JP2004182804A - Resin composition and film adhesive composed thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition which has a low glass transition temperature, excels in low temperature adhesion properties and, simultaneously, exhibits such excellent heat resistance as to maintain sufficient bond strength even at 260°C, and a film adhesive composed thereof. <P>SOLUTION: The resin composition comprises 100 pts.wt. polyimide resin and 1-100 pts.wt. epoxy compound to be represented by formula (1). The film adhesive is composed of the resin composition. The film adhesive is obtained by laminating the resin composition on one surface or both surfaces of a film. A metal laminate is obtained by laminating the resin composition on at least one surface of a metallic foil. <P>COPYRIGHT: (C)2004,JPO&NCIPI

Description

【００１１】
で表されるエポキシ化合物１〜１００重量部を含有することを特徴とする樹脂組成物。
（２）上記ポリイミド樹脂が、一般式（２）
【化５】

【００１２】
（Ｙは、４価の有機基を表し、Ｚは、
【化６】

よりなる２価の基を表し、ｎは０〜４の整数を表す。）で表される繰り返し構造単位を含有することを特徴とする（１）記載の樹脂組成物。
【００１３】
（３）（１）または（２）記載の樹脂組成物からなるフィルム状接着剤。
（４）フィルムの片面あるいは両面に、（１）または（２）記載の樹脂組成物を積層させてなるフィルム状接着剤。
（５）金属箔の少なくとも片面に、（１）または（２）記載の樹脂組成物を積層させてなる金属積層体に関する。
【００１４】
【発明の実施の形態】
以下、本発明を詳細に説明する。
本発明の樹脂組成物は、式（１）で表されるエポキシ化合物とポリイミド樹脂からなる樹脂組成物であり、用いられる式（１）で表されるエポキシ化合物のポリイミド樹脂への混合割合は、ポリイミド樹脂１００重量部に対して、１〜１００重量部、好ましくは５〜５０重量部である。エポキシ化合物の配合量が１重量部未満では、本発明の目的とする耐熱性の向上に効果はなく、また、１００重量部を超えると硬化後のフィルム形成能、応力緩和特性、耐熱性等が低下するため好ましくない。
【００１５】
本発明に使用する式（１）で表されるエポキシ化合物は、商品名がＶＧ３１０１である、三井化学株式会社製のものを使用できる。
【００１６】
本発明に使用するポリイミド樹脂は特に限定されないが、好ましくは熱可塑性ポリイミドであり、より好ましくは、一般式（２）
【化７】

【００１７】
（Ｙは、４価の有機基を表し、Ｚは、
【化８】

【００１８】
よりなる２価の基を表し、ｎは０〜４の整数を表す。）で表される繰り返し構造単位を含有することを特徴とする熱可塑性ポリイミドである。ｎは、好ましくは１〜４、更に好ましくは２である。
【００１９】
一般式（２）で表されるポリイミドは、一般式（３）、
【００２０】
【化９】

