JP4108161B2 - Anisotropic conductive composition and film - Google Patents
Anisotropic conductive composition and film Download PDFInfo
- Publication number
- JP4108161B2 JP4108161B2 JP27843897A JP27843897A JP4108161B2 JP 4108161 B2 JP4108161 B2 JP 4108161B2 JP 27843897 A JP27843897 A JP 27843897A JP 27843897 A JP27843897 A JP 27843897A JP 4108161 B2 JP4108161 B2 JP 4108161B2
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- JP
- Japan
- Prior art keywords
- anisotropic conductive
- type
- resin
- film
- conductive composition
- Prior art date
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Classifications
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
- H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
- H05K3/321—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by conductive adhesives
Landscapes
- Conductive Materials (AREA)
Description
【0001】
【発明の属する技術分野】
本発明の異方導電性組成物及びフィルムは、液晶パネル、プラズマディスプレイ、ELディスプレイへのTAB、FPC接続や、LSIベアチップのCOG接続、LSIベアチップのプリント基板上へのCOB接続、COF接続や、フレキシブル基板のディスプレイパネルへの接続、フレキシブル基板とリジッド基板との接続に用いることができる。特に、液晶テレビ、携帯電話、液晶カメラ、時計、ワープロ、コピー機、電話、パソコン、プラズマディスプレイ、ELパネル、計算機などのファインピッチ用途に有効である。
【0002】
【従来の技術】
これまでに、液晶用ドライバーICの接続などに異方導電性フィルムが数多く用いられてきている。液晶自体も小型化、接続端子のファインピッチ化が急速に進んできている。
従来より多くの異方導電性フィルムが開示されてきているが、例えば、特開平7−197001号公報、特開平4−242010号公報に示されるような樹脂ボール上に金属メッキを施した導電粒子を用いた異方導電性フィルムや、ニッケル粉、はんだ粉、金メッキニッケル粉などの金属粉を用いた異方導電性フィルムが開示されている(例えば特開昭61−55809号公報)。
【0003】
異方導電性フィルムは、導電粒子を有機バインダー中に分散したフィルム状のものであり、接続したい基板上の電極あるいは端子上に予め貼り合わせておき、被接続基板や被接続LSIをアライメントした後に加圧、加熱して有機バインダーを乾燥あるいは加熱硬化する。この時、電極間に挟まっている導電粒子のみが変形して電極間方向にのみ導電性を有し、隣接電極同士は絶縁性が保持されるものである。液晶、プラズマディスプレイ、ELなどのパネルの駆動用ICのTAB接続や、LSIベアチップの接続、フレキシブル基板のパネル接続などに用いられてきた。
【0004】
【発明が解決しようとする課題】
従来より用いられてきた異方導電性フィルムは以下の制限があった。すなわち、金属メッキ樹脂粉は導通がメッキ金属層でしかないため、50μのファインピッチ接続の場合には、導通に寄与する粒子数が減少するために、ますます接続抵抗が増加して高い駆動電圧が必要になる。また、金属メッキ樹脂粉の場合には、加圧で導電粉末が変形する場合に、メッキ剥がれを生じ絶縁不良を頻繁に引き起こしている。また、金属粉の場合には、ニッケル粉では、本来固有抵抗も高いが、耐環境性が悪く、接続抵抗が上昇する。また、ニッケル粉は硬いために接続時の圧力が数十kg/cm2と必要であり、このため、基板へのダメージが大きく、例えば、ガラス基板に用いた場合には基板の破損の問題を起こしていた。半田粉では、金属粉の中でももともと固有抵抗が高く、ファインピッチ接続の対応ができず、また、融点が低いために加熱接続時に半融の状態がしばしば起こる。金メッキニッケル粉の場合には、金メッキが加圧時に剥がれ落ちることや、やはりニッケルを用いると高加圧力が必要になる。また、電極が柔らかいと、電極を変形させてしまうことがしばしばあった。銀粉末の場合には、隣接電極間での絶縁性低下が吸水などで起きやすく、ファインピッチ接続への対応ができない状態であった。
【0005】
また、最近の高生産性の点から加圧時間を数秒と短時間で行いたい要求があるが、上記の物を用いたものでは、熱伝導性が悪く、数秒の接続では硬化不足で接続不良が著しかった。また、ファインピッチ接続では、フィルム中の導電粉末の分散不足で、しばしば接続不良の端子が生じていた。さらに、ファインピッチであるが高電流を流したい要求が高まってきているが、公知のものでは、抵抗が高いのみならず熱伝導性が悪く、抵抗値が上昇して電流をある程度以上流せないのが現状であった。
【0006】
また、導電粒子を分散させている有機バインダーとしては、熱硬化タイプとしてエポキシ樹脂を接着性の点から用いる場合が多いが、従来の異方導電性フィルムでは、LSIのベアチップ実装化が進む中で、チップとの熱膨張係数が著しくことなる有機基板への接続できる異方導電性組成物が要求されてきたが、アスペクト比の高いチップなどでは、端のバンプでのストレスにより接続不良が頻繁に起こっている。有機基板においては、高温度でも良いから3〜5秒と短時間で高生産性良く接続するこが要求されているが、異方導電性フィルム耐熱性が不十分であったり、導電フィラーの熱伝導性が不十分であったりした。また、ベアチップ実装後に他の部品を接続するために260℃前後でのリフローを繰り返し行うが、このための耐熱性が不十分であった。また、低分子量エポキシなどでは、室温度で長期に保存していた場合には、異方導電性フィルムでのベースフィルムからのはみ出しなどが有り、リールから引き出すときに、背面転写などを引き起こしていた。
【0007】
【課題を解決するための手段】
そこで上記問題点を解決するために、本発明では、
1.一般式M x Cu 1-x (MはAg、Auより選ばれた1種以上、0.01≦x≦0.6、xは原子比)で表され、且つ粉末表面の銀あるいは金濃度が平均の銀あるいは金濃度より高く、平均粒子径2〜15μの金属粉末1重量部に対し、エポキシ樹脂を含む有機バインダーを0.1〜120重量部、さらに前記エポキシ樹脂100重量部に対して硬化剤としてマイクロカプセル型のイミダゾール誘導体エポキシ化合物5〜250重量部有する異方導電性組成物であって、前記エポキシ樹脂はナフタレン骨格に少なくとも2官能以上のグリシジルエーテル結合を有するナフタレン型エポキシ樹脂を含有し、前記マイクロカプセル型イミダゾール誘導体エポキシ化合物の平均粒子径が1〜10μ、最小粒子径/最大粒子径比が0.001〜0.6、であることを特徴とする異方導電性組成物、
2. 有機バインダ−として、ナフタレン骨格の2,3,4官能グリシジルエーテル結合を有するナフタレン型エポキシ樹脂以外に、ビスフェノールA型、ビスフェノールF型、フェノールノボラック型、クレゾールノボラック型、脂環式、アルキル多価フェノール型、ウレタン変性型、脂肪酸変性型、ゴム変性型エポキシ樹脂、及びフェノキシ樹脂、ウレタン樹脂、ポリエステル樹脂、アクリル樹脂、SBR、NBR、シリコーン樹脂より選ばれた1種以上の樹脂を含有していることを特徴とする1.記載の異方導電性組成物、
3. 金属粉末の粒度分布において、平均粒子径±2μ以内の粉末が30〜100体積%以上であることを特徴とする1.又は2.に記載の異方導電性組成物、
4. 1.〜3.いずれかに記載の異方導電性組成物をフィルム状としたことを特徴とする異方導電性フィルム、を提供するものである。
【0008】
