JP2013110110A - 仮圧着工程性を改善した異方性導電フィルム及び半導体装置(Anisotropicconductivefilmwitheasypre−bondingprocessandthesemiconductordevice) - Google Patents
仮圧着工程性を改善した異方性導電フィルム及び半導体装置(Anisotropicconductivefilmwitheasypre−bondingprocessandthesemiconductordevice) Download PDFInfo
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- JP2013110110A JP2013110110A JP2012250429A JP2012250429A JP2013110110A JP 2013110110 A JP2013110110 A JP 2013110110A JP 2012250429 A JP2012250429 A JP 2012250429A JP 2012250429 A JP2012250429 A JP 2012250429A JP 2013110110 A JP2013110110 A JP 2013110110A
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- adhesive layer
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- conductive film
- acrylate
- anisotropic conductive
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- 230000008023 solidification Effects 0.000 description 1
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Classifications
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- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
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Abstract
【解決手段】本発明は、導電性接着層及び絶縁性接着層が積層された異方性導電フィルムに関するもので、前記導電性接着層の反応性モノマー含量を絶縁性接着層の反応性モノマー含量より高くしてガラスに対する導電性接着層の粘着力が強化することで、仮圧着時の工程不良の問題を改善した、異方性導電フィルムに関するものである。
【選択図】なし
Description
本発明に用いられる前記配線基板、半導体チップは特に限定されなく、当該技術分野で知られているものを用いることができる。
本発明に使用されるバインダー樹脂として、例えば、熱可塑性樹脂、アクリル系樹脂、ポリウレタン系樹脂、ポリウレタンアクリレート樹脂、ポリエステルウレタン樹脂、またはNBR系樹脂などがある。
本発明で使用できる熱可塑性樹脂としては、アクリロニトリル系、フェノキシ系、ブタジエン系、アクリル系、ポリウレタン系、ウレタンアクリレート系、ポリアミド系、オレフィン系、シリコン系、及びNBR(Nitrile butadiene rubber)系樹脂からなる群より選ばれる1種以上を使用することができるが、これらに限定されない。
本発明で使用できるアクリル系樹脂は、アクリル系単量体及び/又はこれと重合できる単量体を重合して得ることができる。例えば、アクリル系樹脂は炭素数2ないし10のアルキル基を有する(メタ)アクリレート、(メタ)アクリル酸、ビニルアセテート及びこれから変性されたアクリル系単量体からなる群より選ばれる1種以上の単量体を重合して製造することができる。重合方法は特に限定されない。
本発明で使用できるポリウレタン系樹脂はウレタン結合を有する高分子樹脂で、イソホロンジイソシアネート、ポリテトラメチレングリコールなどを重合して製造されるが、これらに限定されない。ポリウレタン系樹脂は重量平均分子量が50,000ないし100,000g/molの樹脂であり得る。
本発明で使用できるポリウレタンアクリレート樹脂は、イソシアネート、ポリオール、ジオール類及びヒドロキシアクリレートを共重合した樹脂であり得る。
本発明で使用できるポリエステルウレタン樹脂は、ポリエステルポリオールとジイソシアネートの反応により得ることができる。
ジカルボン酸の例として、テレフタル酸、イソフタル酸、アジピン酸、セバシン酸などがあり、前記のような芳香族ジカルボン酸、又は脂肪族ジカルボン酸が好ましい。
本発明で使用できるNBR系樹脂は、アクリロニトリルとブタジエンの乳化重合により製造される共重合体で、共重合体の中でアクリロニトリルとブタジエンの各々の含量は特に限定されなく、重合方法も特に限定されない。NBR系樹脂は重量平均分子量が50,000ないし2,000,000g/molの樹脂であることができる。