（Ｙは４価の有機基を表す。）で表される酸二無水物と一般式（４）、
【００２１】
【化１０】

（Ｚは
【００２２】
【化１１】

よりなる２価の基を表し、ｎは０〜４の整数を表す。）表されるジアミン化合物を必須成分として反応させ得られるポリアミド酸を熱的あるいは化学的にイミド化することにより得られる。尚、ｎは、好ましくは１〜４、更に好ましくは２である。
【００２３】
一般式（３）で表されるテトラカルボン酸二無水物は特に制限はなく、従来公知のテトラカルボン酸二無水物を用いることにより、様々なガラス転移温度を有するポリイミドを得ることができる。
【００２４】
本発明の樹脂組成物は、低いガラス転移温度を有し、好ましくは、２０℃〜１００℃、より好ましくは４０℃〜８０℃のものである。
【００２５】
一般式（３）の式中、Ｙは４価の有機基を表し、具体的には、炭素数２〜２７の、脂肪族基、脂環族基、単環式芳香族基、縮合多環式芳香族基、さらに芳香族基が直接または架橋員によって相互に連結された非縮合環式芳香族基を挙げることができる。
【００２６】
ここで使用されるテトラカルボン酸二無水物の具体例としては、例えば、ピロメリット酸二無水物、３，３’，４，４’−ベンゾフェノンテトラカルボン酸二無水物、３，３’，４，４’−ビフェニルテトラカルボン酸二無水物、オキシ−４，４’−ジフタル酸二無水物、エチレングリコールビストリメリート二無水物、２，２−ビス（４−（３，４−ジカルボキシフェノキシ）フェニル）プロパン二無水物、α，ω−ポリジメチルシロキサンテトラカルボン酸二無水物、α，ω−ビス（３，４−ジカルボキシフェニル）ポリジメチルシロキサン二無水物等が挙げられ、これらは単独あるいは２種以上混合して用いられる。好ましくは、オキシ−４，４’−ジフタル酸二無水物、α，ω−ポリジメチルシロキサンテトラカルボン酸二無水物である。
【００２７】
また、一般式（４）の具体的な例としては、１，３−ビス（３−アミノフェノキシ）ベンゼン、ビス（３−（３−アミノフェノキシ）フェニル）エーテル、１，３−ビス（３−（３−アミノフェノキシ）フェノキシ）ベンゼン、ビス（３−（３−（３−アミノフェノキシ）フェノキシ）フェニル）エーテル、１，３−ビス（３−（３−（３−アミノフェノキシ）フェノキシ）フェノキシ）ベンゼン、４，４’−ビス（３−アミノフェノキシ）ビフェニル等が挙げられる。好ましくは、１，３−ビス（３−（３−アミノフェノキシ）フェノキシ）ベンゼン、４，４’−ビス（３−アミノフェノキシ）ビフェニルである。
【００２８】
また、一般式（４）のジアミン化合物の他に、低温接着性を付与するためにジアミノシロキサン化合物を好適に用いることができる。ジアミノシロキサン化合物の具体的な種類としては、α，ω−ビス（２−アミノエチル）ポリジメチルシロキサン、α，ω−ビス（３−アミノプロピル）ポリジメチルシロキサン、α，ω−ビス（４−アミノブチル）ポリジメチルシロキサン、α，ω−ビス（４−アミノフェニル）ポリジメチルシロキサン、α，ω−ビス（３−アミノプロピル）ポリジフェニルシロキサン等が挙げられる。好ましくは、α，ω−ビス（３−アミノプロピル）ポリジメチルシロキサンである。
【００２９】
ジアミノシロキサン化合物の使用量は、全ジアミン成分の０〜８０モル％が好ましい。８０モル％を超えるとガラス転移温度が室温以下になり、フィルム状接着剤とした場合、タック性がでてしまい取り扱いが困難になる可能性がある。
【００３０】
本発明に係るポリイミドの製造方法としては、ポリイミドを製造可能な方法が公知方法を含め全て適用できる。中でも、有機溶媒中で反応を行うことが好ましい。このような反応において用いられる溶媒として、例えば、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ−メチル−２−ピロリドン、１，２−ジメトキシエタン、テトラヒドロフラン、１，３−ジオキサン、１，４−ジオキサン、ジメチルスルホキシド、ベンゼン、トルエン、キシレン、メシチレン、フェノール、クレゾール等が挙げられる。これらは単独あるいは２種以上混合して用いられる。
【００３１】
この反応における反応原料の濃度は、通常、２〜５０重量％、好ましくは５〜４０重量％であり、テトラカルボン酸二無水物とジアミン化合物との反応モル比は０．８〜１．２の範囲であることが好ましい。０．８未満でも１．２を超えても耐熱性が低下する場合がある。
【００３２】
反応温度は、通常、６０℃以下、好ましくは５０℃以下である。反応圧力は特に限定されず、常圧で十分実施できる。また、反応時間は反応原料の種類、溶媒の種類および反応温度によって異なるが、通常０．５〜２４時間で十分である。このような重縮合反応により、本発明に係るポリイミドの前駆体であるポリアミド酸が生成される。このポリアミド酸を好ましくは１００〜４００℃に加熱してイミド化するか、または無水酢酸等のイミド化剤を用いて化学イミド化することにより、ポリアミド酸に対応する繰り返し単位構造を有するポリイミドが得られる。
【００３３】
また、好ましくは１３０℃〜２５０℃で反応を行うことにより、ポリアミド酸の生成と熱イミド化反応が同時に進行し、本発明に係るポリイミドを得ることができる。すなわち、ジアミン成分、酸二無水物成分とを有機溶媒中に懸濁または溶解させ、１３０〜２５０℃の加熱下に反応を行い、ポリアミド酸の生成と脱水イミド化とを同時に行わせることにより、本発明に係るポリイミドを得ることができる。
【００３４】