本発明で用いる金属粉末は、一般式MxCu1ーx(MはAg、Auより選ばれた1種以上、0.01≦x≦0.6、xは原子比)で表され、且つ粉末表面の銀あるいは金濃度が平均の銀あるいは金濃度より高いことを特徴とする平均粒子径2〜15μの金属粉末であるが、銅と銀、金の両者の高導電性を有する導電粉末であるために、接続時の高導電性、ファインピッチでの粒子数が減少しても高導電性が維持できることにある。この場合、xが0.6を超える場合には、銀成分が多く隣接電極間でのマイグレーションの問題が起こり短絡につながる。xが0.01未満の場合には、耐酸化性が不足して導通抵抗が著しく上がる。好ましくは、xが0.04〜0.4である。基板あるいは被接続基板の電極あるいは端子は銅を主成分にするものが多く。このため、ヒートサイクルなどの試験においても熱膨張係数が近く接続抵抗の変化が少ないなどの特徴を有する。また、銅を主成分とした金属粉末表面の銀及び金濃度が平均の銀及び金濃度より高いことで電極との接続点での金属粉末の酸化劣化が防止でき、且つ銀のマイグレーション性を防止できる。金属粉末表面の銀あるいは金濃度は平均の銀あるいは金濃度より高いことが好ましい。
【0009】
粉末表面の銀あるいは金濃度とは、XPS(X線光電子分光分析計;XSAM800;KRATOS社製)で測定した、Cu2p、Ag3d、Auの面積値から装置内補正係数を用いて算出した値(Ag+Au/(Cu+Ag+Au))である。金属粉末の平均銀、金、銅濃度は、金属粉末を濃硝酸あるいは王水溶液中に溶解してICP(高周波誘導結合型プラズマ分析計(セイコー電子工業製;JY38P2)を用いて測定した。また、本発明で用いる銅合金粉末は、特性を損なわない程度で有れば、Pt、Sn、Zn、Pd、P、B、C、Ti、Si、V、Mg、Al、Hf、Pb、Mn、Niなどを添加しても構わない。
【0010】
また、金属粉末の平均粒子径は2〜15μが好ましく、2μ未満であると、加圧時に電極間に挟まる導電粒子が電極面の粗さレベルになり、導電性が不良になるのと耐環境性が悪くなる。15μを超える場合には、ファインピッチでの電極間接合で、電極間の導電粒子数が不十分になり接続抵抗が不安定になる。好ましくは平均粒子径が2〜13μである。また、好ましくは、平均粒子径±2μ以内の粉末の存在率が30%以上であることが電極間で有効に導通に関与する導電粉末が多く存在するために好ましい。しかし、粒径分布を有しているのが接続基板上に異方導電性組成物を印刷したり、異方導電性フィルムの均一な膜を作製するために好ましい。本発明で用いる平均粒子径とは、レーザー回折型測定装置RODOS SR型(SYMPATEC HEROS&RODOS)を用いて体積積算平均粒子径を用いた。また、平均粒子径±2μ内の金属粉末の存在は、体積積算粒度分布計より読みとった。
【0011】
本発明で用いる金属粉末は、例えば不活性ガスアトマイズ法を用いて作製されるのが好ましい。不活性ガスアトマイズ法は窒素、ヘリウム、水素、アルゴン及びこれらの混合ガスを用いるのが好ましく、例えば、かかる組成の銀、金、銅の融液を高速の不活性ガスを衝突させて微粉化急冷凝固するものである。形状は、球状、鱗片状、樹枝状などを用いることができる。また、銅粉末、銅合金粉末の表面に銀や金のメッキをかけたものでも構わない。
【0012】
本発明の異方導電性組成物あるいはフィルムは、該組成の金属粉末1重量部に対しエポキシ樹脂を含む有機バインダーを0.1〜120重量部有し、前記エポキシ樹脂としてナフタレン骨格に少なくとも2官能以上のグリシジルエーテル結合を有するナフタレン型エポキシ樹脂を含有することを特徴とする異方導電性組成物及びフィルムを提供するものである。有機バインダーの量は好ましくは、0.1〜80,より好ましくは0.3〜60重量部である。
【0013】
ここで、ナフタレン骨格に少なくとも2官能以上のグリシジルエーテル基を有する多官能エポキシ樹脂を含有するが、ナフタレン骨格を用いることで耐熱性を向上できる。また、グリシジルエーテル型多官能基により反応性を向上させるものであり、特に、アスペクト比が高く、バンプ数が多いベアチップ接続においては、従来技術のものでは、リフロー時に端のバンプにストレスがかかり、接続不良が発生していたりした。本発明の異方導電性組成物により初めて耐リフロー性能を著しく向上できるに至った。すなわち、かかる組成の金属粉末を用いることで、導通性能を向上できる。さらに、ヒートサイクルなどの熱衝撃を受けた場合には、金属粉末は、チップバンプなどの金バンプ、銅バンプと熱膨張係数が近く、ヒートサイクルに耐えることができ、かつ、ナフタレン骨格のエポキシ樹脂により、有機バインダー全体の熱膨張係数を小さくでき、ファインピッチのヒートサイクル試験には著しく安定な接続性を示すことを見いだした。また、本発明で用いる金属紛末はほぼ球状に近い形をしており、バインダー樹脂との濡れ性に優れ、金属粉末の分散性を向上でき、ファインピッチ接続での隣接端子間での絶縁性が確保できることである。
【0014】
本発明のナフタレン型エポキシ樹脂は2〜4官能のグリシジルエーテル結合を有することが好ましい。4官能を越える場合には、溶融粘度が高く、圧接時に高圧が必要になる。2官能未満の場合には硬化樹脂強度が低い。
特に、ナフタレン骨格のエポキシ樹脂としては、常温で半固形タイプのものが好ましい。例えば、エポキシ当量としては、130〜260g/eq程度のものが好ましい。中でも1,6にグリシジルエーテル結合を有するナフタレンエポキシ樹脂が好ましい。
【0015】
ナフタレン骨格のエポキシ樹脂としては、有機バインダー100重量部中に10重量部以上含有していることが反応性の点から好ましい。
さらに、本発明は、有機バインダ−として、ナフタレン骨格の2,3,4官能グリシジルエーテル型エポキシ樹脂以外に、ビスフェノールA型、ビスフェノールF型、フェノールノボラック型、クレゾールノボラック型、脂環式、アルキル多価フェノール型、ウレタン変性型、脂肪酸変性型、ゴム変性型エポキシ樹脂、及びフェノキシ樹脂、ウレタン樹脂、ポリエステル樹脂、アクリル樹脂、SBR、NBR、シリコーン樹脂より選ばれた1種以上の樹脂を含有していることを特徴とする異方導電性組成物を提供するが、ナフタレン骨格のエポキシ樹脂以外に上記から選ばれた1種以上の樹脂を含むことで、塗工及びフィルム状態にした場合の塗膜粘度を幅広く調整する事が可能である。すなわち、本発明のバインダー及び金属粉末との組み合わせにより、塗工時の金属粒子の変形性も無く、圧接時に充分な変形性を有する硬さを有し、本発明で用いる有機バインダーの塗膜粘度を反応性を落とすことなく塗膜粘度を調整できる点で有る。仮に従来のビスフェノールAタイプのものだけでは粘度が柔らかすぎ、また耐熱性が悪い点があり、製造プロセス上、特性上問題であった。塗膜粘度が柔らかすぎると樹脂の保存中でのシミ出しがおこり転写性が劣るためである。
【0016】
さらに、ナフタレン骨格のエポキシ樹脂の熱膨張係数が小さいこと、さらには本発明の金属粒子の熱伝導性が良く、熱膨張がバンプなどの材料と近いことでヒートサイクルによる接続不良を著しく改良できる。
ナフタレン骨格のエポキシ樹脂以外のエポキシ樹脂としては、上記に示されるが、膜粘度調整のため、ビスフェノールA、F型、脂環式、ノボラック型などのエポキシ樹脂を用いるのが好ましく、さらには、フェノキシ樹脂を同時に用いるのが好ましい。
【0017】
本発明で用いる有機バインダー中のエポキシ樹脂の硬化剤として、エポキシ樹脂100重量部に対して、硬化剤としてマイクロカプセル型のイミダゾール誘導体エポキシ化合物を0.5〜250重量部を含有するのが好ましく、マイクロカプセル型のイミダゾール誘導体エポキシ化合物としては、イミダゾール誘導体とエポキシ化合物との反応生成物を粉砕等により微粉末とした物をさらにイソシアネート化合物などと反応させて、カプセル化することで常温での安定性を高めた物である。マイクロカプセル型のイミダゾール誘導体エポキシ化合物を用いることで、異方導電性組成物及びフィルムの保存時の安定性を向上できる。また、加圧、加熱接合の数秒という僅かな時間での均一な硬化が可能である。加熱時に徐々に反応が進むのではなく、数秒の時間の間で膜の内部への拡散が進み、均一な硬化が可能である。また、本発明で用いる金属粉末は熱を伝えやすいために、有機バインダー中に分散しているマイクロカプセル型硬化剤への熱を伝えやすくなり均一な硬化を促進できる利点もある。すなわち数秒の短時間でも充分な硬化性が得られる。また、本発明での金属粉末を用いることで、マイクロカプセルのイソシアネート被膜を金属粉末が加圧変形時に突き破り、硬化を急速に加速することができる。
【0018】
