JP2015149128A - 異方性導電フィルム及びその製造方法 - Google Patents
異方性導電フィルム及びその製造方法 Download PDFInfo
- Publication number
- JP2015149128A JP2015149128A JP2014019863A JP2014019863A JP2015149128A JP 2015149128 A JP2015149128 A JP 2015149128A JP 2014019863 A JP2014019863 A JP 2014019863A JP 2014019863 A JP2014019863 A JP 2014019863A JP 2015149128 A JP2015149128 A JP 2015149128A
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- Prior art keywords
- resin layer
- insulating resin
- anisotropic conductive
- conductive film
- layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Abstract
【解決手段】異方性導電フィルム1は、第1絶縁性樹脂層2及び第2絶縁性樹脂層3を有する。第1絶縁性樹脂層2は光重合樹脂で形成され、第2絶縁性樹脂層3が熱カチオン若しくは熱アニオン重合性樹脂、光カチオン若しくは光アニオン重合性樹脂、熱ラジカル重合性樹脂、又は光ラジカル重合性樹脂で形成され、第1絶縁性樹脂層2の第2絶縁性樹脂層3側表面に、異方性導電接続用の導電粒子10が単層で配置されている。異方性導電フィルム全体の弾性率が0.13MPa以上である。
【選択図】図1
Description
また、異方性導電フィルムの腰が弱く、異方性導電接続をする場合の仮圧着後にリペアすると、フィルムが破断したり、接続面に樹脂が残ったりするという問題もあった。
第1絶縁性樹脂層が、光重合樹脂で形成され、
第2絶縁性樹脂層が、熱カチオン若しくは熱アニオン重合性樹脂、光カチオン若しくは光アニオン重合性樹脂、熱ラジカル重合性樹脂、又は光ラジカル重合性樹脂で形成され、
第1絶縁性樹脂層の第2絶縁性樹脂層側表面に、異方性導電接続用の導電粒子が単層で配置され、
異方性導電フィルム全体の弾性率が0.13MPa以上である異方性導電フィルムを提供する。
工程(A)
光重合性樹脂層に、導電粒子を単層で配置する工程;
工程(B)
導電粒子を配置した光重合性樹脂層に対して紫外線を照射することにより光重合反応させ、表面に導電粒子が固定化された第1絶縁性樹脂層を形成する工程;
工程(C)
熱カチオン若しくは熱アニオン重合性樹脂、光カチオン若しくは光アニオン重合性樹脂、熱ラジカル重合性樹脂、又は光ラジカル重合性樹脂で形成された第2絶縁性樹脂層を形成する工程;
を有し、
工程(B)において、異方性導電フィルム全体の弾性率が0.13MPa以上となるように光重合反応を行うことで第1絶縁性樹脂層を形成し、
工程(C)で形成した第2絶縁性樹脂層を、工程(B)で形成した第1絶縁性樹脂層の導電粒子側に積層する製造方法を提供する。
工程(A)
光重合性樹脂層に、導電粒子を単層で配置する工程;
工程(B)
導電粒子を配置した光重合性樹脂層に対して紫外線を照射することにより光重合反応させ、表面に導電粒子が固定化された第1絶縁性樹脂層を形成する工程;
工程(C)
熱カチオン若しくは熱アニオン重合性樹脂、光カチオン若しくは光アニオン重合性樹脂、熱ラジカル重合性樹脂、又は光ラジカル重合性樹脂で形成された第2絶縁性樹脂層を形成する工程;
工程(D)
工程(B)で形成した第1絶縁性樹脂層の導電粒子側に、結晶性樹脂で形成された中間層と第2絶縁性樹脂層が順次積層している積層体を形成する工程;
を有する製造方法を提供する。
一方、本発明の異方性導電フィルムにおいて、第2絶縁性樹脂層が光で反応する重合性樹脂で形成されている場合、それを用いた第1電子部品と第2電子部品の異方性導電接続は、接続ツールによる押し込みを、光反応が終了するまでに行えばよい。この場合においても、接続ツール等は樹脂流動や粒子の押し込みを促進するため加熱してもよい。また第2絶縁性樹脂層において、熱で反応する重合性樹脂と光で反応する重合性樹脂が併用されている場合も、上記と同様に光反応が終了するまでに接続ツールによる押し込みを行い、かつ加熱を行えばよい。