本発明において、ポリイミド樹脂という表現は、１００％イミド化したポリイミド樹脂以外に、その前駆体であるポリアミド酸が一部共存した樹脂も含んでいる。
【００３５】
また、本発明の樹脂組成物は、必要に応じて上記エポキシ化合物及びポリイミド樹脂の他に、硬化促進の目的で硬化剤を配合することもできる。
【００３６】
硬化剤としては、エポキシ化合物と反応性を有し、エポキシ化合物を硬化させることができるものであれば特に限定されるものではない。例えば、イミダゾール系硬化剤、フェノール系硬化剤、アミン系硬化剤、酸無水物系硬化剤等が挙げられる。樹脂組成物の保存安定性という観点から、好ましくは、熱潜在性及び長い可使時間を有するものが良い。
【００３７】
硬化剤の配合量は、エポキシ化合物１００重量部に対して、０〜２０重量部の範囲内であることが好ましい。２０重量部を超えると樹脂溶液状態でゲルが生じやすくなり可能性があり、樹脂溶液の保存安定性が著しく低下する可能性がある。
【００３８】
本発明の樹脂組成物には、必要に応じて、公知の有機フィラーあるいは無機フィラーを配合しても良い。
有機フィラーとしては、エポキシ樹脂、メラミン樹脂、尿素樹脂、フェノール樹脂等の樹脂溶解溶剤に不溶になるまで高分子化あるいは架橋した微粒子タイプのフィラーが具体例として挙げられ、無機フィラーとしては、アルミナ、酸化アンチモン、フェライト等の金属酸化物の微粒子、あるいはタルク、シリカ、マイカ、カオリン、ゼオライト等のケイ酸塩類、硫酸バリウム、炭酸カルシウム等の微粒子が具体例として挙げられる。上記フィラーは単独または２種以上混合して使用することができる。
【００３９】
上記フィラーの配合量はポリイミド樹脂１００重量部に対して好ましくは０〜２００重量部、０〜１００重量部の範囲内であることがより好ましい。２００重量部を超えると、樹脂組成物の接着性が低下する可能性がある。
【００４０】
また、本発明の樹脂には、必要に応じて、カップリング剤を添加しても良い。カップリング剤は、本発明の目的を損なわないものであれば特に限定されるものではないが、樹脂溶解溶剤への溶解性が良好なものが好ましい。例えば、シラン系カップリング剤、チタン系カップリング剤等が具体例として挙げられる。
【００４１】
カップリング剤の配合量は、ポリイミド樹脂１００重量部に対して、好ましくは０〜５０重量部、更に好ましくは０〜３０重量部の範囲内である。５０重量部を超えると、樹脂組成物の耐熱性を損なう場合がある。
【００４２】
さらに、本発明の樹脂組成物には、本発明の目的を損なわない範囲で他の樹脂、例えばポリエチレン、ポリプロピレン、ポリカーボネート、ポリアリレート、ポリアミド、ポリスルホン、ポリエーテルスルホン、ポリエーテルケトン、ポリエーテルエーテルケトン、ポリフェニルスルフィド、変性ポリフェニレンオキシド、ポリアミドイミド、ポリエーテルイミド等を適当量配合することも可能である。
【００４３】
本発明の樹脂組成物は、上記ポリイミド樹脂、エポキシ化合物、硬化剤等を溶剤に溶解させて用いることができる。ここで用いられる溶剤としては、例えば、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ−メチル−２−ピロリドン、１，２−ジメトキシエタン、テトラヒドロフラン、１，３−ジオキサン、１，４−ジオキサン、ジメチルスルホキシド、ベンゼン、トルエン、キシレン、メシチレン、フェノール、クレゾール等が挙げられる。これらは単独あるいは２種以上混合して用いられる。
【００４４】
次いで、必要に応じてフィラー及びカップリング剤を加えて混合する。この場合、通常の攪拌機、三本ロール、ボールミル等の分散機を適宜組み合わせて、混練を行う。
【００４５】
本発明のフィルム状接着剤あるいは金属積層体を製造する方法は特に制限されるものではなく、例えば、樹脂溶液を、樹脂フィルム、耐熱性フィルム、あるいは金属箔の上に塗布した後、加熱して溶剤を揮発させフィルム化する方法が挙げられる。
【００４６】
尚、樹脂溶液は、樹脂フィルム、耐熱性フィルム等のフィルム、あるいは金属箔の片面あるいは両面に積層することが可能である。
【００４７】
ここで、樹脂フィルムとしては、公知の樹脂フィルムであればどのような材質でも良い。好ましくは剥離性に優れた樹脂フィルムが良い。例えば表面にシリコーン処理あるいはテフロン（登録商標）処理されたポリエチレンテレフタレートフィルム等が挙げられる。
【００４８】
耐熱性フィルムとしては、ポリイミド、ポリフェニレンスルフィド、ポリエーテル、ポリエーテルケトン、ポリエーテルエーテルケトンの耐熱性樹脂からなるフィルム、エポキシ樹脂−ガラスクロス、エポキシ樹脂−ポリイミド−ガラスクロス等の複合耐熱フィルム等が挙げられる。好ましくは、ポリイミドが挙げられる。
【００４９】
また、金属箔としては、圧延銅箔、電解銅箔、銅合金箔、ステンレス箔等が挙げられ、好ましくは、圧延銅箔、電解銅箔が挙げられる。
【００５０】
【実施例】
以下、本発明を、実施例によりさら詳細に説明するが、本発明はこれらの実施例に限定されるものではない。
【００５１】
（合成例１）
