ型フェノキシ樹脂、多核体を含有するビスフェノールＦを用いたビスフェノールＡとビスフェノールＦの共重合体フェノキシ樹脂やそれらすべての臭素化誘導体、またはフェノール水酸基などのエポキシ樹脂と反応する２つ以上の官能基を有する化合物と上記フェノキシ樹脂をあらかじめ反応させた誘導体などを用いることができる。又、ＦＰＣ材料に必要な難燃性能を付与し、かつ接着剤膜の屈曲性、接着性、柔軟性を良好とする上で、臭素化フェノキシ樹脂を用いることができる。臭素化フェノキシ樹脂のエポキシ当量は２０００以上が好ましい。２０００未満であると、接着剤膜に必要十分となる柔軟性を付与することができない。
【００２１】
また、ここで用いられるフェノキシ樹脂は、エポキシ樹脂１００重量部あたり、１００〜５００重量部含まれることが好ましく、１００〜３００重量部がより好ましい。すなわち、５００重量部より多く添加すると電気絶縁特性が低下する問題が生じ、１００未満であると硬化後の接着剤組成物の柔軟性を達成することができない。
【００２２】
また、エポキシ樹脂、硬化剤、フェノキシ樹脂以外に、必要に応じてフェノール樹脂、硬化促進剤、エラストマーなどを添加してもよい。
【００２３】
たとえば、フェノール樹脂として、ノボラック型フェノール樹脂、レゾール型フェノール樹脂等の公知のフェノール樹脂がいずれも使用できる。たとえば、フェノール、クレゾール、ｐ−ｔ−ブチルフェノール、ノニルフェノール、ｐ−フェニルフェノール等のアルキル置換フェノール、テルペン、ジシクロペンタジエン等の環状アルキル変性フェノール、ニトロ基、ハロゲン基、シアノ基、アミノ基等のヘテロ原子を含む官能基を有するもの、ナフタレン、アントラセン等の骨格を有するもの、ビスフェノールＦ、ビスフェノールＡ、ビスフェノールＳ、レゾルシノール、ピロガロール等の多官能性フェノールメラミン変性又はトリアジン変性フェノール等の窒素含有フェノールからなる樹脂が挙げられる。
【００２４】
また、硬化促進剤としては三フッ化ホウ素トリエチルアミン錯体等の三フッ化ホウ素のアミン錯体、２−アルキル−４−メチルイミダゾール、２−フェニル−４−アルキルイミダゾール等のイミダゾール誘導体、無水フタル酸、無水トリメリット酸等の有機酸、ジシアンジアミド等が挙げられ、これらを単独または２種以上混合して用いても良い。
【００２５】
その他、エラストマー成分としては、アクリルゴム、アクリロニトリルブタジエンゴム、カルボキシル基含有アクリロニトリルブタジエンゴム（以下ＮＢＲ−Ｃと称する）等の変性タイプを添加することができる。例えばＮＢＲ−Ｃの例として、アクリロニトリルとブタジエンを約１０／９０〜５０／５０のモル比で共重合させた共重合ゴムの末端基をカルボキシル化したもの、あるいはアクリロニトリル、ブタジエンとアクリル酸、マレイン酸などのカルボキシル基含有重合性単量体の三元共重合ゴムなどが挙げられる。具体的なＮＢＲ−Ｃとしては、ＰＮＲ−１Ｈ（日本合成ゴム（株）製）、“ニポール”１０７２Ｊ、“ニポール”ＤＮ６１２、“ニポール”ＤＮ６３１（以上日本ゼオン（株）製）、“ハイカー”ＣＴＢＮ（ＢＦグッドリッチ社製）等があげられる。
【００２６】
さらに上記成分以外に必要に応じて微粒子状の無機粒子剤を添加できる。微粒子状の無機粒子剤としては水酸化アルミニウム、水酸化マグネシウム、カルシウム・アルミネート水和物等の金属水酸化物や、酸化亜鉛、酸化マグネシウム、シリカ、アルミナ、酸化ジルコニウム、三酸化アンチモン、五酸化アンチモン、酸化チタン、酸化鉄、酸化コバルト、酸化クロム、タルク等の金属酸化物、アルミニウム、金、銀、ニッケル、鉄、等の金属微粒子、あるいはカーボンブラック、ガラスが挙げられるが、特に難燃性の点で水酸化アルミニウムが好ましい。またこれらを単独または２種以上混合して用いても良い。微粒子状の無機粒子剤平均粒子径は透明性と分散安定性を考慮すると、０．２〜５μｍが好ましい。
【００２７】
また、接着剤の特性を損なわない範囲で酸化防止剤、イオン捕捉剤、メラミン及びその誘導体、９，１０−ジヒドロ−９−オキサ−１０−ホスファフェナントレン−１０−オキシドやその誘導体と、１，４−ベンゾキノン、１，２−ベンゾキノン、トルキノン、１，４−ナフトキノン等が反応して得られる化合物や各種リン酸エステルなどのリン化合物、シリコーン系化合物等の有機、無機成分を添加することは何ら制限されるものではない。
【００２８】
本発明の接着剤シートは、少なくとも１層の有機絶縁性フィルム層と少なくとも１層の上記接着剤層から構成されるが、本発明でいう絶縁性フィルムとは、ポリイミド、ポリエステル、ポリフェニレンスルフィド、ポリエーテルスルホン、ポリエーテルエーテルケトン、アラミド、ポリカーボネート、ポリアリレート等のプラスチックからなる厚さ５〜２００μｍのフィルムであり、これらから選ばれる複数のフィルムを積層して用いても良い。また必要に応じて、加水分解、コロナ放電、低温プラズマ、物理的粗面化、易接着コーティング処理等の表面処理を施すことができる。
【００２９】
また本発明の半導体装置用接着剤シートは、有機絶縁性フィルムが剥離可能な保護フィルム（離型フィルム）であってもよく、その材料は接着剤層及びそれを用いた接着剤シートの形態を損なうことなく剥離できれば特に限定されない。たとえばシリコーンあるいはフッ素化合物のコーティング処理を施したポリエステルフィルム、ポリオレフィンフィルム、およびこれらをラミネートした紙が挙げられる。その構成例は、例えば、剥離可能なポリエステル保護フィルム（１２．５〜１５０μｍ）／接着剤層（１０〜１００μｍ）／剥離可能なポリエステル保護フィルム（１２．５〜１５０μｍ）等が挙げられる。また、それぞれの保護フィルム層の接着剤層に対する剥離力をＦ１、Ｆ２（Ｆ１＞Ｆ２）としたとき、Ｆ１−Ｆ２は好ましくは５Ｎ／ｍ以上、さらに好ましくは１０Ｎ／ｍ以上が必要である。Ｆ１−Ｆ２が５Ｎ／ｍより小さい場合は、剥離面がいずれの保護フィルム側になるか安定しないので、好ましくない。また、剥離力Ｆ１、Ｆ２はいずれも１〜２００Ｎ／ｍ、好ましくは３〜１５０Ｎ／ｍ、さらに好ましくは３〜１００Ｎ／ｍである。１Ｎ／ｍより小さい場合は保護フィルムの脱落が生じ、２００Ｎ／ｍを越えると剥離が困難になる。さらに保護フィルムは、加工時に視認性が良いように顔料による着色が施されていても良い。これにより、先に剥離する側の保護フィルムが簡便に認識できるため、誤使用を避けることができる。
【００３０】
また本発明の半導体装置用接着剤シートとして、銅張りポリイミドフィルムに形成したパターン回路の保護層として使われるカバーレイフィルムやテープオートメーティッドボンディング（ＴＡＢ）用接着剤付きテープが挙げられる。本発明のカバーレイフィルムの主な構成としては、ポリイミドフィルムまたはアラミドフィルム等の有機絶縁性フィルム（１２．５〜１２５μｍ）／接着剤層（５〜５０μｍ）／剥離可能な保護フィルム（１２．５〜１２５μｍ）等が挙げられる。
【００３１】