マイクロカプセル型のイミダゾール誘導体エポキシ化合物は、室温度では安定であり、数十度の温度で溶融し、圧着温度近辺で著しくエポキシの固化を進めるものである。この時のイミダゾール誘導体としては、例えばイミダゾール、2メチルイミダゾール、2−エチルイミダゾール、2−エチルー4ーメチルイミダゾール、2−フェニルイミダゾール、2ーフェニルー4メチルイミダゾール、1ーベンジル−2メチルイミダゾール、1−ベンジルー2エチルイミダゾール、1ーベンジルー2ーエチルー5ーメチルイミダゾール、2フェニルー4メチルー5ーヒドロキシメチルイミダゾール、2ーフェニル4、5ージヒドロキシメチルイミダゾール等が挙げられる。また、エポキシ化合物としては、ビスフェノールA、ビスフェノールF、フェノールノボラック、ブロム化ビスフェノールA等のグルシジルエーテル型エポキシ樹脂、ダイマー酸ジグリシジルエステル、フタル酸ジグリシジルエステル等が挙げられる。マイクロカプセル型イミダゾール誘導体エポキシ化合物硬化剤は、好ましくは、エポキシ樹脂100重量部に対して5〜250重量部である。5重量部未満であると硬化不足になる。250重量部を超える場合には、保存安定性が悪くなる。好ましくは、5〜150重量部である。
【0019】
また、マイクロカプセル型硬化剤の粒径としては、平均粒子径で1〜10μが好ましい。それは、10μを超えるものが多いと異方導電性フィルムにした場合に、塗膜厚みムラを引き起こす。1μ未満であると、マイクロカプセル型硬化剤の表面積が大きくなりすぎて保存安定性が悪くなる。また、マイクロカプセル型硬化剤の粒子径が金属粉末の粒子径と同等のために、金属粉末同士が並ぶことによる絶縁低下を防止に有効である。
【0020】
マイクロカプセル型イミダゾール誘導体エポキシ化合物の平均粒子径が1〜10μであり、かつ最小粒子径/最大粒子径比が0.001〜0.6であるのが好ましく、最小粒子径/最大粒子径比が0.001未満では、仕込みの硬化剤が圧接時に充分な機械的破壊や熱破壊が起こりにくく硬化不足やムラを生じやすい。粒子径比が0.6を越える場合には、接続チップや基板と被接続基板とが充分な平行度が保たれている場合は良いが、基板の反りがある場合には、電極間のギャップが異なり、接続ムラがかえって生じやすい。
【0021】
特に、電極間が圧接過程で、狭くなるにつれて連続的に小粒子径のマイクロカプセルが機械的に破壊されていくために、圧接過程の最終時にまで十分な硬化性能を維持することができ安定な接続が可能である。
このため、LSIチップのバンプのように高さのバラつきが多い接続にも硬化剤大きさも分布で硬化性のバラツキが緩衝できる利点がある。
【0022】
マイクロカプセルの硬化剤の平均粒子径及び最小粒子径、最大粒子径は、金属粉末と同じ測定機で測定したものである。最小粒子径については体積積算粒子径で5%での粒子径を指す。最大粒子径は体積積算粒子径で98%での粒子径を指す。
硬化剤については、マイクロカプセル型の硬化剤以外にも、必要に応じて脂肪族アミン、芳香族アミン、カルボン酸無機物、チオール、アルコール、フェノール化合物、ホウソ化合物、無機酸、ヒドラジド、及びイミダゾールを加えても良い。
【0023】
また、本発明の異方導電性組成物を塗布する場合には、必要に応じて適当な溶剤を用いることができる。この場合には、マイクロカプセル型硬化剤にダメージを与えない物が好ましい。例えば、メチルエチルケトン、トルエン、ベンゼン、キシレン、メチルイソブチルケトン、酢酸エチル、酢酸ブチル、エチレングリコールモノエチルアセテート、ジオキサンなどの芳香族炭化水素、エーテル系、ケトン系、エステル系などが良い。
【0024】
また、本発明の異方導電性組成物には、金属粒子の分散性を良くするために、カップリング剤等を加えることができる。例えば、チタンカップリング剤、シランカップリング剤、アルミカップリング剤などをエポキシ樹脂100重量部に対して10重量部程度まで加えることができる。
本発明の異方導電性組成物の製造法としては、先ず金属粉末とエポキシ樹脂及び必要に応じてエポキシ以外の熱可塑性性あるいは熱硬化性樹脂、必要に応じて溶剤、カップリング剤を所定量計測してプラネタリーミキサー、ニーダー、三本ロール、羽根付き攪拌機、ボールミルなどの公知の混合機にて混合して、銅合金粉末が均一に分散されている混合物を作製する。
【0025】
こうして得られた異方導電性組成物の粘度は、1000cpsから5万CPS程度の用途に応じた粘度が好ましい。
このままで、接続基板上の電極や端子上にディスペンサーやスクリーン印刷等で塗布して用いることもできる。
また、フィルム状の異方導電性フィルムを作製する場合には、異方導電性組成物をブレード、ダイコーター等の公知の塗布方法で絶縁性フィルムなどのベースフィルム上に塗布する。塗布され溶剤を含む物は乾燥する。異方導電性フィルムの厚みとしては、5〜500μ程度であり、幅は特にしてはなく、接続する場合にスリッテイングして用いることができ、例えば幅0.2〜200mm程度の物でリール巻したものとかが良い。リールはプラスチック製が取り扱い易さに優れ好ましく、また、リール巻くもフィルムとしては、数m巻から1000m程度までは巻ズレやフィルムの変形が起こらずに作製できる。リールはガイド付きの物が好ましい。本発明の異方導電性フィルムは、好ましくはフィルムの少なくとも一方に絶縁性のフィルム(ここではベースフィルムと呼ぶ)を有しているのが保存性や接続時の作業性が良くなり好ましい。この時のベースフィルムとしては、異方導電性組成物の塗布膜の下地層として用いる物であり、リール等に巻いて用い場合に機械的な強度が得られるフィルムが良い。PET、テフロン、ポリイミド、ポリエステル、ポリアミド、アルミナや窒化アルミナ等の無機フィルムや、異方導電性組成物との粘着性のコントロールのためにこれらのベースフィルムに酸化チタン、シリコーン樹脂処理、アルキッド樹脂処理などの処理を施したフィルムが好ましい。ベースフィルムの厚みとしては、1〜300μ程度のものを用いるのが好ましい。こうしてベースフィルムに塗布されたものは2層の異方導電性フィルムと呼ぶが、必要に応じてカバーフィルム(すなわちベースフィルムとは反対側を異方導電性組成物を挟み込む)を用いることができる。この場合には、ベースフィルムより粘着性が低い物が好ましい。これもベースフィルムに用いることができるPET、テフロン、ポリイミド、ポリエステル、ポリエチレン、ポリプロピレン、ポリアミド、無機フィルムやこれらにシリコーン樹脂処理、アルキッド樹脂処理、酸化チタン処理を施したものの組み合わせで作製することができる。このカバーフィルムを用いる場合を3層構造という。ベースフィルム、必要に応じてカバーフィルムを用いてフィルム状に形成された異方導電性組成物を異方導電性フィルムと呼ぶ。使用する場合には、当然カバーフィルムとベースフィルムを剥がして接続にもちることは言うまでもない。
【0026】
異方導電性組成物の用い方としては、以下のとおりである。異方導電性組成物をそのまま用いる場合には、ディスペンサーやスクリーン印刷を用いて塗布する。この場合には、硬化時に溶剤などの揮発があるとボイド発生の原因になるために無溶剤タイプが好ましい。電極上の塗布された異方導電性組成物を挟み込むように被接続基板上の電極あるいはLSIチップ電極(バンプ)をアライメントして被接続基板あるいLSIチップ上からツールで加熱、加圧してエポキシを硬化する。この時、電極間に位置する導電粉末のみが変形をうけて電極間方向のみに導通が得られる。隣接電極間同士では絶縁性が維持される。
【0027】
異方導電性フィルムの場合には、カバーフィルムのあるものは、先ずカバーフィルムを剥がして接続基板上の電極上に異方導電性組成物のタック性を利用して貼り合わせる。この時、貼り合わせ時に、剥がれない程度に適度に加圧、加熱して仮圧着しておく。さらに、ベースフィルムを剥がして、異方導電性組成物のみが接続基板上に貼りつけられている状態にする。被接続基板あるいはLSIチップの電極をアライメントして接続基板上の電極と向かい合わせになるようにして異方導電性組成物を挟み込むようにしてツールで押し当てる。この時、加圧、加熱してエポキシを硬化し、金属粒子の変形により向かい合う電極間同士で導通を得る。隣接する電極間同士は電気的導通を有さない。本発明の異方導電性組成物あるいは異方導電性フィルムは、加圧時の圧力が低圧でも金属粒子を変形させ、電極間での高導電性を得ることができる。圧力は、2kg/cm2から数百kg/cm2程度の圧力で接続できる利点がある。好ましくは、5kg/cm2から500kg/cm2である。また、加熱温度は、80〜220℃の範囲での接続ができる。また、加熱時間は、数秒から数十秒の時間でできる。これは、本発明で用いる導電粒子の熱伝導性が良いために、組成物のエポキシ樹脂への熱導体としての役割をできる。そのため、短時間で作製でき生産性に優れる点が良い。