攪拌機、窒素導入管、温度計、メシチレンを満たしたディーンスターク管を備えた３００ｍｌの五つ口のセパラブルフラスコに、１，３−ビス（３−（３−アミノフェノキシ）フェノキシ）ベンゼン１５．００ｇ、シリコーンジアミン（α，ω−ビス（３−アミノプロピル）ポリジメチルシロキサン（東レ・ダウコーニング・シリコーン株式会社製、ＢＹ１６−８５３Ｕ、平均分子量９２０）４３．４４ｇ、Ｎ−メチル−２−ピロリドン１１０．６１ｇ、メシチレン４７．４０ｇを計り取り、窒素雰囲気下で５０℃に加熱し溶解させ、そこにオキシ−４，４’−ジフタル酸二無水物１８．４９ｇ、エチレングリコールビストリメリート二無水物８．１５ｇを少量ずつ添加した。その後、窒素導入管を溶液内に挿入し（バブリング状態にし）、系内の温度を１７０℃〜１８０℃に加熱し、突沸に注意しながら３０時間保持し、水を共沸除去することでポリイミド樹脂を得た。このポリイミド樹脂の対数粘度を、Ｎ−メチル−２−ピロリドンに０．５ｇ／ｄｌの濃度で溶解した後、３５℃において測定した結果、０．４９ｄｌ／ｇであった。
【００５２】
（合成例２）
攪拌機、窒素導入管、温度計、メシチレンを満たしたディーンスターク管を備えた３００ｍｌの五つ口のセパラブルフラスコに、４，４’−ビス（３−アミノフェノキシ）ビフェニル１２．００ｇ、シリコーンジアミン（α，ω−ビス（３−アミノプロピル）ポリジメチルシロキサン（東レ・ダウコーニング・シリコーン株式会社製、ＢＹ１６−８５３Ｕ、平均分子量９２０）４４．９５ｇ、Ｎ−メチル−２−ピロリドン１０９．８７ｇ、メシチレン４７．０９ｇを計り取り、窒素雰囲気下で５０℃に加熱し溶解させ、そこにオキシ−４，４’−ジフタル酸二無水物１９．１３ｇ、エチレングリコールビストリメリート二無水物８．４４ｇを少量ずつ添加した。その後、窒素導入管を溶液内に挿入し（バブリング状態にし）、系内の温度を１７０℃〜１８０℃に加熱し、突沸に注意しながら３０時間保持し、水を共沸除去することでポリイミド樹脂を得た。このポリイミド樹脂の対数粘度を、Ｎ−メチル−２−ピロリドンに０．５ｇ／ｄｌの濃度で溶解した後、３５℃において測定した結果、０．５２ｄｌ／ｇであった。
【００５３】
（合成例３）
攪拌機、窒素導入管、温度計、メシチレンを満たしたディーンスターク管を備えた３００ｍｌの五つ口のセパラブルフラスコに、１，３−ビス（３−アミノフェノキシ）ベンゼン１０．００ｇ、シリコーンジアミン（α，ω−ビス（３−アミノプロピル）ポリジメチルシロキサン（東レ・ダウコーニング・シリコーン株式会社製、ＢＹ１６−８５３Ｕ、平均分子量９２０）４７．２１ｇ、Ｎ−メチル−２−ピロリドン１１２．０２ｇ、メシチレン４８．０１ｇを計り取り、窒素雰囲気下で５０℃に加熱し溶解させ、そこにオキシ−４，４’−ジフタル酸二無水物２０．１０ｇ、エチレングリコールビストリメリート二無水物８．８６ｇを少量ずつ添加した。その後、窒素導入管を溶液内に挿入し（バブリング状態にし）、系内の温度を１７０℃〜１８０℃に加熱し、突沸に注意しながら３０時間保持し、水を共沸除去することでポリイミド樹脂を得た。このポリイミド樹脂の対数粘度を、Ｎ−メチル−２−ピロリドンに０．５ｇ／ｄｌの濃度で溶解した後、３５℃において測定した結果、０．４８ｄｌ／ｇであった。
【００５４】
（実施例１）
合成例１で得られたポリイミド樹脂１００重量部に対して、式（１）で表されるエポキシ化合物（三井化学株式会社製、ＶＧ３１０１）２０重量部、イミダゾール系硬化剤（四国化成工業株式会社、２ＭＡＯＫ−ＰＷ）１重量部を配合し、攪拌機にて十分に混合し、樹脂組成物を得た。得られた樹脂組成物を表面処理ＰＥＴフィルム（帝人デュポンフィルム株式会社製、Ａ３１、厚さ５０μｍ）上にキャストし、９０℃で２０分間加熱後、ＰＥＴフィルムを剥離し、厚さ２５μｍの単層フィルム状接着剤を得た。得られたフィルム状接着剤のガラス転移温度（Ｔｇ）をＴＭＡ（株式会社マック・サイエンス製、ＴＭＡ４０００）により測定した結果、４９℃であった。
耐熱性を評価するために、５ｍｍ角に切断した単層フィルム状接着剤を５ｍｍ角のシリコンチップと２０ｍｍ角のシリコンチップの間に挟み、２００℃、０．１Ｎ荷重、１秒間加熱圧着した後、１８０℃、無荷重、３時間、加熱硬化した。得られた試験片の剪断強度を、シェアテスターを用いて、２６０℃、３０秒間加熱時に測定した結果、７ＭＰａであった。
【００５５】
（実施例２）
合成例２で得られたポリイミド樹脂を使用した以外は実施例１と同様に樹脂配合、耐熱性評価を行った。結果を表１に示す。
【００５６】
（実施例３）
合成例３で得られたポリイミド樹脂を使用した以外は実施例１と同様に樹脂配合、耐熱性評価を行った。結果を表１に示す。
【００５７】
（比較例１）
実施例１におけるエポキシ化合物（三井化学株式会社製、ＶＧ３１０１）を市販されている脂肪族系エポキシ化合物（大日本インキ化学工業株式会社製、ＨＰ７２００）に代えた以外は実施例１と同様に樹脂配合、耐熱性評価を行った。結果を表２に示す。
【００５８】
（比較例２）
合成例１で得られたポリイミド樹脂をそのまま用いた（エポキシ化合物、硬化剤の配合なし）以外は実施例１と同様に耐熱性評価を行った。結果を表２に示す。
【００５９】
（比較例３）
合成例２で得られたポリイミド樹脂をそのまま用いた（エポキシ化合物、硬化剤の配合なし）以外は実施例１と同様に耐熱性評価を行った。結果を表２に示す。
【００６０】
（比較例４）
合成例３で得られたポリイミド樹脂をそのまま用いた（エポキシ化合物、硬化剤の配合なし）以外は実施例１と同様に耐熱性評価を行った。結果を表２に示す。
以上より、式（１）のエポキシ化合物（三井化学株式会社製、ＶＧ３１０１）とポリイミド樹脂からなる樹脂組成物からなるフィルム状接着剤は、低いガラス転移温度を有し低温接着性に優れ、２６０℃における強い熱時剪断強度を発現し耐熱性に優れていることがわかる。
【００６１】
【表１】