<<異方性導電フィルム>>
本発明の異方性導電フィルム1A、1Bを構成する第1絶縁性樹脂層2は、光重合樹脂で形成されている。例えば、アクリレート化合物と光ラジカル重合開始剤とを含む光ラジカル重合性樹脂層を光ラジカル重合させて形成される。第1絶縁性樹脂層2が光重合していることにより、導電粒子10を適度に固定化できる。即ち、異方性導電接続時に異方性導電フィルム1Aが加熱されても第1絶縁性樹脂層2は流れ難いので、樹脂流れにより導電粒子10が不用に流されてショートが発生することを大きく抑制することができる。
このような第1絶縁性樹脂層2の弾性率の調整は、第1絶縁性樹脂層2を形成する光重合性樹脂層への紫外線の照射量や弾性体の配合等で硬化率を調整することにより行うことができる。
アクリレート単位となるアクリレート化合物としては、従来公知の光重合性アクリレートを使用することができる。例えば、単官能(メタ)アクリレート(ここで、(メタ)アクリレートにはアクリレートとメタクリレートとが包含される)、二官能以上の多官能(メタ)アクリレートを使用することができる。本発明においては、異方性導電接続時に絶縁性樹脂層を熱硬化できるように、アクリル系モノマーの少なくとも一部に多官能(メタ)アクリレートを使用することが好ましい。
第1絶縁性樹脂層の形成に使用する光重合開始剤としては、公知の光重合開始剤の中から適宜選択して使用することができる。例えば、アセトフェノン系光重合開始剤、ベンジルケタール系光重合開始剤、リン系光重合開始剤等の光ラジカル重合開始剤等が挙げられる。
第1絶縁性樹脂層2には、必要に応じて、エポキシ化合物と、熱カチオン若しくは熱アニオン重合開始剤又は光カチオン若しくは光アニオン重合開始剤を含有させてもよい。これにより、層間剥離強度を向上させることができる。エポキシ化合物と共に使用する重合開始剤については、第2絶縁性樹脂層3で説明する。第1絶縁性樹脂層2には、必要に応じて、更にフェノキシ樹脂、不飽和ポリエステル樹脂、飽和ポリエステル樹脂、ウレタン樹脂、ブタジエン樹脂、ポリイミド樹脂、ポリアミド樹脂、ポリオレフィン樹脂などの膜形成樹脂を併用することができる。
導電粒子10としては、従来公知の異方性導電フィルムに用いられているものの中から適宜選択して使用することができる。例えばニッケル、コバルト、銀、銅、金、パラジウムなどの金属粒子、金属被覆樹脂粒子などが挙げられる。2種以上を併用することもできる。
第2絶縁性樹脂層3は、熱カチオン若しくは熱アニオン重合性樹脂、光カチオン若しくは光アニオン重合性樹脂、熱ラジカル重合性樹脂、又は光ラジカル重合性樹脂で形成される。より具体的には、エポキシ化合物と、熱カチオン若しくは熱アニオン重合開始剤又は光カチオン若しくは光アニオン重合開始剤とを含有する、熱又は光により重合する重合性樹脂層、又はアクリレート化合物と、熱ラジカル又は光ラジカル重合開始剤とを含有する熱又は光によりラジカル重合する重合性樹脂層からなるものである。
(エポキシ化合物)
第2絶縁性樹脂層3を形成するエポキシ化合物としては、分子内に2つ以上のエポキシ基を有する化合物もしくは樹脂が好ましく挙げられる。これらは液状であっても、固体状であってもよい。
第2絶縁性樹脂層3を形成する熱カチオン重合開始剤としては、エポキシ化合物の熱カチオン重合開始剤として公知のものを採用することができ、例えば、熱により酸を発生するヨードニウム塩、スルホニウム塩、ホスホニウム塩、フェロセン類等を用いることができ、特に、温度に対して良好な潜在性を示す芳香族スルホニウム塩を好ましく使用することができる。
第2絶縁性樹脂層3を形成する熱アニオン重合開始剤としては、エポキシ化合物の熱アニオン重合開始剤として公知のものを採用することができ、例えば、熱により塩基を発生する脂肪族アミン系化合物、芳香族アミン系化合物、二級又は三級アミン系化合物、イミダゾール系化合物、ポリメルカプタン系化合物、三フッ化ホウ素−アミン錯体、ジシアンジアミド、有機酸ヒドラジッド等を用いることができ、特に温度に対して良好な潜在性を示すカプセル化イミダゾール系化合物を好ましく使用することができる。
エポキシ化合物用の光カチオン重合開始剤又は光アニオン重合開始剤としては、公知のものを適宜使用することができる。