【0028】
こうして、接続基板と被接続基板あるいはLSIチップとの電気的接続が異方導電性組成物あるいはフィルムを介して達成できる。
接続基板としては、液晶ディスプレイ、プラズマディスプレイ、エレクトロルミネッサンスディスプレイ、プリント基板、ビルドアップ基板(絶縁層、導体回路層を交互に積み上げて得られる多層基板で、感光性樹脂なども用いることができる)、低温焼成基板などの電気的配線が施されている基板などを用いることができる。また、被接続基板あるいは被接続チップ部品としては、フレキシブルあるいはリジッドなプリント基板、コンデンサー、抵抗器、LSIチップ、コイルや、LSIチップが既に接続されているフレキシブル基板(TCP;テープキャリヤーパッケージ)、QFP、DIP、SOPなどのLSIパッケージなどの接続に用いることができる。
【0029】
接続基板あるいは被接続基板の材質は特に制限はなく、例えば、ポリイミド、ガラスエポキシ、紙フェノール、ポリエステル、ガラス、ポリエーテルイミド、ポリエーテルケトン、ポリエチレンテレフタレート、ポリフェニレンエーテル、熱硬化型ポリフェニレンエーテル、ポリフェニレンサルファイド、ガラスポリイミド、アルミナ、窒化アルミナ、テトラフルオロエチレン、ポリフェニレンテレフタレート、BTレジン、ポリアミド、感光性エポキシアクリレート、低温焼成セラミックス、ビルドアップ基板等を用いることができる。
【0030】
接続基板あるいは被接続基板上に形成されている接続用電極の導体は特に制限はなく、ITO(インジウム−スズ−酸化物)、IO(インジウム酸化物)、銅、銀、銀銅合金、銀パラジウム、金、白金、ニッケル、アルミニウム、銀白金、スズ鉛はんだ、スズ銀半田、すず、クロムや、これらの導体に金メッキ、スズメッキ、ニッケルメッキ、スズ鉛半田メッキ、クロムなどのメッキを施した導体や、銀や銀パラジウム、銅などを主体にした導電性ペーストなどである。
【0031】
被接続のチップ部品としては、コンデンサー、磁気センサー、抵抗器、コイル、LSIチップ、QFP、SOPなどを用いることができるが、接続電極としては、銀、銀パラジウム、アルミニウム、銅、銀銅合金、白金、金、アルミニウム、銅ニッケル合金などやこれらに、すず、半田、ニッケル、金などのメッキしたものを用いることができ、LSIチップなどの場合にはバンプ(電極)を用いても接続できる。バンプは、金メッキや金ワイヤーボンデイング、ハンダボール、ニッケルボール、銅ボールなどで形成されている物で構わない。
【0032】
LSIチップを直接ガラス基板やプリント基板上に実装する場合をCOG(チップオングラス)、COB(チップオンボード)、COF(チップオンフィルム)と呼んでいるが、この場合にも接続媒体として本発明の異方導電性組成物あるいはフィルムを用いることができる。接続する電極のピッチとしては、本発明の異方導電性フィルムあるいは組成物を用いれば、10〜1000μピッチの幅広いピッチでの接続で効果を特に発揮できる。
【0033】
接続基板上の導体及び電極は、メッキ法、エッチング法、導電ペースト硬化、導電ペースト焼結、導体ボール、電着などにより作製された物で良い。
【0034】
【発明の実施の形態】
以下に本発明の異方導電性組成物あるいは異方導電性フィルムの実施例を示す。
【0035】
【実施例】
表1に本発明で用いる銅合金粉末の作製例を示す。
先ず、所定量の銅と銀、金の粒子を黒鉛るつぼに入れ、高周波誘導加熱を用いて不活性ガス雰囲気中で加熱溶解する。溶解後、不活性ガス雰囲気中ヘリウムまたは窒素中へ噴出し、同時に高速の不活性ガスを融液に対して噴出して急冷凝固して微粉末を作製する。さらに、気流分級機にて所定の大きさにカットした。得られた銅合金粉末は球状に近い形状をしており、平均組成及び表面組成、平均粒子径、粒子径分布は、前記記載の方法で測定した。さらに、銅紛を金メッキしたもの、アトマイズ紛をさらに金メッキしたものも作成した。
ただし、粉末作成例10は、空気でアトマイズした。
【0036】
表1で得られた金属粉末に混合して用いる有機バインダー、硬化剤を表2に示す。
表1、2に示される金属粉末及び有機バインダー及びマイクロカプセル型硬化剤を混合してなる異方導電性組成物及び異方導電性フィルムを表3評価例を表4に示す。異方導電性組成物は、溶剤で適度な粘度(1000CPS)に調整した。異方導電性フィルムは、PETフィルム基材のベースフィルム及びカバーフィルムを用いて、塗工幅100mmでダイコータ−で50m塗工したものである。塗工性は、1.5mm幅にスリッテイング後、室温度で2ヶ月放置後にベースフィルムからの10cm/秒の速度で剥がれ性と、且つガラス基板への2kg/cm2 70℃ 2秒での転写性が良好な場合をそれぞれ○とした。
【0037】
表3中の実施例(3)はペースト状態のままで、室温度2ヶ月保存後に、1mm幅20μ厚みライン状に印刷し、室温放置30分後に、ダレ幅が0.2mm以内に収まる状態を良好とした。また、180℃15秒で硬化させた時の表面粗さ計で表面の平滑性が±5μ以内である場合を転写性良好とした。
導通性は、4端子法で測定し、基板上の各端子の接続抵抗であり、環境試験(ー55〜125℃ 各30分での3000サイクル試験)を行って両端(チップでは一番端でストレスが最もかかる位置)の接続電極における初期接続抵抗値に対して変化率10%以下を○とした。
【0038】
耐リフロー性は、到達温度260℃ 5分リフロー炉通過4回後での評価で接続抵抗が初期の10%未満の変化率の場合を○とした。
絶縁性試験は、隣接電極あるいは端子同士での絶縁抵抗(200V)を測定し、1012オーム以上で絶縁性が良好を○とした。
密着強度については、リフロー炉4回通過後に機械的な剥がし強度が500gf/cm(換算値)以上を○とした。
【0039】
【比較例】
表5に比較例の異方導電性組成物及びフィルムを示す。
表6に表5の比較例の異方導電性組成物及びフィルムの評価結果を示す。評価方法は実施例と同じである。
【0040】
【表1】
【0041】
【表2】
【0042】
【表3】
【0043】
【表4】
【0044】
【表5】
【0045】
【表6】
【0046】
【発明の効果】
本発明の異方導電性組成物及びフィルムは、以下の点に優れた効果を有する。
1.粒子表面に、銀、あるいは金の濃度が高く、変形性、熱伝導性に優れるために短時間での接続ができ、耐環境性に優れ、接続抵抗が低い。
2.ナフタレン骨格のエポキシ樹脂との組み合わせにより、LSIチップ接続での熱膨張変化によりストレスを緩衝でき、繰り返しリフロー時での端部での接続不良を減少できる。
3.マイクロカプセル型硬化剤が粒度分布を有しており、バンプ高さなどのバラツキが合っても接続過程(電極間が狭くなるにつれて)で充分な硬化性バラツキの緩衝効果を発揮できる。
4.膜粘度が高く、2ヶ月室温放置でも充分な剥がし性、転写性を有する。[0001]
BACKGROUND OF THE INVENTION
The anisotropic conductive composition and film of the present invention include a TAB and FPC connection to a liquid crystal panel, a plasma display and an EL display, a COG connection of an LSI bare chip, a COB connection to a printed circuit board of an LSI bare chip, a COF connection, It can be used for connection of a flexible substrate to a display panel and connection of a flexible substrate and a rigid substrate. In particular, it is effective for fine pitch applications such as liquid crystal televisions, mobile phones, liquid crystal cameras, watches, word processors, copiers, telephones, personal computers, plasma displays, EL panels, and computers.