本発明の、接着剤層を介して有機絶縁性フィルムと銅箔を張り合わせた銅張りポリイミドフィルムの主な構成は、例えば片面品：銅箔（９〜３５μｍ）／接着剤層（５〜２０μｍ）／ポリイミドフィルム（１２．５〜１２５μｍ）、両面品：銅箔（９〜３５μｍ）／接着剤層（５〜２０μｍ）／ポリイミドフィルム（１２．５〜１２５μｍ）／接着剤層（５〜２０μｍ）／銅箔（９〜３５μｍ）等が挙げられる。また銅箔とは、一般的に圧延銅箔、電解銅箔等を用いることができるが、銅張りポリイミドフィルム、フレキシブルプリント配線基板、ＦＰＣの屈曲特性をより安定させる上で、圧延銅箔が好適である。
【００３２】
また、テープオートメーティッドボンディング（ＴＡＢ）用接着剤付きテープは、剥離可能なポリエステル保護フィルム（１２．５〜１５０μｍ）／接着剤層（５〜２００μｍ）／剥離可能なポリエステル保護フィルム（１２．５〜１５０μｍ）等を所定の規格幅（２９．７〜６０．６ｍｍ）にスリットした接着剤シートを、幅３５〜７０ｍｍの規格幅の絶縁性フィルムの中央部に１００〜１６０℃、１０Ｎ／ｃｍ、５ｍ／ｍｉｎの条件で熱ロールラミネートして作成されたもの等が例示される。
【００３３】
次に、本発明の半導体装置用接着剤シート及び銅張りポリイミドフィルム、カバーレイフィルム、テープオートメーティッドボンディング（ＴＡＢ）用接着剤付きテ−プの製造方法を例示して説明する。
【００３４】
（１）半導体装置用接着剤シートの作成：本発明の接着剤組成物を溶剤に溶解した塗料を、両面ともに離型処理を行ったポリエステルフィルム上に塗布、乾燥する。接着剤層の膜厚は１０〜１００μｍとなるように塗布することが好ましい。乾燥条件は、１００〜２００℃、１〜５分である。溶剤は特に限定されないが、トルエン、キシレン、クロルベンゼン等の芳香族系、メチルエチルケトン、メチルエチルイソブチルケトン（ＭＩＢＫ）等のケトン系、ジメチルホルムアミド（ＤＭＦ）、ジメチルアセトアミド、Ｎメチルピロドリン等の非プロトン系極性溶剤単独あるいは混合物が好適である。
【００３５】
塗工、乾燥した接着剤層上にさらに高い離型性を有するポリエステルあるいはポリオレフィン系の保護フィルムをラミネートして、本発明の接着剤シートを得る。さらに接着剤厚みを増す場合は、接着剤シートを複数回積層すればよく、場合によってはラミネート後に、例えば４０〜１００℃で１〜２００時間程度エージングして硬化度を調整してもよい。
【００３６】
（２）銅張りポリイミドフィルムの作成：ＭＥＫ（メチルエチルケトン）、ＭＩＢＫ（メチルイソブチルケトン）、ＣＢ（クロロベンゼン）、ＢＡ（ベンジルアルコール）等を溶媒とし、エポキシ樹脂、フェノキシ樹脂、硬化剤、硬化促進剤、無機フィラー、難燃剤などを溶解して接着剤溶液を作成する。この接着剤をバーコータで、厚さ２５μｍのポリイミドフィルム（東レデュポン（株）製”カプトン”１００Ｖ−Ｐ）に約１０μｍの乾燥厚さとなるように塗布し、１５０℃で５分間乾燥し、シリコーン離型剤付きの厚さ２５μｍのポリエステルフィルムをラミネートして接着剤シートを得る。その後、上記接着剤シートのポリエステルフィルムをはがして、１／２ｏｚの圧延銅箔の非光沢面に１００℃、２．７ＭＰａでラミネートし、その後エアオーブン中で、１５０℃×５時間の加熱を行い、銅張りポリイミドフィルムを作成する。両面銅張りポリイミドフィルムを作成する場合は、上記のように片面接着剤シートを作成した後、反対側の面に再度同様に接着剤を塗布し、両面接着剤シートを作成し、その両面に銅箔をラミネートすることで作成することができる。
【００３７】
（３）カバーレイフィルムの作成：（２）と同様の方法で調合した接着剤溶液を用いて、バーコータで、厚さ２５μｍのポリイミドフィルム（東レデュポン（株）製”カプトン”１００Ｖ−Ｐ）に約３０μｍの乾燥厚さとなるように塗布し、１５０℃で５分間乾燥し、シリコーン離型剤付きの厚さ２５μのポリエステルフィルムをラミネートしてカバーレイフィルムを得る。その後、接着剤の浸みだし量が適正になるように５０℃×２０〜５０時間のエージングを施し、硬化度を調整することが一般的である。
【００３８】
（４）テープオートメーティッドボンディング（ＴＡＢ）用接着剤付きテープ接着剤付きテープの作成：ポリイミド等の絶縁性フィルムに接着剤組成物溶液をコーティング法により塗工、乾燥した後所定の幅にスリットし、接着剤付きテープを得る。また、離型性を付与したポリエステルフィルム等の保護フィルム上に接着剤組成物溶液をコーティング法により塗工、乾燥した後、２９．７〜６０．６ｍｍの規格幅にスリットした接着剤付きテープを、幅３５〜７０ｍｍの規格幅の絶縁性フィルムの中央部に１００〜１６０℃、１０Ｎ／ｃｍ、５ｍ／ｍｉｎの条件で熱ロールラミネートする方法でＴＡＢ用接着剤付きテープ形状として用いても良い。
【００３９】
本発明の半導体装置用接着剤シート、カバーレイフィルム、銅張りポリイミドフィルムの用途は、例えば銅張りポリイミドフィルム及びカバーレイフィルムからなるフレキシブルプリント回路基板だけでなく、それら複数のフレキシブルプリント回路基板を接着剤シートを用いて重ね合わせた多層銅張りポリイミドフィルム回路基板や、リジッド積層板とフレキシブルプリント回路基板を接着剤シート等を用いて積層し混合形態としたフレックスリジッド回路基板、さらにはＴＡＢ用基板、各種パーケージ用途（ＣＳＰ、ＢＧＡ）などに用いられる。尚、ＴＡＢ用基板の製造方法及び一般的な半導体接続用回路基板の基板は以下の通りである。
【００４０】
（５）ＴＡＢ用基板の製造例
上記（４）の接着剤付きテープサンプルに３〜３５μｍの電解または圧延銅箔を、１１０〜１８０℃、３０Ｎ／ｃｍ、１ｍ／ｍｉｎの条件でラミネートする。必要に応じてエアオーブン中で、８０〜３００℃、１〜２４時間段階的加熱硬化処理を行ない、ＴＡＢ用基板を作成する。 この際に、銅箔張り合わせ前に接着剤付きテープサンプルにデバイス孔およびハンダボール孔を穿孔しても良い。
【００４１】
（６）半導体接続用回路基板の製造例
上記（２）、（５）で得られた銅張りポリイミドフィルム、ＴＡＢ用基板の銅箔面に常法によりフォトレジスト膜形成、エッチング、レジスト剥離、電解金メッキ、ソルダーレジスト膜形成を行ない、半導体接続用回路基板を作成する。
【００４２】
【実施例】
以下に実施例を挙げて本発明を説明するが、本発明はこれらの実施例に限定されるものではない。実施例の説明に入る前に銅張りポリイミドフィルム・カバーレイフィルムの評価用サンプル作成方法・各特性の評価方法について述べる。
（１）各特性の評価方法
Ａ．剥離強度（ピール）
銅張ポリイミドフィルム及び３５μｍの電解銅箔（日鉱グールド・フォイル（株）製、ＪＴＣ銅箔）の光沢面に、１６０℃×３０分×４ＭＰａの条件でプレスしたカバーレイ評価サンプルを用いて、ＪＩＳ−Ｃ６４８１に準拠して行った。
【００４３】
＜銅張ポリイミドフィルム＞
エッチングにより２ｍｍ幅の銅箔パターンを作成し、テンシロン（オリエンテック（株）製、ＵＴＭ−１１−５ＨＲ型）を用いて２ｍｍ幅の銅箔を９０度方向に引き剥がした場合の強度を測定する（引張速度：５０ｍｍ／分）。
【００４４】
＜カバーレイ評価用サンプル＞
ポリイミド表面に２ｍｍ幅の切れ込みを入れ、テンシロン（オリエンテック（株）製、ＵＴＭ−１１−５ＨＲ型）を用いて２ｍｍ幅のポリイミドを９０度方向に引き剥がした場合の強度を測定する（引張速度：５０ｍｍ／分）。