第2絶縁性樹脂層3を形成するアクリレート化合物は、第1絶縁性樹脂層2に関して説明したアクリレート化合物の中から適宜選択して使用することができる。
また、第2絶縁性樹脂層3にアクリレート化合物を含有させる場合に、アクリレート化合物と共に使用する熱ラジカル重合開始剤としては、第1絶縁性樹脂層2に関して説明した熱ラジカル重合開始剤の中から適宜選択して使用することができる。
アクリレート化合物用の光ラジカル重合開始剤としては、公知の光ラジカル重合開始剤を使用することができる。
第2絶縁性樹脂層3の層厚は、異方性導電接続時の導電粒子捕捉性の点から、好ましくは3〜20μm、より好ましくは5〜15μmである。
中間層4は、図2に示した第2実施例の異方性導電フィルム1Bにおいて、第1絶縁性樹脂層と第2絶縁性樹脂層との間に設けられる層であって、結晶性樹脂で形成されている。
中間層4を形成する結晶性樹脂としては、常温で硬いものが好ましく、中間層4と第1絶縁性樹脂層2との積層フィルムの弾性率が0.14MPa以上となるようにすることが好ましい。これにより、異方性導電フィルム1B全体としての弾性率を0.13MPa以上とすることができる。したがって、絶縁性樹脂層のはみ出しを抑制し、また、仮圧着後のリペア性を向上させることができる。
本発明の第1実施例の異方性導電フィルム1Aは、次の工程(A)〜(C)を行い、製造することができる。
図3Aに示すように、必要に応じて剥離フィルム30上に形成した光重合性樹脂層20に、導電粒子10を単層で配置する。導電粒子10を単層で光重合性樹脂層20に配置する方法としては、特に制限はなく、特許第4789738号の実施例1の導電粒子を粘着剤で固定した樹脂フィルムの2軸延伸操作を利用する方法や、特開2010−33793号公報の金型を使用する方法等を採用することができる。なお、導電粒子10の配置としては、縦横に所定間隔で配列させることが好ましい。また、接続対象のサイズ、導通信頼性、絶縁性、導電粒子捕捉率等を考慮し、2次元的な最近接粒子間距離を1〜100μm程度とすることが好ましい。
次に、導電粒子10を配置した光重合性樹脂層20に対して紫外線(UV)を照射することにより光重合反応させ、表面に導電粒子10が固定化された第1絶縁性樹脂層2を形成する。この場合、好ましくは図3Bに示すように、導電粒子10側から紫外線(UV)を照射する。これにより、図3Cに示すように、第1絶縁性樹脂層2において、導電性粒子10が第2絶縁性樹脂層3側に存在する領域2X(第1絶縁性樹脂層2の剥離フィルム30側表面2bと導電粒子10との間に位置する領域)の第1絶縁性樹脂層の硬化率を、導電粒子10が第2絶縁性樹脂層3側に存在しない領域2Yの硬化率よりも低くすることができる。したがって異方導電接続時の導電粒子10の押し込みが容易になり、且つ導電粒子10の接続平面方向の流動を抑制することもできる。
また、この光重合反応では、異方性導電フィルム1A全体の弾性率が0.13MPa以上となるように第1絶縁性樹脂層2の硬化率を調整する。
一方、図3Dに示すように、剥離フィルム31上に、熱カチオン若しくは熱アニオン重合性樹脂、光カチオン若しくは光アニオン重合性樹脂、熱ラジカル重合性樹脂、又は光ラジカル重合性樹脂で形成された第2絶縁性樹脂層3を常法により形成する。
次に、工程(D)で、図4C又は図6に示すように、工程(B)で形成した第1絶縁性樹脂層の導電粒子側に、結晶性樹脂で形成された中間層と第2絶縁性樹脂層が順次積層している積層体を形成するが、この工程(D)は次の(i)又は(ii)の方法で行うことができる。
工程(C)で形成した第2絶縁性樹脂層3の表面に、図4Aに示すように、結晶性樹脂で形成された中間層4を積層する。次に、図4Bに示すように、その積層体の中間層4と工程(B)で導電粒子10を固定した第1絶縁性樹脂層2の導電粒子10側の表面とを対向させ、図4Cに示すように、これらを熱圧着する。そして剥離フィルム30、31を取り除くことにより図2の異方性導電フィルム1Bを得ることができる。
工程(B)で導電粒子10を固定した第1絶縁性樹脂層2の導電粒子10側の表面に、図5に示すように、結晶性樹脂で形成された中間層4を積層し、その上に工程(C)で形成した第2絶縁性樹脂層3を対向させ、図6に示すように、これらを熱圧着して積層する。そして剥離フィルム30、31を取り除くことにより第2実施例の異方性導電フィルム1Bを得ることができる。
