JP2022093343A - フィラー含有フィルム - Google Patents
フィラー含有フィルム Download PDFInfo
- Publication number
- JP2022093343A JP2022093343A JP2022056054A JP2022056054A JP2022093343A JP 2022093343 A JP2022093343 A JP 2022093343A JP 2022056054 A JP2022056054 A JP 2022056054A JP 2022056054 A JP2022056054 A JP 2022056054A JP 2022093343 A JP2022093343 A JP 2022093343A
- Authority
- JP
- Japan
- Prior art keywords
- filler
- resin layer
- containing film
- film
- anisotropic conductive
- 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.)
- Granted
Links
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- 238000000034 method Methods 0.000 claims description 15
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- 239000010408 film Substances 0.000 description 315
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- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical compound Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 description 1
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- AOWKSNWVBZGMTJ-UHFFFAOYSA-N calcium titanate Chemical compound [Ca+2].[O-][Ti]([O-])=O AOWKSNWVBZGMTJ-UHFFFAOYSA-N 0.000 description 1
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- 150000002500 ions Chemical class 0.000 description 1
- HFGPZNIAWCZYJU-UHFFFAOYSA-N lead zirconate titanate Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ti+4].[Zr+4].[Pb+2] HFGPZNIAWCZYJU-UHFFFAOYSA-N 0.000 description 1
- 229910052451 lead zirconate titanate Inorganic materials 0.000 description 1
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- 238000000691 measurement method Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
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- 238000000206 photolithography Methods 0.000 description 1
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- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
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- 229910052725 zinc Inorganic materials 0.000 description 1
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Images
Classifications
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Abstract
Description
平面視におけるフィラーの面積占有率が25%以下、
樹脂層の層厚Laとフィラーの平均粒子径Dとの比La/Dが0.3以上1.3以下、