【００４５】
Ｂ．半田耐熱性
ＪＩＳ−Ｃ６４８１に準拠した方法で行なった。上記Ａ．で作成した銅張ポリイミドフィルム及びカバーレイ評価サンプルを２０ｍｍ角にカットし、４０℃、９０％ＲＨの雰囲気下で２４時間調湿した後、すみやかに所定の温度の半田浴上に３０秒間浮かべ、ポリイミドフィルムの膨れおよび剥がれのない最高温度を測定した。
【００４６】
Ｃ．しゅう動屈曲特性
Ａ．の方法で作成した銅張りポリイミドフィルムにＪＩＳ Ｃ６４７１で開示される耐屈曲試験試料のパターンを作製し、これにカバーレイフィルムを１６０℃×３０分×４ＭＰａでプレス接着し最終試験試料を作製した。これを用いて、ＦＰＣ高速屈曲試験器（信越エンジニアリング（株）製）にて、振動数１５００ｃｐｍ、ストローク２０ｍｍ、曲率２．５ｍｍＲに設定し、カバーレイ面側を外側にして取り付けたサンプルの、８０℃各雰囲気温度下での抵抗値変化を測定し、抵抗が初期から２０％以上に上昇する回数を屈曲回数とした。
【００４７】
Ｄ．そり
カバーレイ：１５０ｍｍ角のカバーレイから離型フィルムを剥がした後、四隅が浮くようにして平板上に置き、平板からの最大距離を測定する。
【００４８】
銅張りポリイミド：１５０ｍｍ角の片面銅張りポリイミドから銅箔を全面エッチングした後、１５０℃×１ｈｒオーブンに投入後、四隅が浮くようにして平板上に置き、常温放置での平板からの最大距離を測定する。
【００４９】
実施例１
臭素化ビスフェノールＡ型フェノキシ樹脂（東都化成（株）製、ＹＰＢ４０）、エポキシ樹脂（大日本インキ工業（株）製、エピクロン８３０）、ジシアンジアミド（ジャパンエポキシレジン（株）製硬化剤、ＤＩＣＹ７）、イミダゾール系硬化促進剤（ジャパンエポキシレジ（株）製、ＥＭＩ２４）及びダイマー酸変性エポキシ樹脂（大日本インキ工業（株）製、１６００−７５Ｘ）を表１の組成比（単位：固形分重量部）となるように加え、ＭＩＢＫ（メチルイソブチルケトン）またはＭＥＫ（メチルエチルケトン）を加えて０．５Ｐａ・ｓ以下に調整した後、３０℃で撹拌、混合して接着剤溶液を作成した。この接着剤をバーコータで、厚さ２５μｍのポリイミドフィルム（東レデュポン（株）製”カプトン”１００Ｖ−Ｐ）に約１０μｍの乾燥厚さとなるように塗布し、１５０℃で５分間乾燥し、シリコーン離型剤付きの厚さ２５μｍのポリエステルフィルムをラミネートして接着剤シートを得た。その後、１／２ｏｚの圧延銅箔（日鉱グールド・フォイル（株）製、ＪＴＣ箔）の非光沢面を合わせるようにラミネートし、銅張ポリイミドフィルムを作成した。また同接着剤を用いて、バーコータで、厚さ２５μｍのポリイミドフィルム（東レデュポン（株）製”カプトン”１００Ｖ−Ｐ）に約３０μｍの乾燥厚さとなるように塗布し、１５０℃で５分間乾燥し、シリコーン離型剤付きの厚さ２５μｍのポリエステルフィルムをラミネートしてカバーレイフィルムを得た。各特性を表１に示す。また高温高屈曲特性は上記銅張ポリイミドフィルムとカバーレイフィルムを組み合わせて作成したＦＰＣサンプルを用いて測定した。
【００５０】
実施例２〜５および比較例１〜２
実施例１と同一の方法で、それぞれ表１に示した原料および組成比（単位：固形分重量部）で調合した接着剤を用い銅張ポリイミドフィルム、カバーレイフィルムを作成した。特性を表１に示す。
【００５１】
表１の２〜５の実施例及び比較例１〜２から本発明により得られる銅張りポリイミドフィルム、カバーレイは、良好な高温屈曲特性を有しかつ高接着性、高半田耐熱性、柔軟性、電気特性に優れていた。
【００５２】
【表１】

【００５３】
尚、表１において、
（１）エピクロン８３０：ビスフェノールＦ型エポキシ樹脂（大日本インキ（株）製）
（２）Ｅｐ８３４：ビスフェノールＡ型エポキシ樹脂（ジャパンエポキシレジン（株）製）
（３）ＹＬ６９５４ＢＨ３０：ビスフェノールＦ型フェノキシ樹脂（ジャパンエポキシレジン（株）製）
（４）ＹＰＢ４０：臭素化ビスフェノールＡ型フェノキシ樹脂（東都化成（株）製）
（５）１６００−７５Ｘ：ダイマー酸変性エポキシ樹脂（大日本インキ工業（株）製）
（６）ＰＮＲ−１Ｈ：カルボキシル化ＮＢＲ（日本合成ゴム（製））
（７）ＤＩＣＹ７：ジシアンジアミド（ジャパンエポキシレジン（株）製）
（８）ＥＭＩ２４：２エチル４メチルイミダゾール（ジャパンエポキシレジン（株）製）。
【００５４】
【発明の効果】
高温環境下で良好な屈曲特性を有すると同時に、常温領域での高接着力、高半田耐熱、高柔軟性を同時に満足する半導体装置用接着剤組成物並びにそれを用いた接着剤シート、銅張りポリイミドフィルム、カバーレイを提供できる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an adhesive composition for semiconductor devices, a coverlay film and an adhesive sheet using the same, and a copper-clad polyimide film.
[0002]
[Prior art]
FPC (Flexible Printed Circuit Board) generally applies lithography technology to a copper-clad polyimide film (CCL) with a copper foil provided on one or both sides of a base film (such as a polyimide film or polyethylene terephthalate film) via an adhesive layer. In this configuration, a pattern circuit is formed, and a cover lay film serving as a protective layer is pasted thereon.
[0003]
An FPC material that is flexible and has excellent bending performance is suitable as a substrate for movable parts such as HDDs, CDs, DVDs, and hinges of various electronic devices. In recent years, along with further miniaturization of HDDs (2.5 inches), image recording units for home VTRs and game machines, data recording units for portable devices such as digital cameras and portable audio, or data recording units for in-vehicle car navigation Applications to various applications are also progressing.