なお、図5及び図6では、第1絶縁性樹脂層2からの導電粒子10の突出量が、図2に示した第2実施例の異方性導電フィルム1Bよりも少ないが、これは、本発明において、第1絶縁性樹脂層2からの導電粒子10の突出量は、種々変えられることを示している。
本発明の異方性導電フィルム1A、1Bは、ICチップ、ICモジュールなどの第1電子部品と、フレキシブル基板、ガラス基板などの第2電子部品とを異方性導電接続する際に好ましく適用することができる。このようにして得られる接続構造体も本発明の一部である。なお、異方性導電フィルムの第1絶縁性樹脂層2側をフレキシブル基板等の第2電子部品側に配し、第2絶縁性樹脂層3側をICチップなどの第1電子部品側に配することが、接続信頼性を高める点から好ましい。
特許第4789738号の実施例1の操作に準じて導電粒子が単層に配列しており、表1に示す配合(質量部)に従って形成した第1絶縁性樹脂層と、中間層と、第2絶縁性樹脂層が積層した異方性導電フィルムを、第1絶縁性樹脂層の弾性率、又は中間層の弾性率を変えて作製した。
実施例7
光ラジカル重合型樹脂層への紫外線照射を、導電粒子側と、導電粒子と反対側から、積算光量2000mJ/cm2ずつ行う以外は実施例2と同様にして異方性導電フィルムを得た。
各実施例及び比較例の異方性導電フィルムについて、(a)異方性導電フィルム全体の弾性率、(b)第1絶縁性樹脂層の弾性率、(c)第1絶縁性樹脂層と中間層の積層体の弾性率、(d)異方性導電フィルムの仮圧着リペア性、(e)異方性導電フィルムを用いて異方性導電接続した接続構造体サンプルの実装粒子捕捉率、(f)同接続構造体サンプルの初期導通性、を次のように評価ないし測定した。結果を表1に示す。
回転式レオメータ(TA Instruments社)を用い、30℃にてねじり方向に定変位(測定圧力 0〜5g)をかけ、時間による応力の変化を測定し、0.1min経過時点でのフィルムの応力(弾性率)を求めた。
フィルムの圧着性の評価用ガラス(全表面ITOコート、ガラス厚み0.7mm)に対し、各異方性導電フィルムの仮圧着を行った。この場合、評価用ガラスに、1.5mm幅にスリットした異方性導電フィルムの第1絶縁性樹脂層を、ツール幅1.5mmの仮圧着機にて、緩衝材として150μm厚のテフロン(登録商標)を使用し、70℃、1MPa、2秒の条件で仮圧着した。
その後、異方性導電フィルムを評価用ガラスから90°方向に機械的に引っ張ることにより剥離し、剥離途中で異方性導電フィルムが破断して評価用ガラスの表面に樹脂が残る状態をNG、異方性導電フィルムが破断せず、異方性導電フィルム全体を剥離できた場合をOKと評価した。
各異方性導電フィルムを用いて、0.5×1.8×20.0mmの大きさのICチップ(バンプサイズ30×85μm、バンプ高さ15μm、バンプピッチ50μm)を、0.5×50×30mmの大きさのコーニング社製のガラス配線基板(1737F)に180℃、80MPa、5秒という条件で実装して接続構造体サンプルを得た。
[加熱・加圧前の接続構造体サンプルのバンプ上に存在する導電粒子の数]に対する、[加熱・加圧後の接続構造体サンプルのバンプ上で実際に捕捉されている導電粒子の数]の割合(%)を以下の式により求め、実装粒子捕捉率とした。
なお、加熱加圧前の接続構造体サンプルのバンプ上に存在する導電粒子の数は、加熱・加圧前のACFの導電粒子の個数密度とバンプ面積から算出し、加熱加圧後の接続構造体サンプルのバンプ上に存在する導電粒子の数は光学顕微鏡の観察により求めた。
実用上、50%以上であることが好ましい。
接続構造体サンプルの導通抵抗を測定した。
実施例7は、実施例2に対して実装粒子捕捉率がやや劣っていたが、実用上問題はなく、フィルム全体の弾性率、仮圧着リペア性、初期導通性については実施例2と同様に好ましい結果を示した。
なお、各実施例及び比較例の異方性導電フィルムにおいて、実装捕捉率及び初期導通性は良好であった。
2 第1絶縁性樹脂層
2a 第1絶縁性樹脂層の表面
2b 第1絶縁性樹脂層の表面
2X 第1絶縁性樹脂層において、第2絶縁性樹脂層側に導電粒子が存在する領域
2Y 第1絶縁性樹脂層において、第2絶縁性樹脂層側に導電粒子が存在しない領域
3 第2絶縁性樹脂層
4 中間層
10 導電粒子
20 光重合性樹脂層
30 剥離フィルム
31 剥離フィルム
Claims (11)