フィラー全体に対し、フィラー同士が互いに非接触で存在する個数割合が95%以上であるフィラー含有フィルムを提供する。特に本発明は、フィラー含有フィルムの好ましい一態様として、フィラーが導電粒子であり、フィラー分散層の樹脂層が絶縁性樹脂層であり、異方性導電フィルムとして使用されるフィラー含有フィルムを提供する。
図1Aは、本発明のフィラー含有フィルム(その一態様である異方性導電フィルム)10Aについて、フィラー(又は導電粒子)1の配置を説明する平面図である。また、図1Bは、フィラー含有フィルム10AのX-X断面図である。
フィラー1は、フィラー含有フィルムの用途に応じて、公知の無機系フィラー(金属、金属酸化物、金属窒化物など)、有機系フィラー(樹脂粒子、ゴム粒子など)、有機系材料と無機系材料が混在したフィラー(例えば、コアが樹脂材料で形成され、表面が金属メッキされている粒子(金属被覆樹脂粒子)、導電粒子の表面に絶縁性微粒子を付着させたもの、導電粒子の表面を絶縁処理したもの等)から、硬さ、光学的性能などの用途に求められる性能に応じて適宜選択される。例えば、光学フィルムや艶消しフィルムでは、シリカフィラー、酸化チタンフィラー、スチレンフィラー、アクリルフィラー、メラミンフィラーや種々のチタン酸塩等を使用することができる。コンデンサー用フィルムでは、酸化チタン、チタン酸マグネシウム、チタン酸亜鉛、チタン酸ビスマス、酸化ランタン、チタン酸カルシウム、チタン酸ストロンチウム、チタン酸バリウム、チタン酸ジルコン酸バリウム、チタン酸ジルコン酸鉛及びこれらの混合物等を使用することができる。接着フィルムではポリマー系のゴム粒子、シリコーンゴム粒子等を含有させることができる。異方性導電フィルムでは導電粒子を含有させる。導電粒子としては、ニッケル、コバルト、銀、銅、金、パラジウムなどの金属粒子、ハンダなどの合金粒子、金属被覆樹脂粒子、表面に絶縁性微粒子が付着している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。中でも、金属被覆樹脂粒子が、接続された後に樹脂粒子が反発することで端子との接触が維持され易くなり、導通性能が安定する点から好ましい。また、導電粒子の表面には公知の技術によって、導通特性に支障を来たさない絶縁処理が施されていてもよい。上述の用途別に挙げたフィラーは、当該用途に限定されるものではなく、必要に応じて他の用途のフィラー含有フィルムが含有してもよい。また、各用途のフィラー含有フィルムでは、必要に応じて2種以上のフィラーを併用することができる。
本発明のフィラー含有フィルム(その一態様である異方性導電フィルム)においては、導電粒子等のフィラー1がフィルムの平面視にてランダムではなく、規則的に配置されている。フィルムの平面視にてフィラー1は互いに接触することなく存在し、フィルム厚方向にもフィラー1が互いに重なることなく存在していることが好ましい。そのため、フィラー全体に対し、フィラー1同士が互いに非接触で存在する個数割合は95%以上、好ましくは98%以上、より好ましくは99.5%以上である。また、各フィラー1のフィルム厚方向の位置も揃っていることが好ましい。例えば、図1Aに示したようにフィラー1を6方格子配列とし、後述するようにフィラー1のフィルム厚方向の埋込量Lbを揃えることができる。なお、フィラー同士が互いに非接触で存在する個数割合が95%以上のフィラーの分散状態において、フィラーの所定の規則的な配置に対してフィラーが抜けている箇所Pxがあってもよい(図1A)。このフィラーの抜けは、特性が許容できる範囲において、フィルムの所定の方向に規則的に存在することで確認できる。また、フィラーの抜けをフィルムの長手方向に繰り返し存在させること、あるいはフィラーの抜けている箇所をフィルムの長手方向に漸次増加または減少させることにより、ロット管理が可能となり、フィラー含有フィルム及びそれを用いた接続構造体にトレーサビリティ(追跡を可能とする性質)を付与することも可能となる。これは、フィラー含有フィルムやそれを用いた接続構造体の偽造防止、真贋判定、不正利用防止等にも有効となる。
本発明において、フィラーの個数密度は、1辺が100μm以上の矩形領域を任意に複数箇所(5箇所以上、好ましくは10箇所以上)設定し、測定領域の合計面積を2mm2以上として求めることができる。個々の領域の大きさや数は、個数密度の状態によって適宜調整すればよい。ファインピッチ用途の比較的個数密度が大きい場合の一例として、フィラー含有フィルム10Aから任意により選択した面積100μm×100μm領域の200箇所について、金属顕微鏡などによる観測画像を用いて個数密度を測定し、それを平均することにより得ることができる。面積100μm×100μm領域は、バンプ間スペース50μm以下の接続対象物において、1個以上のバンプが存在する領域になる。