【００６２】
【表２】

【００６３】
【発明の効果】
本発明の樹脂組成物及びそれよりなるフィルム状接着剤は、低いガラス転移温度を有し、低温接着性に優れており、かつ、２６０℃においても十分な接着強度を保持する優れた耐熱性を発現し、半導体実装材料等の用途に好適に用いることができる。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a resin composition having excellent low-temperature adhesiveness and heat resistance, a film adhesive comprising the same, and a metal laminate. More specifically, the present invention relates to a resin composition containing a specific epoxy compound and a polyimide resin as main components, a film adhesive comprising the same, and a metal laminate.
[0002]
[Prior art]
In recent years, a film adhesive has come to be used for bonding between semiconductor elements such as ICs and LSIs and for bonding them to a lead frame material, instead of a paste adhesive conventionally used. . Especially in high-density mounting semiconductor packages with a small mounting area, such as chip size packages, stack packages, and system-in-packages, film adhesives that are superior in thickness accuracy and control over protrusion compared to paste adhesives are widely used. It is becoming.
[0003]
Along with these high-density mountings, semiconductor devices are becoming thinner. Affixing a film-like adhesive to a wafer having a thickness of 100 μm or less requires a surface used for thinning in order to prevent damage to the wafer. This is performed with a protective tape attached. If the bonding temperature in the bonding step is high, the surface protection tape having low heat resistance is thermally deteriorated, and the wafer is warped, which causes a serious problem in storing and transporting the wafer in the cartridge. Therefore, a film adhesive that can be bonded at a lower temperature has been demanded.
[0004]
As a film adhesive excellent in low-temperature adhesiveness, for example, a film adhesive composed of a silicone-modified polyimide resin having a relatively low glass transition temperature is known (see Patent Document 1). However, such a film adhesive made of a thermoplastic polyimide has a very low storage modulus at a temperature equal to or higher than the glass transition temperature, so that when it is used in a semiconductor package, it swells at the time of mounting and a package crack occurs. There was a risk of doing it.
[0005]
In order to prevent package cracking, a three-component resin composition of a silicone-modified polyimide resin, an epoxy compound, and a compound having an active hydrogen that reacts with the epoxy compound (curing agent) is disclosed (Patent Document 2). reference). However, the glass transition temperature of this resin composition is as high as 100 ° C. or higher, and it is difficult to say that the resin composition has excellent low-temperature adhesion. Further, the epoxy compound used here is not particularly limited, and it is considered preferable if the solubility with the polyimide resin is good, but the present inventors have proposed an aliphatic epoxy compound. When used, the heat resistance was not sufficient (see Comparative Examples below).
[0006]
On the other hand, in recent years, as environmental problems have been seriously considered, lead-free solder used for joining a semiconductor package and a substrate has been progressing. Sn-Ag-Cu-based solder has been cited as a promising candidate for lead-free solder, and its melting point is about 220 ° C, which is about 40 ° C higher than the current melting point of about 180 ° C for Sn-Pb-based solder. It is said that the surface temperature of the semiconductor package at the time of mounting using lead-free solder reaches 250 to 260 ° C. Therefore, there has been a demand for a film adhesive excellent in heat resistance that maintains a sufficient adhesive strength even at 260 ° C.
[0007]
[Patent Document 1]
Japanese Patent Application Laid-Open No. 5-331444 [Patent Document 2]
JP-A-9-59589
[Problems to be solved by the invention]
An object of the present invention is to provide a resin composition which has a low glass transition temperature, is excellent in low-temperature adhesiveness, and exhibits excellent heat resistance maintaining sufficient adhesive strength even at 260 ° C., and a film formed therefrom. The purpose is to provide an adhesive.
[0009]
[Means for Solving the Problems]
Means for Solving the Problems As a result of intensive studies, the present inventors have found that a polyimide resin composition containing a specific epoxy compound can solve the above problems, and completed the present invention.
[0010]
That is, the present invention
(1) Formula (1) is added to 100 parts by weight of the polyimide resin.
Embedded image

[0011]
A resin composition comprising 1 to 100 parts by weight of an epoxy compound represented by the formula:
(2) The above polyimide resin has a general formula (2)
Embedded image

[0012]
(Y represents a tetravalent organic group, and Z is
Embedded image

And n represents an integer of 0 to 4. (1) The resin composition according to (1), comprising a repeating structural unit represented by (1).
[0013]
(3) A film adhesive comprising the resin composition according to (1) or (2).
(4) A film adhesive obtained by laminating the resin composition according to (1) or (2) on one or both surfaces of a film.
(5) A metal laminate obtained by laminating the resin composition according to (1) or (2) on at least one surface of a metal foil.
[0014]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the present invention will be described in detail.
The resin composition of the present invention is a resin composition comprising an epoxy compound represented by the formula (1) and a polyimide resin, and the mixing ratio of the epoxy compound represented by the formula (1) to the polyimide resin is as follows: It is 1 to 100 parts by weight, preferably 5 to 50 parts by weight, based on 100 parts by weight of the polyimide resin. If the amount of the epoxy compound is less than 1 part by weight, there is no effect on the improvement of the heat resistance aimed at by the present invention, and if it exceeds 100 parts by weight, the film forming ability after curing, the stress relaxation property, the heat resistance, etc. It is not preferable because it lowers.
[0015]
As the epoxy compound represented by the formula (1) used in the present invention, a compound manufactured by Mitsui Chemicals, Inc. having a trade name of VG3101 can be used.
[0016]
The polyimide resin used in the present invention is not particularly limited, but is preferably a thermoplastic polyimide, and more preferably a general formula (2)
Embedded image

[0017]
(Y represents a tetravalent organic group, and Z is
Embedded image

[0018]
And n represents an integer of 0 to 4. A thermoplastic polyimide containing a repeating structural unit represented by the formula (1). n is preferably 1 to 4, and more preferably 2.
[0019]
The polyimide represented by the general formula (2) is represented by the general formula (3):
[0020]
Embedded image

(Y represents a tetravalent organic group) and an acid dianhydride represented by the general formula (4):
[0021]
Embedded image