- 第1絶縁性樹脂層及び第2絶縁性樹脂層が積層している異方性導電フィルムであって、
第1絶縁性樹脂層が、光ラジカル重合樹脂で形成され、
第2絶縁性樹脂層が、熱カチオン若しくは熱アニオン重合性樹脂、光カチオン若しくは光アニオン重合性樹脂、熱ラジカル重合性樹脂、又は光ラジカル重合性樹脂で形成され、
第1絶縁性樹脂層の第2絶縁性樹脂層側表面に、異方性導電接続用の導電粒子が単層で配置され、
異方性導電フィルム全体の弾性率が0.13MPa以上である異方性導電フィルム。 - 第1絶縁性樹脂層の弾性率が0.06MPa以上である請求項1記載の異方性導電フィルム。
- 第1絶縁性樹脂層と第2絶縁性樹脂層との間に結晶性樹脂で形成された中間層を有する請求項1記載の異方性導電フィルム。
- 第1絶縁性樹脂層と中間層の積層フィルムの弾性率が0.14MPa以上である請求項1又は2記載の異方性導電フィルム。
- 請求項1記載の異方性導電フィルムの製造方法であって、以下の工程(A)〜(C):
工程(A)
光重合性樹脂層に、導電粒子を単層で配置する工程;
工程(B)
導電粒子を配置した光重合性樹脂層に対して紫外線を照射することにより光重合反応させ、表面に導電粒子が固定化された第1絶縁性樹脂層を形成する工程;
工程(C)
熱カチオン若しくは熱アニオン重合性樹脂、光カチオン若しくは光アニオン重合性樹脂、熱ラジカル重合性樹脂、又は光ラジカル重合性樹脂で形成された第2絶縁性樹脂層を形成する工程;
を有し、
工程(B)において、異方性導電フィルム全体の弾性率が0.13MPa以上となるように光重合反応を行うことで第1絶縁性樹脂層を形成し、
工程(C)で形成した第2絶縁性樹脂層を、工程(B)で形成した第1絶縁性樹脂層の導電粒子側に積層する製造方法。 - 工程(B)において、光重合性樹脂層に対して紫外線を導電粒子側から照射する請求項5記載の異方性導電フィルムの製造方法。
- 請求項1記載の異方性導電フィルムの製造方法であって、以下の工程(A)〜(D):
工程(A)
光重合性樹脂層に、導電粒子を単層で配置する工程;
工程(B)
導電粒子を配置した光重合性樹脂層に対して紫外線を照射することにより光重合反応させ、表面に導電粒子が固定化された第1絶縁性樹脂層を形成する工程;
工程(C)
熱カチオン若しくは熱アニオン重合性樹脂、光カチオン若しくは光アニオン重合性樹脂、熱ラジカル重合性樹脂、又は光ラジカル重合性樹脂で形成された第2絶縁性樹脂層を形成する工程;
工程(D)
工程(B)で形成した第1絶縁性樹脂層の導電粒子側に、結晶性樹脂で形成された中間層と第2絶縁性樹脂層が順次積層している積層体を形成する工程;
を有する製造方法。 - 工程(C)で第2絶縁性樹脂層を形成した後、該第2絶縁性樹脂層に、結晶性樹脂で形成された中間層を積層し、その積層体と工程(B)で形成した第1絶縁性樹脂層を積層することにより工程(D)を行う請求項7記載の製造方法。
- 工程(B)で形成した第1絶縁性樹脂層の導電粒子側に、結晶性樹脂で形成された中間層及び工程(C)で形成した第2絶縁性樹脂層を順次積層することにより工程(D)を行う請求項7記載の製造方法。
- 工程(B)において、光重合性樹脂層に対して紫外線を導電粒子側から照射する請求項7〜9のいずれかに記載の異方性導電フィルムの製造方法。
- 請求項1〜4のいずれかに記載の異方性導電フィルムで第1電子部品を第2電子部品に異方性導電接続した接続構造体。
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US10902973B2 (en) | 2021-01-26 |
US20170140850A1 (en) | 2017-05-18 |
KR20160117462A (ko) | 2016-10-10 |
JP6273875B2 (ja) | 2018-02-07 |
KR102439365B1 (ko) | 2022-09-01 |
TW201544316A (zh) | 2015-12-01 |
WO2015119033A1 (ja) | 2015-08-13 |
CN105940562B (zh) | 2019-01-22 |
TWI648156B (zh) | 2019-01-21 |
CN105940562A (zh) | 2016-09-14 |
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