本発明のフィラー含有フィルムの一態様である異方性導電フィルムでは、異方性導電接続時等における押圧治具に必要とされる推力が過度に大きくならないようにする点から導電粒子等のフィラーの面積占有率が25%以下、好ましくは23%以下、より好ましくは20%未満である。また、導通安定性の確保の点から0.5%以上が好ましく、1%以上がより好ましく、2%以上が更に好ましい。フィラーの面積占有率は、「=[平面視におけるフィラーの個数密度]×[フィラー1個の平面視面積の平均]×100」により算出される。フィラー含有フィルムにおける面積占有率はその用途によって適宜選択すればよく、製造に支障をきたさない限り制限はないが、異方性接続以外の接続においても上記のような安定性のことが言えるため、上記同様の範囲が好ましくなる。
(樹脂層の粘度)
樹脂層2の最低溶融粘度は、特に制限はなく、フィラー含有フィルムの用途や、フィラー含有フィルムの製造方法等に応じて適宜定めることができる。例えば、後述の凹み2b、2cを形成できる限り、フィラー含有フィルムの製造方法によっては1000Pa・s程度とすることもできる。一方、フィラー含有フィルムの製造方法として、フィラーを樹脂層の表面に所定の配置で保持させ、そのフィラーを樹脂層に押し込む方法を行うとき、樹脂層がフィルム成形を可能とする点から樹脂層の最低溶融粘度を1100Pa・s以上とすることが好ましい。
図1B、図6に示すようなフィラー含有フィルム(その一態様である異方性導電フィルム)の 「凹み」2b、2cは、「傾斜」もしくは「起伏」という観点から説明することもできる。以下に、図面を参照しながら説明する。
樹脂層2は、フィラー含有フィルムの用途に応じて導電性でも絶縁性でもよく、また、可塑性でも硬化性であってもよいが、好ましくは絶縁性の硬化性樹脂組成物から形成することができ、例えば、熱重合性化合物と熱重合開始剤とを含有する絶縁性の熱重合性組成物から形成することができる。熱重合性組成物には必要に応じて光重合開始剤を含有させてもよい。絶縁性の硬化性樹脂組成物から形成するものとして、異方性導電フィルムが挙げられる。
本発明のフィラー含有フィルムの一態様である異方性導電フィルムでは、樹脂層2の層厚Laとフィラー1の粒子径Dとの比(La/D)が0.3以上1.3以下である。ここで、フィラー1の粒子径Dは、その平均粒子径を意味する。樹脂層2の層厚Laが大き過ぎてこの比が過度に大きくなると、異方性導電接続時にフィラーが端子に押し付けられにくくなると共に、樹脂流動によりフィラーが流されやすくなる。そのためフィラーが位置ずれしやすくなり、端子におけるフィラーの捕捉性が低下する。また、フィラーを端子に押し付けるために押圧治具に必要とされる推力も増大し、低圧実装の妨げになる。反対に樹脂層2の層厚Laが小さすぎてこの比が過度に小さくなると、フィラー1を樹脂層2によって所定の配置に維持することが困難となる。特に、樹脂層2におけるフィラー1の配置の維持の点から、この比(La/D)は、好ましくは0.3より大きく、より好ましくは0.4以上とする。また、異方性導電接続時の過度な樹脂流動の抑制及び低圧実装の実現の点から、好ましくは1以下である。フィラー1を樹脂層2から露出させることを容易とし、低圧実装をより容易にする点からは、この比(La/D)を1未満とすることが好ましく、より好ましくは0.6未満、さらに好ましくは0.5以下である。この場合、フィラー1は樹脂層2を貫通していてもよい。
本実施例のフィラー含有フィルム(その一態様である異方性導電フィルム)10Aでは、フィラー1は、図1Bに示すように、埋込率(Lb/D)が30%以上100%以下で、フィラー1が樹脂層2の片面から突出するように埋め込まれている。この他、本発明のフィラー含有フィルムとしては、図2に示すフィラー含有フィルム(その一態様である異方性導電フィルム)10Bのように、埋込率100%あるいはその近傍で、フィラー1が樹脂層2の片面から露出し、そのフィルム面とフィラー1の頂部1aとが略面一となるように埋め込まれている態様、図3に示すフィラー含有フィルム(その一態様である異方性導電フィルム)10Cのように、樹脂層2の片面においてフィラー1がそのフィルム面と略面一となり、反対面においてフィラー1がフィルム面から露出せずに突出している態様、図4に示すフィラー含有フィルム(その一態様である異方性導電フィルム)10Dのように樹脂層2の片面においてフィラー1がフィルム面よりも埋め込まれて露出し、他面からはフィラー1が露出せずにフィルム面から突出している態様、図5に示すフィラー含有フィルム(その一態様である異方性導電フィルム)10Eのように、樹脂層2の表面に凹みがなく、フィラー1がその頂部1aの1点で樹脂層2から露出している態様、図6に示すフィラー含有フィルム(その一態様である異方性導電フィルム)10Fのように、フィラー1が樹脂層2から露出せず、フィラー1の直上の樹脂層2の表面に凹み(周囲の樹脂層の表面よりも凹んでいる部分)2cを有している態様などを挙げることができる。