[0002]
[Prior art]
Up to now, many anisotropic conductive films have been used for connection of driver ICs for liquid crystals. The liquid crystal itself is also becoming smaller and the fine pitch of the connection terminals is rapidly progressing.
Many anisotropic conductive films have been disclosed, and for example, conductive particles obtained by performing metal plating on resin balls as disclosed in JP-A-7-197001 and JP-A-4-242010. An anisotropic conductive film using metal and an anisotropic conductive film using metal powder such as nickel powder, solder powder and gold-plated nickel powder are disclosed (for example, JP-A-61-55809).
[0003]
An anisotropic conductive film is a film in which conductive particles are dispersed in an organic binder, and is bonded in advance on the electrode or terminal on the substrate to be connected, and the connected substrate or connected LSI is aligned. The organic binder is dried or heat-cured by applying pressure and heating. At this time, only the conductive particles sandwiched between the electrodes are deformed to have conductivity only in the direction between the electrodes, and the adjacent electrodes are kept insulative. It has been used for TAB connection of driving ICs for panels of liquid crystal, plasma display, EL, etc., connection of LSI bare chips, panel connection of flexible substrates, and the like.
[0004]
[Problems to be solved by the invention]
The anisotropic conductive films that have been used conventionally have the following limitations. In other words, since the metal plating resin powder is only a plated metal layer, the number of particles that contribute to conduction is reduced in the case of 50μ fine pitch connection, so the connection resistance increases and the drive voltage increases. Is required. Further, in the case of metal plating resin powder, when the conductive powder is deformed by pressurization, the plating is peeled off, frequently causing poor insulation. In the case of metal powder, nickel powder originally has a high specific resistance, but its environmental resistance is poor and the connection resistance increases. Also, since nickel powder is hard, the pressure during connection is several tens of kg / cm.2For this reason, the damage to the substrate is large. For example, when it is used for a glass substrate, there has been a problem of breakage of the substrate. Solder powder has inherently high specific resistance among metal powders, cannot be used for fine pitch connection, and has a low melting point. In the case of gold-plated nickel powder, the gold plating is peeled off during pressurization, and high pressure is required when nickel is used. Further, when the electrode is soft, the electrode is often deformed. In the case of silver powder, a decrease in insulation between adjacent electrodes is likely to occur due to water absorption and the like, and it is not possible to cope with fine pitch connection.
[0005]
In addition, there is a demand for pressurization time as short as several seconds from the point of recent high productivity. However, those using the above-mentioned materials have poor thermal conductivity, and poor connection due to insufficient curing in connection of several seconds. Was authoritative. Moreover, in fine pitch connection, terminals with poor connection often occur due to insufficient dispersion of the conductive powder in the film. Furthermore, there is an increasing demand for flowing a high current though it is a fine pitch, but in the known one, not only the resistance is high but also the thermal conductivity is bad, the resistance value increases and the current cannot flow more than a certain amount. Was the current situation.
[0006]
In addition, as an organic binder in which conductive particles are dispersed, an epoxy resin is often used as a thermosetting type from the viewpoint of adhesiveness. However, with the conventional anisotropic conductive film, LSI bare chip mounting is progressing. However, an anisotropic conductive composition that can be connected to an organic substrate having a significantly different coefficient of thermal expansion from the chip has been required. However, in a chip having a high aspect ratio, connection failure frequently occurs due to stress at the end bumps. is happening. Organic substrates are required to be connected with high productivity in a short time of 3 to 5 seconds because it may be high temperature, but the anisotropic conductive film has insufficient heat resistance or the heat of the conductive filler. The conductivity was insufficient. In addition, reflow at around 260 ° C. is repeated to connect other components after bare chip mounting, but the heat resistance for this is insufficient. In addition, low molecular weight epoxies, etc., which had been stored at room temperature for a long time, had protrusions from the base film with anisotropic conductive films, which caused backside transfer when pulled out from the reel. .
[0007]
[Means for Solving the Problems]
Therefore, in order to solve the above problems, in the present invention,
1. Formula M x Cu 1-x (M is one or more selected from Ag and Au, 0.01 ≦ x ≦ 0.6, and x is an atomic ratio), and the silver or gold concentration on the powder surface is higher than the average silver or gold concentration An organic binder containing an epoxy resin is used in an amount of 0.1 to 120 parts by weight with respect to 1 part by weight of a metal powder having an average particle diameter of 2 to 15 μm, and a microcapsule type imidazole derivative as a curing agent with respect to 100 parts by weight of the epoxy resin. An anisotropic conductive composition having 5 to 250 parts by weight of an epoxy compound, wherein the epoxy resin contains a naphthalene type epoxy resin having at least a bifunctional glycidyl ether bond in a naphthalene skeleton, and the microcapsule type imidazole derivative epoxy The average particle size of the compound is 1 to 10 μm, and the minimum particle size / maximum particle size ratio is 0.001 to 0.6. An anisotropic conductive composition,
2. In addition to naphthalene type epoxy resin having 2,3,4 functional glycidyl ether bond of naphthalene skeleton as organic binder, bisphenol A type, bisphenol F type, phenol novolac type, cresol novolac type, alicyclic, alkyl polyhydric phenol Contains at least one resin selected from molds, urethane-modified, fatty acid-modified, rubber-modified epoxy resins, phenoxy resins, urethane resins, polyester resins, acrylic resins, SBR, NBR, and silicone resins Characterized by The anisotropic conductive composition as described,
3. In the particle size distribution of the metal powder, the powder having an average particle size within ± 2 μ is 30 to 100% by volume or more. Or 2. An anisotropic conductive composition as described in
4). 1. ~ 3. An anisotropic conductive film characterized in that the anisotropic conductive composition according to any one of the above is formed into a film shape,Is to provide.