[0004]
However, in recent years, with the evolution of mobile phones and small electronic devices, the demand for the high bending property of FPC has become much stricter. In particular, there is a need for a high-bending specification in a high-temperature environment at a location where the heat generation amount of the components and elements in the electronic device and the CPU increase significantly with the increase in the average temperature in the device. Yes. In other words, the operating environment temperature of laptop computers and in-vehicle devices during continuous use may reach about 80 ° C, and the softening of the adhesive layer at the above-mentioned operating environment temperature is possible with FPC materials that were assumed to be used at room temperature. This is because the phenomenon appears and the flexural properties are significantly deteriorated due to a decrease in the storage elastic modulus.
[0005]
In order to achieve the required bending performance of the FPC used for such movable parts, local strain accumulated on the metal copper foil during bending is suppressed, and internal cracks inherent in the copper foil are also suppressed. It is important how to suppress the growth, but as a method of improving such problems, the adhesive layer having a specific high elastic modulus suppresses softening of the adhesive, and good bending characteristics can be obtained even in a high temperature environment. A method for providing a heat-resistant and high-flexion FPC material has been proposed (see, for example, Patent Document 1).
[0006]
However, when the elastic modulus of the adhesive layer at room temperature to 100 ° C. is increased in order to give good bending characteristics in a high temperature environment, the FPC material characteristics at room temperature tend to be adversely affected. In other words, the toughness of the adhesive layer is impaired, the adhesive strength of the metal copper foil part and solder heat resistance in the FPC material are reduced, and the dimensional change rate deterioration and warpage of the copper-clad polyimide film (CCL) after the pattern circuit is formed The problem that the flexibility of FPC was impaired, such as generation | occurrence | production occurred.
[0007]
[Patent Document 1]
JP 2001-98243 A (47 to 48 stages)
[0008]
[Problems to be solved by the invention]
Provided is an adhesive composition for a semiconductor device that has good bending characteristics under a high temperature environment, simultaneously satisfies high adhesive strength, high solder heat resistance, and high flexibility in a normal temperature region, and is excellent in electrical characteristics. Furthermore, an adhesive sheet, a copper-clad polyimide film, and a coverlay film using the same are provided.
[0009]
[Means for Solving the Problems]
That is, the present invention is an adhesive composition for a semiconductor device comprising an epoxy resin, a phenoxy resin, a curing agent, and a dimer acid-modified epoxy resin.