本発明のフィラー含有フィルムとしては、フィラー分散層3に、樹脂層2を構成する樹脂よりも好ましくは最低溶融粘度が低い第2の樹脂層4を積層することができる(図7~図9)。この第2の樹脂層4は、樹脂層2よりも最低溶融粘度が低いため、フィラー含有フィルムを異方性導電フィルムとして構成した場合、異方性導電接続時に電子部品のバンプ等の端子によって形成される空間を充填し、対向する電子部品同士の接着性を向上させることができる。即ち、異方性導電フィルムを用いた電子部品の低圧実装を可能とするため、及び異方性導電接続時の樹脂層2の樹脂流動を抑制してフィラー1の粒子捕捉性を向上させるため、樹脂層2の粘度を高くすると共に、フィラー1が位置ずれを起こさない限りで樹脂層2の厚さは薄くすることが望ましいが、樹脂層2の厚さを過度に薄くすると、対向する電子部品同士を接着させる樹脂量の不足を招くことから接着性の低下が懸念される。これに対し、異方性導電接続時に樹脂層2よりも粘度が低い第2の樹脂層4を設けることにより、電子部品同士の接着性も向上させることができ、第2の樹脂層4の流動性が高いことから端子によるフィラーの挟持や押し込みを阻害し難くすることができる。
第2の樹脂層4と樹脂層2を挟んで反対側に第3の樹脂層が設けられていてもよい。第3の樹脂層をタック層として機能させることができる。第2の樹脂層4と同様に、電子部品の電極やバンプによって形成される空間を充填させるために設けてもよい。
フィラー含有フィルムの用途によっては、複数のフィラー分散層を積層してもよく、積層したフィラー分散層間に、第2の樹脂層のようにフィラーを含有していない層を介在していてもよく、最外層に第2の樹脂層や第3の樹脂層を設けてもよい。
フィラー分散層3の単層から形成されている本発明のフィラー含有フィルムは、例えば、樹脂層2の表面にフィラー1を所定の配列で保持させ、そのフィラー1を平板又はローラーで樹脂層2に押し込む。
本発明のフィラー含有フィルムは、従前のフィラー含有フィルムと同様に使用することができ、フィラー含有フィルムを貼り合わせることができれば物品に特に制限はない。フィラー含有フィルムの用途に応じた種々の物品に圧着により、好ましくは熱圧着により貼着することができる。この貼り合わせ時には光照射を利用してもよく、熱と光を併用してもよい。例えば、フィラー含有フィルムの樹脂層が、該フィラー含有フィルムを貼り合わせる物品に対して十分な粘着性を有する場合、フィラー含有フィルムの樹脂層を物品に軽く押し付けることによりフィラー含有フィルムが一つの物品の表面に貼着したフィルム貼着体を得ることができる。この場合に、物品の表面は平面に限られず、凹凸があってもよく、全体として屈曲していてもよい。物品がフィルム状又は平板状である場合には、圧着ローラーを用いてフィラー含有フィルムをそれらの物品に貼り合わせてもよい。これにより、フィラー含有フィルムのフィラーと物品を直接的に接合させることもできる。
(1)異方性導電フィルムの製造
表1に示した配合で、導電粒子分散層を形成する絶縁性樹脂層形成用樹脂組成物、及び第2の絶縁性樹脂層形成用樹脂組成物をそれぞれ調製した。絶縁性樹脂層の最低溶融粘度は3000Pa・s以上であり、この絶縁性樹脂層の最低溶融粘度と第2の絶縁性樹脂層の最低溶融粘度の比は2以上であった。
(1)で作製した実施例及び比較例の異方性導電フィルムについて、接続に十分な面積で裁断し、以下のようにして(a)初期導通抵抗、(b)導通信頼性、(c)平均粒子捕捉数、(d)ショート率を評価した。結果を表2に示す。
以下に示す評価用ICとガラス基板とを180℃、60MPa、5秒で異方性導電フィルムを介して加熱加圧し、評価用接続物を得た。このとき、押圧治具に必要な推力は125Nであった。
外形 1.8×20.0mm
厚み 0.5mm
バンプ仕様 サイズ30×85μm、バンプ間距離50μm、バンプ高さ15μm
ガラス材質 コーニング社製1737F
外形 30×50mm
厚み 0.5mm
電極 ITO配線
(a)で得た評価用接続物を、温度85℃、湿度85%RHの恒温槽に500時間おいた後の導通抵抗を、初期導通抵抗と同様に測定した。導通抵抗は実用上5Ω以下であることが好ましい。
(a)と同様の評価用ICを使用し、この評価用ICと端子パターンが対応するITOパターンガラス基板とを、(a)と同様の条件で加熱加圧し、加熱加圧後の端子対100個について導電粒子の捕捉数を計測し、その平均を求めた。平均粒子捕捉数は、実用上、端子あたり3個以上が好ましい。
ショート率の評価用ICを使用し、(a)初期導通抵抗の評価と同様にして評価用接続物を得、得られた評価用接続物のショート数を計測してショート率(即ちショート発生率)を求め、次の基準で評価した。
外形 15×13mm
厚み 0.5mm
バンプ仕様 サイズ25×140μm、バンプ間距離7.5μm、バンプ高さ15μm
A:50ppm未満
B:50ppm以上200ppm未満
C:200ppm以上
2 樹脂層(絶縁性樹脂層)
2b 凹み(傾斜)
2c 凹み(起伏)
3 フィラー分散層(導電粒子分散層)
4 第2の樹脂層
10A、10B、10C、10D、10E、10F、10G、10H、10I フィラー含有フィルム(その一態様である異方性導電フィルム)