(Z is [0022]
Embedded image

And n represents an integer of 0 to 4. ) Is obtained by thermally or chemically imidizing a polyamic acid obtained by reacting the represented diamine compound as an essential component. Incidentally, n is preferably 1 to 4, and more preferably 2.
[0023]
The tetracarboxylic dianhydride represented by the general formula (3) is not particularly limited, and polyimides having various glass transition temperatures can be obtained by using a conventionally known tetracarboxylic dianhydride.
[0024]
The resin composition of the present invention has a low glass transition temperature, preferably from 20C to 100C, more preferably from 40C to 80C.
[0025]
In the formula (3), Y represents a tetravalent organic group, specifically, an aliphatic group, an alicyclic group, a monocyclic aromatic group, a condensed polycyclic group having 2 to 27 carbon atoms. A non-condensed cyclic aromatic group in which aromatic groups are further linked to each other directly or by a bridging member can be given.
[0026]
Specific examples of the tetracarboxylic dianhydride used here include, for example, pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 3,3 ′, 4 , 4'-biphenyltetracarboxylic dianhydride, oxy-4,4'-diphthalic dianhydride, ethylene glycol bistrimellitic dianhydride, 2,2-bis (4- (3,4-dicarboxyphenoxy) ) Phenyl) propane dianhydride, α, ω-polydimethylsiloxane tetracarboxylic dianhydride, α, ω-bis (3,4-dicarboxyphenyl) polydimethylsiloxane dianhydride, etc. Alternatively, two or more kinds are used in combination. Preferred are oxy-4,4'-diphthalic dianhydride and α, ω-polydimethylsiloxane tetracarboxylic dianhydride.
[0027]
Specific examples of the general formula (4) include 1,3-bis (3-aminophenoxy) benzene, bis (3- (3-aminophenoxy) phenyl) ether, and 1,3-bis (3- (3-aminophenoxy) phenoxy) benzene, bis (3- (3- (3-aminophenoxy) phenoxy) phenyl) ether, 1,3-bis (3- (3- (3-aminophenoxy) phenoxy) phenoxy) Benzene, 4,4′-bis (3-aminophenoxy) biphenyl, and the like can be mentioned. Preferred are 1,3-bis (3- (3-aminophenoxy) phenoxy) benzene and 4,4′-bis (3-aminophenoxy) biphenyl.
[0028]
In addition to the diamine compound represented by the general formula (4), a diaminosiloxane compound can be suitably used for imparting low-temperature adhesiveness. Specific types of diaminosiloxane compounds include α, ω-bis (2-aminoethyl) polydimethylsiloxane, α, ω-bis (3-aminopropyl) polydimethylsiloxane, α, ω-bis (4-amino Butyl) polydimethylsiloxane, α, ω-bis (4-aminophenyl) polydimethylsiloxane, α, ω-bis (3-aminopropyl) polydiphenylsiloxane, and the like. Preferably, α, ω-bis (3-aminopropyl) polydimethylsiloxane is used.
[0029]
The amount of the diaminosiloxane compound used is preferably from 0 to 80 mol% of the total diamine component. If it exceeds 80 mol%, the glass transition temperature will be lower than room temperature, and when it is used as a film adhesive, tackiness may be caused and handling may be difficult.
[0030]
As a method for producing a polyimide according to the present invention, any method capable of producing a polyimide, including known methods, can be applied. Among them, the reaction is preferably performed in an organic solvent. As a solvent used in such a reaction, for example, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,2-dimethoxyethane, tetrahydrofuran, 1,3-dioxane, , 4-dioxane, dimethylsulfoxide, benzene, toluene, xylene, mesitylene, phenol, cresol and the like. These may be used alone or in combination of two or more.
[0031]
The concentration of the reaction raw materials in this reaction is usually 2 to 50% by weight, preferably 5 to 40% by weight, and the reaction molar ratio of the tetracarboxylic dianhydride to the diamine compound is 0.8 to 1.2. Preferably, it is within the range. If it is less than 0.8 or more than 1.2, the heat resistance may decrease.
[0032]
The reaction temperature is usually 60 ° C or lower, preferably 50 ° C or lower. The reaction pressure is not particularly limited, and the reaction can be carried out at normal pressure. The reaction time varies depending on the type of the reaction raw material, the type of the solvent and the reaction temperature, but usually 0.5 to 24 hours is sufficient. By such a polycondensation reaction, a polyamic acid which is a precursor of the polyimide according to the present invention is generated. The polyamic acid is preferably imidized by heating to 100 to 400 ° C. or chemically imidized using an imidizing agent such as acetic anhydride to obtain a polyimide having a repeating unit structure corresponding to the polyamic acid. Can be
[0033]
Further, by preferably performing the reaction at 130 ° C. to 250 ° C., the generation of the polyamic acid and the thermal imidization reaction proceed simultaneously, and the polyimide according to the present invention can be obtained. That is, a diamine component and an acid dianhydride component are suspended or dissolved in an organic solvent, a reaction is performed under heating at 130 to 250 ° C., and a polyamic acid is simultaneously generated and dehydrated by imidization. The polyimide according to the present invention can be obtained.
[0034]
In the present invention, the expression “polyimide resin” includes, in addition to a 100% imidized polyimide resin, a resin partially coexisting with a polyamic acid as a precursor thereof.
[0035]
Further, the resin composition of the present invention may optionally contain a curing agent for the purpose of promoting curing, in addition to the epoxy compound and the polyimide resin.
[0036]
The curing agent is not particularly limited as long as it has reactivity with the epoxy compound and can cure the epoxy compound. For example, an imidazole-based curing agent, a phenol-based curing agent, an amine-based curing agent, an acid anhydride-based curing agent, and the like can be given. From the viewpoint of storage stability of the resin composition, those having a heat potential and a long pot life are preferable.
[0037]