[0008]
The metal powder used in the present invention has the general formula MxCu1-x(M is one or more selected from Ag and Au, 0.01 ≦ x ≦ 0.6, and x is an atomic ratio), and the silver or gold concentration on the powder surface is higher than the average silver or gold concentration Although it is a metal powder having an average particle diameter of 2 to 15 μm, it is a conductive powder having high conductivity of both copper, silver and gold, so that it has high conductivity at the time of connection and particles at a fine pitch. High conductivity can be maintained even if the number decreases. In this case, when x exceeds 0.6, there are many silver components and a problem of migration between adjacent electrodes occurs, leading to a short circuit. When x is less than 0.01, the oxidation resistance is insufficient and the conduction resistance is remarkably increased. Preferably, x is 0.04 to 0.4. Many of the electrodes and terminals of the substrate or connected substrate are mainly composed of copper. For this reason, even in tests such as a heat cycle, the coefficient of thermal expansion is close and the change in connection resistance is small. In addition, since the silver and gold concentrations on the surface of the metal powder containing copper as the main component are higher than the average silver and gold concentration, the metal powder can be prevented from oxidative deterioration at the connection point with the electrode, and silver migration is prevented. it can. The silver or gold concentration on the surface of the metal powder is preferably higher than the average silver or gold concentration.
[0009]
The silver or gold concentration on the powder surface is a value (Ag + Au) calculated from the area values of Cu2p, Ag3d, and Au measured with XPS (X-ray photoelectron spectrometer; XSAM800; manufactured by KRATOS) using the correction coefficient in the apparatus. / (Cu + Ag + Au)). The average silver, gold, and copper concentrations of the metal powder were measured using an ICP (high frequency inductively coupled plasma analyzer (Seiko Denshi Kogyo; JY38P2)) after dissolving the metal powder in concentrated nitric acid or aqua regia solution. As long as the copper alloy powder used in the present invention is not damaged, Pt, Sn, Zn, Pd, P, B, C, Ti, Si, V, Mg, Al, Hf, Pb, Mn, Ni Etc. may be added.
[0010]
The average particle diameter of the metal powder is preferably 2 to 15 μm, and if it is less than 2 μm, the conductive particles sandwiched between the electrodes at the time of pressurization become the roughness level of the electrode surface, resulting in poor conductivity. Sexuality gets worse. If it exceeds 15 μm, the number of conductive particles between the electrodes becomes insufficient and the connection resistance becomes unstable in the inter-electrode bonding at a fine pitch. The average particle size is preferably 2 to 13 μm. Moreover, it is preferable that the abundance ratio of the powder having an average particle size within ± 2 μm is 30% or more because there are many conductive powders that are effectively involved in conduction between the electrodes. However, it is preferable to have a particle size distribution in order to print the anisotropic conductive composition on the connection substrate or to produce a uniform film of the anisotropic conductive film. As the average particle size used in the present invention, a volume-integrated average particle size was used using a laser diffraction type measuring device RODOS SR type (SYMPATEC HEROS & RODOS). The presence of metal powder having an average particle size of ± 2 μ was read from a volume cumulative particle size distribution meter.
[0011]
The metal powder used in the present invention is preferably produced using, for example, an inert gas atomization method. The inert gas atomization method preferably uses nitrogen, helium, hydrogen, argon or a mixed gas thereof. For example, a silver, gold, or copper melt having such a composition is collided with a high-speed inert gas to be pulverized and rapidly solidified. To do. The shape can be spherical, scaly, dendritic or the like. Further, the surface of copper powder or copper alloy powder may be plated with silver or gold.
[0012]
The anisotropic conductive composition or film of the present invention has 0.1 to 120 parts by weight of an organic binder containing an epoxy resin with respect to 1 part by weight of the metal powder of the composition, and has at least two functional groups on the naphthalene skeleton as the epoxy resin. The present invention provides an anisotropic conductive composition and film characterized by containing a naphthalene type epoxy resin having the above glycidyl ether bond. The amount of the organic binder is preferably 0.1 to 80, more preferably 0.3 to 60 parts by weight.
[0013]
Here, the naphthalene skeleton contains a polyfunctional epoxy resin having a glycidyl ether group having at least two or more functional groups, but heat resistance can be improved by using the naphthalene skeleton. In addition, the glycidyl ether type polyfunctional group improves the reactivity, especially in the case of a bare chip connection with a high aspect ratio and a large number of bumps, the conventional technology is stressed on the end bumps during reflow, A connection failure occurred. For the first time, the anisotropic conductive composition of the present invention can significantly improve the reflow resistance. That is, the conduction performance can be improved by using the metal powder having such a composition. In addition, when subjected to thermal shock such as heat cycle, the metal powder has a thermal expansion coefficient close to that of gold bumps such as chip bumps and copper bumps, can withstand heat cycles, and has a naphthalene skeleton epoxy resin. Thus, the thermal expansion coefficient of the whole organic binder can be reduced, and it has been found that the fine pitch heat cycle test shows remarkably stable connectivity. In addition, the metal powder used in the present invention has a nearly spherical shape, has excellent wettability with the binder resin, can improve the dispersibility of the metal powder, and insulate between adjacent terminals in fine pitch connection Can be secured.
[0014]
The naphthalene type epoxy resin of the present invention preferably has a bi- to tetra-functional glycidyl ether bond. When the tetrafunctionality is exceeded, the melt viscosity is high, and a high pressure is required during pressure welding. When it is less than bifunctional, the cured resin strength is low.
In particular, the naphthalene skeleton epoxy resin is preferably a semi-solid type at room temperature. For example, the epoxy equivalent is preferably about 130 to 260 g / eq. Of these, naphthalene epoxy resins having glycidyl ether bonds at 1 and 6 are preferred.
[0015]
The epoxy resin having a naphthalene skeleton is preferably 10 parts by weight or more in 100 parts by weight of the organic binder from the viewpoint of reactivity.
In addition to the 2,3,4-functional glycidyl ether type epoxy resin having a naphthalene skeleton, the present invention provides a bisphenol A type, a bisphenol F type, a phenol novolak type, a cresol novolak type, an alicyclic type, an alkyl group, and an organic binder. Contains one or more resins selected from monohydric phenol type, urethane modified type, fatty acid modified type, rubber modified type epoxy resin, phenoxy resin, urethane resin, polyester resin, acrylic resin, SBR, NBR, and silicone resin An anisotropic conductive composition characterized by having a coating film in a coating and film state by including one or more kinds of resins selected from the above in addition to an epoxy resin having a naphthalene skeleton. It is possible to adjust the viscosity widely. That is, the combination of the binder of the present invention and the metal powder has no deformability of the metal particles at the time of coating, has a hardness that has sufficient deformability at the time of pressure contact, and the coating viscosity of the organic binder used in the present invention. The coating film viscosity can be adjusted without reducing the reactivity. If the conventional bisphenol A type alone is used, the viscosity is too soft and the heat resistance is poor, which is a problem in terms of the manufacturing process. This is because if the viscosity of the coating film is too soft, spots appear during storage of the resin and transferability is poor.
[0016]
Furthermore, since the thermal expansion coefficient of the naphthalene skeleton epoxy resin is small, the thermal conductivity of the metal particles of the present invention is good, and the thermal expansion is close to that of a material such as a bump, the connection failure due to heat cycle can be remarkably improved.
As epoxy resins other than the naphthalene skeleton epoxy resin, as shown above, it is preferable to use an epoxy resin such as bisphenol A, F type, alicyclic type, novolac type, etc. It is preferable to use the resin simultaneously.
[0017]
The epoxy resin curing agent in the organic binder used in the present invention preferably contains 0.5 to 250 parts by weight of a microcapsule type imidazole derivative epoxy compound as a curing agent with respect to 100 parts by weight of the epoxy resin. As microcapsule type imidazole derivative epoxy compound, the reaction product of imidazole derivative and epoxy compound is made into fine powder by pulverization, etc., and further reacted with isocyanate compound, etc., and encapsulated to stabilize at normal temperature It is the thing which raised the. By using the microcapsule type imidazole derivative epoxy compound, the stability of the anisotropic conductive composition and the film during storage can be improved. Further, uniform curing is possible in a short time of several seconds of pressurization and heat bonding. The reaction does not proceed gradually during heating, but diffusion to the inside of the film proceeds for several seconds, and uniform curing is possible. In addition, since the metal powder used in the present invention is easy to transfer heat, it is easy to transfer heat to the microcapsule type curing agent dispersed in the organic binder, and there is an advantage that uniform curing can be promoted. That is, sufficient curability can be obtained even in a short time of several seconds. Moreover, by using the metal powder in the present invention, the metal powder can break through the isocyanate coating film of the microcapsule at the time of pressure deformation, and the curing can be accelerated rapidly.