2 樹脂層(絶縁性樹脂層)
2b 凹み(傾斜)
2c 凹み(起伏)
3 フィラー分散層(導電粒子分散層)
4 第2の樹脂層
10A、10B、10C、10D、10E、10F、10G、10H、10I フィラー含有フィルム(その一態様である異方性導電フィルム)
La 樹脂層の層厚
Lb 隣接するフィラー間の中央部における接平面とフィラーの最深部との距離
Lc 傾斜又は起伏におけるフィラーの露出(直上)部分の径
Ld フィラーの周り又は直上の樹脂層の傾斜又は起伏の最大径
Le フィラーの周りの樹脂層における傾斜の最大深さ
Lf フィラーの直上の樹脂層における起伏の最大深さ
Claims (14)
- 樹脂層にフィラーが規則的に配置されているフィラー分散層を有するフィラー含有フィルムであって、
平面視におけるフィラーの面積占有率が25%以下、
樹脂層の層厚Laとフィラーの平均径Dとの比La/Dが0.3以上1.3以下、
フィラー全体に対し、フィラー同士が互いに非接触で存在する個数割合が95%以上
であるフィラー含有フィルム。 - フィラー全体に対し、フィラー同士が互いに非接触で存在する個数割合が99.5%以上である請求項1記載のフィラー含有フィルム。
- フィラーが6方格子、正方格子又は斜方格子に配置されており、任意のフィラーP0との距離が近い順に3個のフィラーを選択した場合に、その3個のフィラーとフィラーP0との距離のうち最大の距離と最小の距離との比が1.2以下である請求項1又は2記載のフィラー含有フィルム。
- フィラーが樹脂層から露出している請求項1~3のいずれかに記載のフィラー含有フィルム。
- 樹脂層よりも最低溶融粘度が低い第2の樹脂層がフィラー分散層に積層されている請求項1~3のいずれかに記載のフィラー含有フィルム。
- フィラー含有フィルムを構成する樹脂層全体の最低溶融粘度が200~4000Pa・sである請求項1~5のいずれかに記載のフィラー含有フィルム。
- 第2の樹脂層にフィラーが食い込んでいる請求項5又は6記載のフィラー含有フィルム。
- フィラー近傍の樹脂層の表面が、隣接するフィラー間の中央部における樹脂層の接平面に対して傾斜もしくは起伏を有し、該傾斜では、フィラーの周りの樹脂層の表面が前記接平面に対して欠けており、該起伏では、フィラー直上の樹脂層の樹脂量が、該フィラー直上の樹脂層の表面が前記接平面にあるとしたときに比して少なくなっている請求項1~7のいずれかに記載のフィラー含有フィルム。
- フィラーが導電粒子であり、フィラー分散層の樹脂層が絶縁性樹脂層であり、異方性導電フィルムとして使用される請求項1~8のいずれかに記載のフィラー含有フィルム。
- 請求項1~9のいずれかに記載のフィラー含有フィルムが物品に貼着しているフィルム貼着体。
- 請求項1~9のいずれかに記載のフィラー含有フィルムを介して第1物品と第2物品とが接続されている接続構造体。
- 請求項9記載のフィラー含有フィルムを介して第1電子部品と第2電子部品とが異方性導電接続されている請求項11記載の接続構造体。
- 請求項1~9のいずれかに記載のフィラー含有フィルムを介して第1物品と第2物品を圧着する接続構造体の製造方法。
- 第1物品、第2物品をそれぞれ第1電子部品、第2電子部品とし、請求項9記載のフィラー含有フィルムを介して第1電子部品と第2電子部品を熱圧着することにより第1電子部品と第2電子部品が異方性導電接続された接続構造体を製造する請求項13記載の接続構造体の製造方法。
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WO2019235560A1 (ja) * | 2018-06-06 | 2019-12-12 | デクセリアルズ株式会社 | フィラー含有フィルム |
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JP7452418B2 (ja) * | 2018-06-26 | 2024-03-19 | 株式会社レゾナック | 異方性導電フィルム及びその製造方法並びに接続構造体の製造方法 |
US11240918B2 (en) * | 2018-08-28 | 2022-02-01 | Research And Business Foundation Sungkyunkwan University | Method for flip-chip bonding using anisotropic adhesive polymer |
JP7321863B2 (ja) * | 2019-09-27 | 2023-08-07 | 株式会社フコク | 異方性感圧導電膜 |
JP7261713B2 (ja) * | 2019-09-27 | 2023-04-20 | パナソニックホールディングス株式会社 | コイン形電池 |
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