[0010]
DETAILED DESCRIPTION OF THE INVENTION
The present invention is an adhesive for a semiconductor device that has been excellent in both high temperature and high bending properties, which have been difficult to achieve at the same time, and high adhesion of copper foil in FPC, high solder heat resistance, high flexibility, and electrical insulation. Yes, you can achieve it.
[0011]
The adhesive composition of the present invention comprises an epoxy resin and a phenoxy resin , It is composed of a curing agent and a dimer acid-modified epoxy resin.
[0012]
Generally, an adhesive composition in which a phenoxy resin, an epoxy resin, and a curing agent are mixed is formed by a cross-linked product of a flexible linear polymer chain formed by a cross-linking reaction of a phenoxy resin and a curing reaction of an epoxy resin. The three-dimensional cured product having a rigid structure is moderately entangled and effective in realizing good FPC bending characteristics in a high temperature environment. However, in order to achieve the FPC high-temperature high-flex characteristic, even if the Tg of the adhesive layer is increased, a decrease in the adhesive strength of the FPC material adhesive layer can be suppressed and warpage can be reduced. Is preferably used. That is, the dimer acid-modified epoxy resin is easy to form a cured product imparted with flexibility due to the structural factor of the dimer acid-modified part when forming an adhesive composition by a curing reaction, and an elastomer is formed in the adhesive layer. By imparting a unique property, the adhesion between the copper foil or organic insulating film and the adhesive layer can be improved. Furthermore, the addition of the dimer acid-modified epoxy resin increases the soft component in the adhesive layer, and even when a high Tg adhesive layer is used, it is possible to achieve both good dimensional change rate and warpage characteristics. Also, since the high Tg adhesive layer tends to be brittle to thermal shock, the solder heat resistance, which is an essential characteristic of FPC materials, also tends to deteriorate. However, the addition of a dimer acid-modified epoxy resin provides good solder heat resistance. Both can be achieved.
[0013]
The dimer acid-modified epoxy resin used in the present invention has high electrical insulation properties in addition to high Tg, high solder heat resistance, low dimensional stability, and high adhesive strength with copper foil as required performance in the FPC adhesive layer. In order to achieve a good balance, it is preferable to have at least one dimer acid selected from the general formulas (1), (2), and (3). The dimer acid-modified epoxy resin refers to a reaction of at least one carboxyl group in the dimer acid structure with a polyfunctional epoxy resin.
[0014]
[Chemical formula 2]

[0015]
The dimer acid-modified epoxy resin used here is preferably added in an amount of 2 to 30 parts by weight, more preferably 2 to 25 parts by weight, per 100 parts by weight of the total adhesive composition. If it is added in an amount of more than 30 parts by weight, the Tg of the cured product is lowered, and if it is less than 2 parts by weight, the solder heat resistance and dimensional stability are lowered.
[0016]
The epoxy resin used here is not particularly limited as long as it contains two or more epoxy groups. For example, bisphenol A, bisphenol F, bisphenol S, resorcinol, dihydroquinaphthalene, dicyclopentadiene diene. Cycloaliphatic epoxy resins such as diglycidyl ether such as phenol, epoxidized phenol novolak, epoxidized cresol novolak, epoxidized trisphenylol methane, epoxidized tetraphenyl ethane, biphenol type epoxy resin or novolak type epoxy resin And all brominated derivatives thereof.
[0017]
In order to achieve non-halogen flame retardant, an epoxy resin containing no halogen, particularly a non-brominated epoxy resin, can be selected. For example, an epoxy resin containing phosphorus or the like can be used. The type is not particularly limited. For example, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and its derivatives, 1,4-benzoquinone, 1,2-benzoquinone , A phosphorus-containing epoxy resin obtained by reacting an epoxy resin in advance with a compound obtained by reaction of tolquinone, 1,4-naphthoquinone, or the like.
[0018]
Furthermore, in order to increase the glass transition temperature (Tg) after curing of the adhesive composition containing an epoxy resin, as an epoxy resin having a bulky substituent, an aromatic ring such as biphenyl or naphthalene skeleton, or a condensed polycycle thereof. A bisphenol-based epoxy resin having a skeleton may be used.
[0019]
Moreover, the hardening | curing agent used for this invention is not specifically limited. For example, aromatic polyamines 3,3′5,5′-tetramethyl-4,4′-diaminodiphenylmethane, 3,3′5,5′-tetraethyl-4,4′-diaminodiphenylmethane, 3,3 ′ -Dimethyl-5,5'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dichloro-4,4'-diaminodiphenylmethane, 2,2'3,3'-tetrachloro-4,4'- Diaminodiphenylmethane, 4,4′-diaminodiphenylsulfide, 3,3′-diaminobenzophenone, 3,3′-diaminodiphenylsulfone, 4,4′-diaminodiphenylsulfone, 3,4′-diaminodiphenylsulfone, 4,4 '-Diaminobenzophenone, 3,4,4'-triaminodiphenyl sulfone, phenol novolac resin, etc. may be further used. Further, in order to control the curing speed and appropriate flexibility of the adhesive film, known curing agents such as dicyandiamide and acid anhydrides can also be used. In the case of an adhesive layer having a high Tg, the storage elastic modulus at room temperature of the adhesive layer tends to be high, and the adhesive strength with the copper foil in the FPC material is reduced, or a copper-clad polyimide film (CCL In order to reduce these problems, it is preferable to use dicyandiamide having excellent adhesion and a flexible structure.
[0020]
The phenoxy resin used in the present invention is a bisphenol A type phenoxy resin, a bisphenol F type phenoxy resin composed of bisphenol F that does not contain a polynuclear body, a bisphenol A and a bisphenol F that use bisphenol F that contains a polynuclear body. Polymer phenoxy resins, all brominated derivatives thereof, or derivatives obtained by previously reacting the above phenoxy resin with a compound having two or more functional groups that react with an epoxy resin such as a phenol hydroxyl group can be used. Further, a brominated phenoxy resin can be used for imparting necessary flame retardancy to the FPC material and improving the flexibility, adhesiveness and flexibility of the adhesive film. The epoxy equivalent of brominated phenoxy resin is preferably 2000 or more. If it is less than 2000, the necessary and sufficient flexibility cannot be imparted to the adhesive film.
[0021]
Moreover, it is preferable that 100-500 weight part is contained per 100 weight part of epoxy resins, and, as for the phenoxy resin used here, 100-300 weight part is more preferable. That is, if it is added in an amount of more than 500 parts by weight, there is a problem that the electrical insulating properties are lowered, and if it is less than 100, the flexibility of the cured adhesive composition cannot be achieved.