The compounding amount of the curing agent is preferably in the range of 0 to 20 parts by weight based on 100 parts by weight of the epoxy compound. If the amount is more than 20 parts by weight, gel may be easily generated in the resin solution state, and the storage stability of the resin solution may be significantly reduced.
[0038]
The resin composition of the present invention may contain a known organic filler or inorganic filler as necessary.
Specific examples of the organic filler include an epoxy resin, a melamine resin, a urea resin, and a fine particle type filler that has been polymerized or cross-linked until insoluble in a resin dissolving solvent such as a phenol resin.As the inorganic filler, alumina, Specific examples thereof include fine particles of a metal oxide such as antimony oxide and ferrite, or fine particles such as silicates such as talc, silica, mica, kaolin, and zeolite, and barium sulfate and calcium carbonate. The above fillers can be used alone or in combination of two or more.
[0039]
The amount of the filler is preferably in the range of 0 to 200 parts by weight, more preferably 0 to 100 parts by weight, based on 100 parts by weight of the polyimide resin. If it exceeds 200 parts by weight, the adhesiveness of the resin composition may be reduced.
[0040]
Further, a coupling agent may be added to the resin of the present invention, if necessary. The coupling agent is not particularly limited as long as the object of the present invention is not impaired, but a coupling agent having good solubility in a solvent for dissolving the resin is preferable. For example, silane-based coupling agents, titanium-based coupling agents, and the like are specific examples.
[0041]
The amount of the coupling agent is preferably 0 to 50 parts by weight, more preferably 0 to 30 parts by weight, based on 100 parts by weight of the polyimide resin. If it exceeds 50 parts by weight, the heat resistance of the resin composition may be impaired.
[0042]
Further, the resin composition of the present invention includes other resins, for example, polyethylene, polypropylene, polycarbonate, polyarylate, polyamide, polysulfone, polyethersulfone, polyetherketone, and polyetheretherketone, as long as the object of the present invention is not impaired. , Polyphenyl sulfide, modified polyphenylene oxide, polyamide imide, polyether imide and the like can be blended in appropriate amounts.
[0043]
The resin composition of the present invention can be used by dissolving the above polyimide resin, epoxy compound, curing agent and the like in a solvent. Examples of the solvent used here include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,2-dimethoxyethane, tetrahydrofuran, 1,3-dioxane, 1,4 -Dioxane, dimethyl sulfoxide, benzene, toluene, xylene, mesitylene, phenol, cresol and the like. These may be used alone or in combination of two or more.
[0044]
Next, a filler and a coupling agent are added and mixed as needed. In this case, kneading is carried out by appropriately combining ordinary dispersers such as a stirrer, a three-roll mill, and a ball mill.
[0045]
The method for producing the film adhesive or the metal laminate of the present invention is not particularly limited.For example, a resin solution is applied on a resin film, a heat-resistant film, or a metal foil, and then heated. A method of volatilizing the solvent to form a film may be used.
[0046]
The resin solution can be laminated on one side or both sides of a film such as a resin film or a heat-resistant film, or a metal foil.
[0047]
Here, the resin film may be any material as long as it is a known resin film. Preferably, a resin film having excellent releasability is preferred. For example, a polyethylene terephthalate film whose surface is treated with silicone or Teflon (registered trademark) is exemplified.
[0048]
Examples of the heat-resistant film include polyimide, polyphenylene sulfide, polyether, polyether ketone, a film made of a polyether ether ketone heat-resistant resin, an epoxy resin-glass cloth, and a composite heat-resistant film such as an epoxy resin-polyimide-glass cloth. No. Preferably, a polyimide is used.
[0049]
Examples of the metal foil include a rolled copper foil, an electrolytic copper foil, a copper alloy foil, a stainless steel foil, and the like, and preferably, a rolled copper foil and an electrolytic copper foil.
[0050]
【Example】
Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.
[0051]
(Synthesis example 1)
15.00 g of 1,3-bis (3- (3-aminophenoxy) phenoxy) benzene was placed in a 300 ml five-neck separable flask equipped with a stirrer, a nitrogen inlet tube, a thermometer, and a Dean-Stark tube filled with mesitylene. , 43.44 g of silicone diamine (α, ω-bis (3-aminopropyl) polydimethylsiloxane (manufactured by Dow Corning Toray Silicone Co., Ltd., BY16-853U, average molecular weight 920), N-methyl-2-pyrrolidone 110. 61 g and 47.40 g of mesitylene are weighed and dissolved by heating to 50 ° C. under a nitrogen atmosphere, and 18.49 g of oxy-4,4′-diphthalic dianhydride and ethylene glycol bistrimellitic dianhydride are added thereto. Then, a nitrogen introduction tube was inserted into the solution (to bubbling state), and the system was added. Was heated to 170 ° C. to 180 ° C., kept for 30 hours while paying attention to bumping, and azeotropically removed water to obtain a polyimide resin. After dissolving in pyrrolidone at a concentration of 0.5 g / dl, it was measured at 35 ° C. and found to be 0.49 dl / g.
[0052]
(Synthesis example 2)
In a 300 ml five-neck separable flask equipped with a stirrer, a nitrogen inlet tube, a thermometer, and a Dean-Stark tube filled with mesitylene, 12.00 g of 4,4′-bis (3-aminophenoxy) biphenyl, silicone diamine ( 44.95 g of α, ω-bis (3-aminopropyl) polydimethylsiloxane (manufactured by Dow Corning Silicone Toray Co., Ltd., BY16-853U, average molecular weight 920), 109.87 g of N-methyl-2-pyrrolidone, mesitylene 47 0.09 g was weighed and dissolved at 50 ° C. under a nitrogen atmosphere, and 19.13 g of oxy-4,4′-diphthalic dianhydride and 8.44 g of ethylene glycol bistrimellitic dianhydride were added little by little. Thereafter, a nitrogen inlet tube was inserted into the solution (to bubbling state), and the temperature in the system was increased to 170 ° C. The mixture was heated to about 180 ° C., kept for 30 hours while paying attention to bumping, and azeotropically removed from water to obtain a polyimide resin whose logarithmic viscosity was 0.5 g in N-methyl-2-pyrrolidone. After dissolving at a concentration of / dl, it was measured at 35 ° C to find that it was 0.52 dl / g.