[0018]
The microcapsule-type imidazole derivative epoxy compound is stable at room temperature, melts at a temperature of several tens of degrees, and remarkably promotes solidification of the epoxy near the pressure bonding temperature. Examples of imidazole derivatives at this time include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2methylimidazole, 1-benzyl-2. Examples include ethylimidazole, 1-benzyl-2-ethyl-5-methylimidazole, 2phenyl-4methyl-5-hydroxymethylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, and the like. Examples of the epoxy compound include glycidyl ether type epoxy resins such as bisphenol A, bisphenol F, phenol novolac, and brominated bisphenol A, dimer acid diglycidyl ester, and phthalic acid diglycidyl ester. The microcapsule type imidazole derivative epoxy compound curing agent is preferably 5 to 250 parts by weight with respect to 100 parts by weight of the epoxy resin. If it is less than 5 parts by weight, curing will be insufficient. When it exceeds 250 parts by weight, the storage stability is deteriorated. Preferably, it is 5-150 weight part.
[0019]
Moreover, as a particle size of a microcapsule type hardening | curing agent, 1-10 micrometers are preferable at an average particle diameter. If it is more than 10 μm, an anisotropic conductive film causes uneven coating thickness. If it is less than 1 μm, the surface area of the microcapsule type curing agent becomes too large, and the storage stability becomes poor. Further, since the particle size of the microcapsule type curing agent is equal to the particle size of the metal powder, it is effective in preventing a decrease in insulation due to the metal powders being aligned.
[0020]
The average particle size of the microcapsule type imidazole derivative epoxy compound is preferably 1 to 10 μm, and the minimum particle size / maximum particle size ratio is preferably 0.001 to 0.6, and the minimum particle size / maximum particle size ratio is If it is less than 0.001, the charged curing agent is less likely to cause sufficient mechanical or thermal destruction at the time of pressure contact, and is liable to cause insufficient curing or unevenness. When the particle size ratio exceeds 0.6, it is good if the connecting chip or the substrate and the substrate to be connected have sufficient parallelism, but if there is warping of the substrate, the gap between the electrodes However, connection unevenness tends to occur.
[0021]
In particular, since the microcapsules with small particle diameters are mechanically destroyed as the gap between the electrodes is in the pressure welding process, and it becomes narrower, sufficient curing performance can be maintained until the end of the pressure welding process, and stable. Connection is possible.
For this reason, there is an advantage that the hardener variation can be buffered by the distribution of the size of the hardener and the connection having a large height variation like the bump of the LSI chip.
[0022]
The average particle size, the minimum particle size, and the maximum particle size of the curing agent for the microcapsules are measured with the same measuring machine as that for the metal powder. About the minimum particle diameter, the particle diameter in 5% is pointed out by volume integration particle diameter. The maximum particle size refers to the particle size at 98% in terms of volume cumulative particle size.
As for the curing agent, in addition to the microcapsule type curing agent, aliphatic amine, aromatic amine, carboxylic acid inorganic substance, thiol, alcohol, phenolic compound, boron compound, inorganic acid, hydrazide, and imidazole are added as necessary. May be.
[0023]
Moreover, when apply | coating the anisotropic conductive composition of this invention, a suitable solvent can be used as needed. In this case, the thing which does not damage a microcapsule type hardening | curing agent is preferable. For example, aromatic hydrocarbons such as methyl ethyl ketone, toluene, benzene, xylene, methyl isobutyl ketone, ethyl acetate, butyl acetate, ethylene glycol monoethyl acetate, dioxane, ether-based, ketone-based, ester-based, and the like are preferable.
[0024]
In addition, a coupling agent or the like can be added to the anisotropic conductive composition of the present invention in order to improve the dispersibility of the metal particles. For example, a titanium coupling agent, a silane coupling agent, an aluminum coupling agent, or the like can be added up to about 10 parts by weight with respect to 100 parts by weight of the epoxy resin.
As a method for producing the anisotropic conductive composition of the present invention, first, metal powder and epoxy resin, and if necessary, thermoplastic or thermosetting resin other than epoxy, if necessary, a solvent and a coupling agent in a predetermined amount. It measures and mixes with well-known mixers, such as a planetary mixer, a kneader, a 3 roll, a bladed stirrer, a ball mill, and produces the mixture by which copper alloy powder is disperse | distributed uniformly.
[0025]
The viscosity of the anisotropically conductive composition thus obtained is preferably a viscosity according to the use of about 1000 cps to 50,000 CPS.
In this state, it can be used by being applied to electrodes or terminals on the connection substrate by a dispenser, screen printing or the like.
Moreover, when producing a film-like anisotropic conductive film, an anisotropic conductive composition is apply | coated on base films, such as an insulating film, by well-known coating methods, such as a braid | blade and a die coater. The applied and solvent-containing material is dried. The thickness of the anisotropic conductive film is about 5 to 500 μm, the width is not particularly limited, and it can be slit and used for connection, for example, a reel having a width of about 0.2 to 200 mm. Something rolled up is good. The reel is preferably made of plastic because it is easy to handle. Also, a reel wound film can be produced from several m rolls to about 1000 m without winding deviation or film deformation. The reel preferably has a guide. The anisotropic conductive film of the present invention preferably has an insulating film (referred to herein as a base film) on at least one of the films, since the storage stability and workability during connection are improved. As the base film at this time, a film that is used as a base layer of a coating film of the anisotropic conductive composition, and a film that can obtain mechanical strength when used on a reel or the like is preferable. In order to control the adhesion to inorganic films such as PET, Teflon, polyimide, polyester, polyamide, alumina and alumina nitride, and anisotropic conductive composition, these base films are treated with titanium oxide, silicone resin, and alkyd resin. A film that has been subjected to such treatment is preferred. The thickness of the base film is preferably about 1 to 300 μm. The film thus applied to the base film is called a two-layer anisotropic conductive film, but a cover film (that is, an anisotropic conductive composition is sandwiched on the opposite side of the base film) can be used as necessary. . In this case, the thing whose adhesiveness is lower than a base film is preferable. This can also be produced by a combination of PET, Teflon, polyimide, polyester, polyethylene, polypropylene, polyamide, an inorganic film that can be used for the base film, and those subjected to silicone resin treatment, alkyd resin treatment, and titanium oxide treatment. . The case of using this cover film is called a three-layer structure. An anisotropic conductive composition formed into a film shape using a base film and, if necessary, a cover film is called an anisotropic conductive film. Needless to say, when used, the cover film and the base film are peeled off and used for connection.
[0026]
The usage of the anisotropic conductive composition is as follows. When the anisotropic conductive composition is used as it is, it is applied using a dispenser or screen printing. In this case, if there is volatilization of a solvent or the like at the time of curing, it will cause voids, so the solventless type is preferred. The electrodes on the connected substrate or LSI chip electrodes (bumps) are aligned so that the anisotropic conductive composition applied on the electrodes is sandwiched, and heated and pressed with a tool from the connected substrate or LSI chip to epoxy To cure. At this time, only the conductive powder located between the electrodes is deformed and conduction is obtained only in the direction between the electrodes. Insulation is maintained between adjacent electrodes.