[0022]
In addition to the epoxy resin, the curing agent, and the phenoxy resin, a phenol resin, a curing accelerator, an elastomer, and the like may be added as necessary.
[0023]
For example, as the phenol resin, any known phenol resin such as a novolac type phenol resin and a resol type phenol resin can be used. For example, alkyl-substituted phenols such as phenol, cresol, pt-butylphenol, nonylphenol, p-phenylphenol, cyclic alkyl-modified phenols such as terpene and dicyclopentadiene, hetero groups such as nitro groups, halogen groups, cyano groups, and amino groups Containing a functional group containing an atom, having a skeleton such as naphthalene or anthracene, or a nitrogen-containing phenol such as bisphenol F, bisphenol A, bisphenol S, resorcinol, pyrogallol, or other polyfunctional phenol melamine modified or triazine modified phenol Resin.
[0024]
Further, examples of the curing accelerator include boron trifluoride amine complexes such as boron trifluoride triethylamine complex, imidazole derivatives such as 2-alkyl-4-methylimidazole and 2-phenyl-4-alkylimidazole, phthalic anhydride, anhydrous Examples include organic acids such as trimellitic acid, dicyandiamide, and the like. These may be used alone or in combination of two or more.
[0025]
In addition, modified types such as acrylic rubber, acrylonitrile butadiene rubber, and carboxyl group-containing acrylonitrile butadiene rubber (hereinafter referred to as NBR-C) can be added as the elastomer component. For example, as an example of NBR-C, a terminal group of a copolymer rubber obtained by copolymerizing acrylonitrile and butadiene at a molar ratio of about 10/90 to 50/50, or acrylonitrile, butadiene and acrylic acid, maleic acid. And terpolymer rubbers of carboxyl group-containing polymerizable monomers such as As specific NBR-C, PNR-1H (manufactured by Nippon Synthetic Rubber Co., Ltd.), “Nipol” 1072J, “Nipol” DN612, “Nipol” DN631 (above Nippon Zeon Co., Ltd.), “Hiker” CTBN (Manufactured by BF Goodrich).
[0026]
In addition to the above components, fine inorganic particles can be added as necessary. Fine inorganic particles include metal hydroxide such as aluminum hydroxide, magnesium hydroxide, calcium aluminate hydrate, zinc oxide, magnesium oxide, silica, alumina, zirconium oxide, antimony trioxide, pentoxide Examples include metal oxides such as antimony, titanium oxide, iron oxide, cobalt oxide, chromium oxide, and talc, metal fine particles such as aluminum, gold, silver, nickel, and iron, or carbon black and glass, but are particularly flame retardant. In this respect, aluminum hydroxide is preferable. Moreover, you may use these individually or in mixture of 2 or more types. In view of transparency and dispersion stability, the average particle size of the fine inorganic particles is preferably 0.2 to 5 μm.
[0027]
In addition, an antioxidant, an ion scavenger, melamine and derivatives thereof, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and derivatives thereof, as long as the properties of the adhesive are not impaired, What is added is an organic or inorganic component such as a compound obtained by a reaction of 4-benzoquinone, 1,2-benzoquinone, tolquinone, 1,4-naphthoquinone, etc., a phosphorous compound such as various phosphate esters, a silicone compound, etc. It is not limited.
[0028]
The adhesive sheet of the present invention is composed of at least one organic insulating film layer and at least one adhesive layer, and the insulating film referred to in the present invention includes polyimide, polyester, polyphenylene sulfide, poly It is a film having a thickness of 5 to 200 μm made of a plastic such as ether sulfone, polyether ether ketone, aramid, polycarbonate, polyarylate, and a plurality of films selected from these may be laminated. If necessary, surface treatment such as hydrolysis, corona discharge, low temperature plasma, physical roughening, and easy adhesion coating treatment can be performed.
[0029]
Further, the adhesive sheet for a semiconductor device of the present invention may be a protective film (release film) from which the organic insulating film can be peeled, and the material thereof is an adhesive layer and an adhesive sheet using the adhesive layer. If it can peel without impairing, it will not specifically limit. For example, a polyester film, a polyolefin film, and a paper obtained by laminating these with a silicone or fluorine compound coating treatment may be mentioned. Examples of the configuration include a peelable polyester protective film (12.5 to 150 μm) / adhesive layer (10 to 100 μm) / peelable polyester protective film (12.5 to 150 μm). Moreover, when the peeling force with respect to the adhesive bond layer of each protective film layer is set to F1 and F2 (F1> F2), F1-F2 is preferably 5 N / m or more, and more preferably 10 N / m or more. When F1-F2 is smaller than 5 N / m, it is not preferable which side of the protective film the release surface is on, which is not stable. The peeling forces F1 and F2 are both 1 to 200 N / m, preferably 3 to 150 N / m, and more preferably 3 to 100 N / m. If it is less than 1 N / m, the protective film will fall off, and if it exceeds 200 N / m, peeling will be difficult. Further, the protective film may be colored with a pigment so as to have good visibility during processing. Thereby, since the protective film of the side which peels previously can be recognized easily, misuse can be avoided.
[0030]
Examples of the adhesive sheet for a semiconductor device of the present invention include a coverlay film used as a protective layer for a patterned circuit formed on a copper-clad polyimide film and a tape with an adhesive for tape automated bonding (TAB). As a main structure of the coverlay film of the present invention, an organic insulating film (12.5 to 125 μm) such as a polyimide film or an aramid film / adhesive layer (5 to 50 μm) / peelable protective film (12.5) ˜125 μm) and the like.
[0031]
The main structure of the copper-clad polyimide film in which the organic insulating film and the copper foil are bonded via the adhesive layer of the present invention is, for example, a single-sided product: copper foil (9 to 35 μm) / adhesive layer (5 to 20 μm). / Polyimide film (12.5 to 125 μm), double-sided product: copper foil (9 to 35 μm) / adhesive layer (5 to 20 μm) / polyimide film (12.5 to 125 μm) / adhesive layer (5 to 20 μm) / Copper foil (9-35 micrometers) etc. are mentioned. In general, rolled copper foil, electrolytic copper foil, and the like can be used as the copper foil, but rolled copper foil is suitable for further stabilizing the bending characteristics of the copper-clad polyimide film, flexible printed wiring board, and FPC. It is.