[0053]
(Synthesis example 3)
In a 300 ml five-neck separable flask equipped with a stirrer, a nitrogen inlet tube, a thermometer, and a Dean-Stark tube filled with mesitylene, 10.00 g of 1,3-bis (3-aminophenoxy) benzene, silicone diamine (α) , Ω-bis (3-aminopropyl) polydimethylsiloxane (BY16-853U, Toray Dow Corning Silicone Co., Ltd., average molecular weight 920) 47.21 g, N-methyl-2-pyrrolidone 112.02 g, mesitylene 48. 01 g was weighed out, heated and dissolved at 50 ° C. under a nitrogen atmosphere, and 20.10 g of oxy-4,4′-diphthalic dianhydride and 8.86 g of ethylene glycol bistrimellitic dianhydride were added little by little. Thereafter, a nitrogen inlet tube was inserted into the solution (to bubbling state), and the temperature in the system was set to 170 ° C. The polyimide resin was heated to 180 ° C., kept for 30 hours while paying attention to bumping, and azeotropically removed water to obtain a polyimide resin whose logarithmic viscosity was 0.5 g / N-methyl-2-pyrrolidone. After dissolving at a concentration of dl, it was measured at 35 ° C. and found to be 0.48 dl / g.
[0054]
(Example 1)
Based on 100 parts by weight of the polyimide resin obtained in Synthesis Example 1, 20 parts by weight of an epoxy compound represented by the formula (1) (VG3101 manufactured by Mitsui Chemicals, Inc.), an imidazole-based curing agent (Shikoku Chemical Industry Co., Ltd.) 2MAOK-PW) was mixed with 1 part by weight and sufficiently mixed with a stirrer to obtain a resin composition. The obtained resin composition is cast on a surface-treated PET film (A31, manufactured by Teijin DuPont Films Co., Ltd., A31, thickness 50 μm), heated at 90 ° C. for 20 minutes, and then the PET film is peeled off to form a monolayer having a thickness of 25 μm. A film adhesive was obtained. The glass transition temperature (Tg) of the obtained film adhesive was 49 ° C. as a result of measurement by TMA (TMA 4000, manufactured by Mac Science Corporation).
In order to evaluate the heat resistance, a single-layered film-like adhesive cut into a square of 5 mm is sandwiched between a silicon chip of 5 mm square and a silicon chip of 20 mm square, and heated and pressed at 200 ° C. under a load of 0.1 N for 1 second. , 180 ° C, no load, and heat-cured for 3 hours. The shear strength of the obtained test piece was measured at 260 ° C. for 30 seconds using a shear tester, and as a result, it was 7 MPa.
[0055]
(Example 2)
Except that the polyimide resin obtained in Synthesis Example 2 was used, the resin blending and heat resistance evaluation were performed in the same manner as in Example 1. Table 1 shows the results.
[0056]
(Example 3)
Except for using the polyimide resin obtained in Synthesis Example 3, the resin formulation and heat resistance evaluation were performed in the same manner as in Example 1. Table 1 shows the results.
[0057]
(Comparative Example 1)
Resin blending in the same manner as in Example 1 except that the epoxy compound (VG3101, manufactured by Mitsui Chemicals, Inc.) in Example 1 was replaced with a commercially available aliphatic epoxy compound (HP7200, manufactured by Dainippon Ink and Chemicals, Inc.) And heat resistance evaluation. Table 2 shows the results.
[0058]
(Comparative Example 2)
The heat resistance was evaluated in the same manner as in Example 1 except that the polyimide resin obtained in Synthesis Example 1 was used as it was (without blending of an epoxy compound and a curing agent). Table 2 shows the results.
[0059]
(Comparative Example 3)
The heat resistance was evaluated in the same manner as in Example 1, except that the polyimide resin obtained in Synthesis Example 2 was used as it was (without blending of an epoxy compound and a curing agent). Table 2 shows the results.
[0060]
(Comparative Example 4)
The heat resistance was evaluated in the same manner as in Example 1, except that the polyimide resin obtained in Synthesis Example 3 was used as it was (without blending of an epoxy compound and a curing agent). Table 2 shows the results.
As described above, the film adhesive composed of the resin composition composed of the epoxy compound of formula (1) (VG3101 manufactured by Mitsui Chemicals, Inc.) and a polyimide resin has a low glass transition temperature, excellent low-temperature adhesion, and 260 ° C. It can be seen that a high heat-induced shear strength is exhibited and the heat resistance is excellent.
[0061]
[Table 1]

[0062]
[Table 2]

[0063]
【The invention's effect】
The resin composition of the present invention and the film adhesive comprising the same have a low glass transition temperature, are excellent in low-temperature adhesiveness, and have excellent heat resistance of maintaining sufficient adhesive strength even at 260 ° C. And can be suitably used for applications such as semiconductor packaging materials.

Claims (5)

Formula (1) is added to 100 parts by weight of the polyimide resin.

A resin composition comprising 1 to 100 parts by weight of an epoxy compound represented by the formula: The polyimide resin has a general formula (2)

(Y represents a tetravalent organic group, and Z is

And n represents an integer of 0 to 4. 2. The resin composition according to claim 1, which contains a repeating structural unit represented by the formula: A film adhesive comprising the resin composition according to claim 1. 3. A film-like adhesive obtained by laminating the resin composition according to claim 1 on one or both sides of a film. A metal laminate obtained by laminating the resin composition according to claim 1 on at least one surface of a metal foil.