[0027]
In the case of an anisotropic conductive film, if there is a cover film, the cover film is first peeled off and bonded onto the electrode on the connection substrate using the tack property of the anisotropic conductive composition. At this time, it is preliminarily pressure-bonded by applying pressure and heating to such an extent that it does not peel off. Further, the base film is peeled off so that only the anisotropic conductive composition is stuck on the connection substrate. The electrodes of the substrate to be connected or the LSI chip are aligned and faced with the electrodes on the connection substrate, and the anisotropic conductive composition is sandwiched and pressed with a tool. At this time, the epoxy is cured by pressurization and heating, and conduction is obtained between the electrodes facing each other by deformation of the metal particles. Adjacent electrodes do not have electrical continuity. The anisotropic conductive composition or anisotropic conductive film of the present invention can obtain high conductivity between electrodes by deforming metal particles even when the pressure during pressurization is low. Pressure is 2kg / cm2To several hundred kg / cm2There is an advantage that it can be connected with a pressure of a degree. Preferably, 5 kg / cm2To 500kg / cm2It is. The heating temperature can be connected in the range of 80 to 220 ° C. The heating time can be several seconds to several tens of seconds. Since the thermal conductivity of the conductive particles used in the present invention is good, this can serve as a thermal conductor to the epoxy resin of the composition. Therefore, it can be manufactured in a short time and is excellent in productivity.
[0028]
Thus, the electrical connection between the connection substrate and the connection target substrate or the LSI chip can be achieved via the anisotropic conductive composition or film.
As connection substrates, liquid crystal displays, plasma displays, electroluminescence displays, printed boards, build-up boards (multilayer boards obtained by alternately stacking insulating layers and conductor circuit layers, and photosensitive resins can also be used) A substrate provided with electrical wiring, such as a low-temperature fired substrate, can be used. In addition, as a substrate to be connected or a chip component to be connected, a flexible or rigid printed circuit board, a capacitor, a resistor, an LSI chip, a coil, a flexible substrate (TCP: tape carrier package) to which an LSI chip has already been connected, QFP It can be used for connection of LSI packages such as DIP, SOP.
[0029]
The material of the connection substrate or the connection substrate is not particularly limited. For example, polyimide, glass epoxy, paper phenol, polyester, glass, polyether imide, polyether ketone, polyethylene terephthalate, polyphenylene ether, thermosetting polyphenylene ether, polyphenylene sulfide Glass polyimide, alumina, alumina nitride, tetrafluoroethylene, polyphenylene terephthalate, BT resin, polyamide, photosensitive epoxy acrylate, low-temperature fired ceramics, build-up substrate, and the like can be used.
[0030]
There are no particular restrictions on the conductor of the connection electrode formed on the connection substrate or the connection substrate, ITO (indium-tin-oxide), IO (indium oxide), copper, silver, silver-copper alloy, silver palladium , Gold, platinum, nickel, aluminum, silver platinum, tin-lead solder, tin-silver solder, tin, chrome, conductors plated with gold, tin, nickel, tin-lead, chrome, etc. And conductive paste mainly composed of silver, silver palladium, copper, or the like.
[0031]
Capacitors, magnetic sensors, resistors, coils, LSI chips, QFP, SOP, etc. can be used as connected chip components, but as connection electrodes, silver, silver palladium, aluminum, copper, silver copper alloy, Platinum, gold, aluminum, copper-nickel alloy, etc., and those plated with tin, solder, nickel, gold or the like can be used. In the case of an LSI chip or the like, it can be connected using bumps (electrodes). The bump may be formed of gold plating, gold wire bonding, solder ball, nickel ball, copper ball, or the like.
[0032]
The case where an LSI chip is directly mounted on a glass substrate or a printed board is called COG (chip on glass), COB (chip on board), or COF (chip on film). An anisotropic conductive composition or film can be used. As the pitch of the electrodes to be connected, if the anisotropic conductive film or composition of the present invention is used, the effect can be exhibited particularly in connection with a wide pitch of 10 to 1000 μm.
[0033]
The conductors and electrodes on the connection substrate may be made by plating, etching, conductive paste curing, conductive paste sintering, conductive balls, electrodeposition, or the like.
[0034]
DETAILED DESCRIPTION OF THE INVENTION
Examples of the anisotropic conductive composition or anisotropic conductive film of the present invention are shown below.
[0035]
【Example】
Table 1 shows an example of producing the copper alloy powder used in the present invention.
First, a predetermined amount of copper, silver and gold particles are placed in a graphite crucible and heated and dissolved in an inert gas atmosphere using high frequency induction heating. After dissolution, it is ejected into helium or nitrogen in an inert gas atmosphere, and at the same time, a high-speed inert gas is ejected to the melt and rapidly solidified to produce a fine powder. Furthermore, it cut into the predetermined magnitude | size with the airflow classifier. The obtained copper alloy powder had a nearly spherical shape, and the average composition, surface composition, average particle size, and particle size distribution were measured by the methods described above. In addition, the copper powder was gold-plated and the atomized powder was further gold-plated.
However, the powder preparation example 10 was atomized with air.
[0036]
Table 2 shows the organic binder and curing agent used by mixing with the metal powder obtained in Table 1.
Table 3 shows evaluation examples of anisotropic conductive compositions and anisotropic conductive films obtained by mixing the metal powder, organic binder, and microcapsule type curing agent shown in Tables 1 and 2. The anisotropic conductive composition was adjusted to an appropriate viscosity (1000 CPS) with a solvent. The anisotropic conductive film is a film coated with a die coater with a coating width of 100 mm using a PET film base film and a cover film. The coatability is 1.5 mm width slitting, left at room temperature for 2 months, and then peeled off at a rate of 10 cm / second from the base film, and 2 kg / cm on the glass substrate.2Each of the cases where the transferability at 70 ° C. for 2 seconds was good was marked as ◯.
[0037]
Example (3) in Table 3 is in a paste state, after being stored for 2 months at room temperature, printed in a line of 1 mm width and 20 μ thickness, and after standing at room temperature for 30 minutes, the sagging width is within 0.2 mm. It was good. In addition, when the surface roughness measured with a surface roughness meter when cured at 180 ° C. for 15 seconds was within ± 5 μm, the transferability was considered good.
Conductivity is measured by the four-terminal method, and is the connection resistance of each terminal on the board. Environmental testing (-55 to 125 ° C, 3000 cycle test at 30 minutes each) performs both ends (at the end of the chip) The rate of change of 10% or less with respect to the initial connection resistance value of the connection electrode at the position where the stress is most applied) was evaluated as ◯.
[0038]
The reflow resistance was evaluated as ○ when the connection resistance had an initial change rate of less than 10% in the evaluation after an arrival temperature of 260 ° C. and 5 minutes after passing through the reflow furnace.
The insulation test measures the insulation resistance (200V) between adjacent electrodes or terminals, and 1012A value of “O” or higher indicates good insulation.
Regarding the adhesion strength, a mechanical peeling strength of 500 gf / cm (converted value) or more after passing through the reflow furnace four times was evaluated as ◯.
[0039]
[Comparative example]
Table 5 shows the anisotropic conductive composition and film of the comparative example.
Table 6 shows the evaluation results of the anisotropic conductive compositions and films of the comparative examples in Table 5. The evaluation method is the same as in the examples.
[0040]
[Table 1]
[0041]
[Table 2]
[0042]
[Table 3]
[0043]
[Table 4]
[0044]
[Table 5]
[0045]
[Table 6]
[0046]
【The invention's effect】
The anisotropic conductive composition and film of the present invention have excellent effects in the following points.
1. Since the concentration of silver or gold is high on the particle surface, and the deformability and thermal conductivity are excellent, the connection can be made in a short time, the environment resistance is excellent, and the connection resistance is low.
2. By combining with an epoxy resin having a naphthalene skeleton, the stress can be buffered by a change in thermal expansion at the time of LSI chip connection, and connection failure at the end during repeated reflow can be reduced.
3. The microcapsule type curing agent has a particle size distribution, and even if variations such as bump height are matched, a sufficient curable variation buffering effect can be exhibited in the connection process (as the distance between the electrodes becomes narrower).
4). The film has a high viscosity and has sufficient peelability and transferability even when left at room temperature for 2 months.
Claims (4)
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| JP27843897A JP4108161B2 (en) | 1997-10-13 | 1997-10-13 | Anisotropic conductive composition and film |
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| JP27843897A JP4108161B2 (en) | 1997-10-13 | 1997-10-13 | Anisotropic conductive composition and film |
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| JPH11120819A JPH11120819A (en) | 1999-04-30 |
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| JP2025104820A (en) * | 2023-12-28 | 2025-07-10 | サカタインクス株式会社 | Epoxy resin composition |
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