[0032]
The tape with adhesive for tape automated bonding (TAB) is a peelable polyester protective film (12.5 to 150 μm) / adhesive layer (5 to 200 μm) / peelable polyester protective film (12.5 to 150 μm) or the like is slit to a predetermined standard width (29.7 to 60.6 mm), and an insulating sheet having a standard width of 35 to 70 mm is placed at the center of an insulating film at 100 to 160 ° C., 10 N / cm, 5 m. Examples are those prepared by hot roll lamination under the conditions of / min.
[0033]
Next, the manufacturing method of the adhesive sheet for semiconductor devices of this invention, a copper clad polyimide film, a coverlay film, and the tape with an adhesive for tape automated bonding (TAB) is illustrated and demonstrated.
[0034]
(1) Preparation of adhesive sheet for semiconductor device: A paint obtained by dissolving the adhesive composition of the present invention in a solvent is applied and dried on a polyester film subjected to release treatment on both sides. It is preferable to apply so that the thickness of the adhesive layer is 10 to 100 μm. Drying conditions are 100 to 200 ° C. and 1 to 5 minutes. Solvents are not particularly limited, but aromatics such as toluene, xylene and chlorobenzene, ketones such as methyl ethyl ketone and methyl ethyl isobutyl ketone (MIBK), aprotic such as dimethylformamide (DMF), dimethylacetamide and N-methylpyrodoline A polar system solvent alone or a mixture is preferred.
[0035]
A polyester or polyolefin protective film having higher releasability is laminated on the coated and dried adhesive layer to obtain the adhesive sheet of the present invention. Further, when the thickness of the adhesive is increased, the adhesive sheet may be laminated a plurality of times. In some cases, after the lamination, for example, the degree of curing may be adjusted by aging at 40 to 100 ° C. for about 1 to 200 hours.
[0036]
(2) Preparation of copper-clad polyimide film: MEK (methyl ethyl ketone), MIBK (methyl isobutyl ketone), CB (chlorobenzene), BA (benzyl alcohol) etc. as a solvent, epoxy resin, phenoxy resin, curing agent, curing accelerator, An adhesive solution is prepared by dissolving an inorganic filler, a flame retardant, and the like. This adhesive was applied to a 25 μm thick polyimide film (“Kapton” 100V-P manufactured by Toray DuPont Co., Ltd.) with a bar coater to a dry thickness of about 10 μm, dried at 150 ° C. for 5 minutes, A 25 μm thick polyester film with a mold is laminated to obtain an adhesive sheet. Thereafter, the polyester film of the adhesive sheet is peeled off, laminated to the non-glossy surface of a 1/2 oz rolled copper foil at 100 ° C. and 2.7 MPa, and then heated in an air oven at 150 ° C. for 5 hours. Create a copper-clad polyimide film. When creating a double-sided copper-clad polyimide film, after creating a single-sided adhesive sheet as described above, apply the adhesive again to the opposite side to create a double-sided adhesive sheet, and then apply copper on both sides. It can be created by laminating foil.
[0037]
(3) Preparation of coverlay film: Using an adhesive solution prepared in the same manner as in (2), using a bar coater, a 25 μm thick polyimide film (“Kapton” 100V-P manufactured by Toray DuPont Co., Ltd.) It is applied to a dry thickness of about 30 μm, dried at 150 ° C. for 5 minutes, and a 25 μm thick polyester film with a silicone release agent is laminated to obtain a coverlay film. Thereafter, it is common to perform aging at 50 ° C. for 20 to 50 hours to adjust the degree of curing so that the amount of oozing out of the adhesive becomes appropriate.
[0038]
(4) Preparation of tape with adhesive for tape automated bonding (TAB) tape: adhesive composition solution is coated on an insulating film such as polyimide by a coating method, dried and slit to a predetermined width. Get an adhesive tape. In addition, after the adhesive composition solution is applied by a coating method on a protective film such as a polyester film to which releasability is imparted and dried, a tape with an adhesive is slit to a standard width of 29.7 to 60.6 mm. Alternatively, a tape with adhesive for TAB may be used by hot roll laminating at a central portion of an insulating film having a standard width of 35 to 70 mm under conditions of 100 to 160 ° C., 10 N / cm, and 5 m / min.
[0039]
The use of the adhesive sheet for semiconductor devices, coverlay film, and copper-clad polyimide film of the present invention is not limited to flexible printed circuit boards made of copper-clad polyimide film and coverlay film, for example. Agent sheet The Stacked multilayer copper-clad polyimide film circuit board, rigid rigid board and flexible printed circuit board are laminated using an adhesive sheet, etc., mixed in a mixed form, TAB board, various package applications (CSP) , BGA) and the like. The TAB substrate manufacturing method and a general semiconductor connection circuit substrate are as follows.
[0040]
(5) TAB substrate manufacturing example
The electrolytic sample or rolled copper foil of 3 to 35 μm is laminated on the tape sample with adhesive (4) under the conditions of 110 to 180 ° C., 30 N / cm, and 1 m / min. If necessary, a stepwise heat curing treatment is performed in an air oven at 80 to 300 ° C. for 1 to 24 hours to prepare a TAB substrate. At this time, device holes and solder ball holes may be drilled in the tape sample with an adhesive before laminating the copper foil.
[0041]
(6) Manufacturing example of circuit board for semiconductor connection
The copper-clad polyimide film obtained in (2) and (5) above, and photoresist film formation, etching, resist stripping, electrolytic gold plating, and solder resist film formation are performed on the copper foil surface of the TAB substrate by a conventional method. Create a circuit board.
[0042]
【Example】
EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples. Before starting the description of the examples, a method for preparing a sample for evaluation of a copper-clad polyimide film and a coverlay film and a method for evaluating each property will be described.
(1) Evaluation method for each characteristic
A. Peel strength (peel)
Using a coverlay evaluation sample pressed on a glossy surface of a copper-clad polyimide film and 35 μm electrolytic copper foil (manufactured by Nikko Gould Foil Co., Ltd., JTC copper foil) under the conditions of 160 ° C. × 30 minutes × 4 MPa, JIS -Performed according to C6481.
[0043]
<Copper-clad polyimide film>
A copper foil pattern with a width of 2 mm is created by etching, and the strength is measured when the copper foil with a width of 2 mm is peeled off in the 90-degree direction using Tensilon (Orientec Co., Ltd., UTM-11-5HR type). (Tensile speed: 50 mm / min).
[0044]
<Sample for coverlay evaluation>
A notch with a width of 2 mm is made on the polyimide surface, and the strength is measured when the polyimide with a width of 2 mm is peeled in the direction of 90 degrees using Tensilon (Orientec Co., Ltd., UTM-11-5HR type) (Tensile speed) : 50 mm / min).
[0045]
B. Solder heat resistance
The method was performed in accordance with JIS-C6481. A. above. Created with Copper Cut a 20mm square sample of a stretched polyimide film and coverlay, adjust the humidity in an atmosphere of 40 ° C and 90% RH for 24 hours, and immediately float on a solder bath at a predetermined temperature for 30 seconds to swell the polyimide film And the maximum temperature without peeling was measured.
[0046]
C. Sliding and bending characteristics
A. A pattern of a bending resistance test sample disclosed in JIS C6471 was prepared on the copper-clad polyimide film prepared by the above method, and a coverlay film was press bonded at 160 ° C. × 30 minutes × 4 MPa to prepare a final test sample. Using this, with a FPC high-speed bending tester (manufactured by Shin-Etsu Engineering Co., Ltd.), a sample set with a frequency of 1500 cpm, a stroke of 20 mm, and a curvature of 2.5 mmR, with the coverlay surface side facing outward, The change in resistance value at each ambient temperature was measured, and the number of times the resistance increased to 20% or more from the initial value was defined as the number of flexing.
[0047]
D. Sled
Cover lay: After peeling off the release film from the 150 mm square cover lay, place it on a flat plate with the four corners floating, and measure the maximum distance from the flat plate.
[0048]
Copper-clad polyimide: After etching the entire copper foil from 150 mm square single-sided copper-clad polyimide, put it in an oven at 150 ° C x 1 hr, place it on a flat plate with the four corners floating, and set the maximum distance from the flat plate at room temperature. taking measurement.
[0049]
Example 1
Brominated bisphenol A type phenoxy resin (manufactured by Toto Kasei Co., Ltd., YPB40), epoxy resin (manufactured by Dainippon Ink Industries, Ltd., Epicron 830), dicyandiamide (curing agent manufactured by Japan Epoxy Resin Co., Ltd., DICY7), imidazole System curing accelerators (made by Japan Epoxy Residual Co., Ltd., EMI24) and dimer acid-modified epoxy resins (made by Dainippon Ink Industries, Ltd., 1600-75X) with the composition ratios (unit: solid content parts by weight) shown in Table 1. Then, MIBK (methyl isobutyl ketone) or MEK (methyl ethyl ketone) was added to adjust to 0.5 Pa · s or less, and the mixture was stirred and mixed at 30 ° C. to prepare an adhesive solution. This adhesive was applied to a 25 μm thick polyimide film (“Kapton” 100V-P manufactured by Toray DuPont Co., Ltd.) with a bar coater to a dry thickness of about 10 μm, dried at 150 ° C. for 5 minutes, A 25 μm thick polyester film with a mold was laminated to obtain an adhesive sheet. Then, it laminated so that the non-gloss surface of 1 / 2oz rolled copper foil (Nikko Gould foil Co., Ltd. product, JTC foil) might match, and the copper-clad polyimide film was created. Also, using the same adhesive, apply to a 25 μm thick polyimide film (“Kapton 100V-P” manufactured by Toray DuPont Co., Ltd.) with a bar coater to a dry thickness of about 30 μm, and dry at 150 ° C. for 5 minutes. Then, a 25 μm thick polyester film with a silicone release agent was laminated to obtain a coverlay film. Each characteristic is shown in Table 1. Moreover, the high temperature high bending property was measured using the FPC sample produced combining the said copper clad polyimide film and the coverlay film.
[0050]
Examples 2-5 and Comparative Examples 1-2
A copper-clad polyimide film and a coverlay film were prepared in the same manner as in Example 1 using adhesives prepared with the raw materials and composition ratios (unit: solid content by weight) shown in Table 1, respectively. The characteristics are shown in Table 1.
[0051]
The copper-clad polyimide films and coverlays obtained by the present invention from Examples 2 to 5 and Comparative Examples 1 and 2 in Table 1 have good high-temperature bending properties and high adhesion, high solder heat resistance, and flexibility. Excellent electrical properties.
[0052]
[Table 1]

[0053]
In Table 1,
(1) Epicron 830: Bisphenol F type epoxy resin (Dainippon Ink Co., Ltd.)
(2) Ep834: Bisphenol A type epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd.)
(3) YL6954BH30: Bisphenol F type phenoxy resin (manufactured by Japan Epoxy Resin Co., Ltd.)
(4) YPB40: Brominated bisphenol A type phenoxy resin (manufactured by Toto Kasei Co., Ltd.)
(5) 1600-75X: Dimer acid-modified epoxy resin (Dainippon Ink Industries, Ltd.)
(6) PNR-1H: Carboxylated NBR (Nippon Synthetic Rubber (made))
(7) DICY7: Dicyandiamide (manufactured by Japan Epoxy Resin Co., Ltd.)
(8) EMI24: 2-ethyl 4-methylimidazole (manufactured by Japan Epoxy Resin Co., Ltd.).
[0054]
【The invention's effect】
Adhesive composition for semiconductor device that has good bending characteristics under high temperature environment and at the same time satisfies high adhesive strength, high solder heat resistance, and high flexibility in normal temperature region, and adhesive sheet using the same, copper-clad A polyimide film and a coverlay can be provided.

Claims (8)

An adhesive composition for a semiconductor device comprising an epoxy resin, a phenoxy resin, a curing agent, and a dimer acid-modified epoxy resin. The adhesive composition for a semiconductor device according to claim 1, wherein the phenoxy resin has a brominated phenoxy resin. The adhesive composition for a semiconductor device according to claim 1, wherein the curing agent is dicyandiamide. The adhesive composition for a semiconductor device according to claim 1, wherein the phenoxy resin is contained in an amount of 100 to 300 parts by weight per 100 parts by weight of the epoxy resin. The adhesive composition for a semiconductor device according to claim 1, wherein the dimer acid-modified epoxy resin is contained in an amount of 2 to 25 parts by weight per 100 parts by weight of the adhesive composition for a semiconductor device. An adhesive sheet for a semiconductor device comprising an adhesive layer comprising the adhesive composition for a semiconductor device according to any one of claims 1 to 5 and at least one organic insulating film. The coverlay film using the adhesive composition for semiconductor devices in any one of Claims 1-5. The copper-clad polyimide film formed by adhere | attaching a polyimide film and copper foil through the adhesive bond layer which consists of an adhesive composition for semiconductor devices in any one of Claims 1-5.