反応性モノマーとは、一般的に分子量が1,000未満の化合物で実質的に硬化反応を起こす化合物を意味する。本発明の反応性モノマーとして、好ましくは(メタ)アクリレートモノマーを使用することができる。
(メタ)アクリレートモノマーは特に限定されないが、6−ヘキサンジオールモノ(メタ)アクリレート、2−ヒドロキシエチル(メタ)アクリレート、2−ヒドロキシプロピル(メタ)アクリレート、2−ヒドロキシブチル(メタ)アクリレート、2−ヒドロキシ−3−フェニルオキシプロピル(メタ)アクリレート、1,4−ブタンジオール(メタ)アクリレート、2−ヒドロキシアルキル(メタ)アクリロイルホスフェート、4−ヒドロキシシクロヘキシル(メタ)アクリレート、ネオペンチルグリコールモノ(メタ)アクリレート、トリメチロールエタンジ(メタ)アクリレート、トリメチロールプロパンジ(メタ)アクリレート、ペンタエリスリトールトリ(メタ)アクリレート、ジペンタエリスリトールペンタ(メタ)アクリレート、ペンタエリスリトールヘキサ(メタ)アクリレート、ジペンタエリスリトールヘキサ(メタ)アクリレート、グリセリンジ(メタ)アクリレート、t−ヒドロフルフリル(メタ)アクリレート、イソデシル(メタ)アクリレート、2−(2−エトキシエトキシ)エチル(メタ)アクリレート、ステアリル(メタ)アクリレート、ラウリル(メタ)アクリレート、2−フェノキシエチル(メタ)アクリレート、イソボルニル(メタ)アクリレート、トリデシル(メタ)アクリレート、エトキシ化ノニルフェノール(メタ)アクリレート、エチレングリコールジ(メタ)アクリレート、ジエチレングリコールジ(メタ)アクリレート、トリエチレングリコールジ(メタ)アクリレート、t−エチレングリコールジ(メタ)アクリレート、ポリエチレングリコールジ(メタ)アクリレート、1,3−ブチレングリコールジ(メタ)アクリレート、トリプロピレングリコールジ(メタ)アクリレート、エトキシ化ビスフェノール−Aジ(メタ)アクリレート、シクロヘキサンジメタノールジ(メタ)アクリレート、フェノキシ−t−グリコール(メタ)アクリレート、2−メタクリロイルオキシエチルホスフェート、ジメチロールトリシクロデカンジ(メタ)アクリレート、トリメチロールプロパンベンゾエートアクリレート、アシッドホスホキシエチル(メタ)アクリレート、2−アクリロイルオキシエチルフタレート、トリメチロールプロパントリアクリレート、テトラメチロールメタンテトラアクリレート、2−ヒドロキシ−1,3−ジアクリロキシプロパン、2,2−ビス[4−(アクリロキシポリメトキシ)フェニル]プロパン、2,2−ビス[4−アクリロキシポリエトキシ)フェニル]プロパン、ジシクロペンテニルアクリレート、トリシクロデカニルアクリレート、トリス(アクリロイルオキシエチル)イソシアヌレート、イソシアヌル酸エチレンオキサイド変性ジアクリレート、ウレタンアクリレート、及びこれらの組合せからなる群より選ばれる1種以上であることができる。
本発明で使用されるラジカル開始剤として、光重合型開始剤又は熱硬化型開始剤の中で、1種以上を組み合わせて使用することができる。好ましくは、熱硬化型開始剤を使用することができる。
光重合型開始剤として、ベンゾフェノン、o−ベンゾイル安息香酸メチル、4−ベンゾイル−4−メチルジフェニル硫化物、イソプロピルチオクサントン、ジエチルチオクサントン、4−ジエチル安息香酸エチル、ベンゾインエーテル、ベンゾイルプロピルエーテル、2−ヒドロキシ−2−メチル−1−フェニルプロパン−1−オン、ジエトキシアセトフェノンなどが使用できるが、これらに限定されることではない。
熱硬化型開始剤として、パーオキサイド系とアゾ系を使用することができるが、これらに限定されることではない。
本発明の導電性接着層に使用できる導電粒子として、金、銀、ニッケル、銅、錫、ハンダなどを含む金属粒子;炭素;ベンゾグアニン、ポリメタクリル酸メチル(PMMA;Polymethylmethacrylate)、アクリルコポリマー、ポリスチレンなどを含む樹脂、及びその変性樹脂を粒子にして、金、銀、ニッケル、銅、錫、ハンダなどを含む金属でコーティングされたもの;及び、その上に絶縁粒子又は絶縁膜を加えてコーティングし絶縁化処理した導電粒子などを使用することができるが、これらに限定されることではない。
(e−1)導電性接着層の厚さ
本発明の導電性接着層の厚さは導電性粒子の大きさに応じて適切な範囲で選択することができ、例えば導電粒子の大きさ(平均粒径)が3μmである場合、導電性接着層の厚さは、好ましくは4ないし6μmであり得る。すなわち、導電性接着層の厚さは、一般的に導電粒子の大きさの1.3倍〜2倍程度の範囲が望ましいものである。
本発明の絶縁性接着層の厚さは電極間のスペース部の大きさ、及び間隔などにより決定され、好ましくは6ないし20μmである。
導電性接着層のピール強度は多層異方性導電フィルム各々を常温(25℃)で1時間放置した後、パターン無しのガラスに実測温度25℃で1MPa、1秒の仮圧着条件で1.5mm幅の異方性導電フィルムを仮圧着してPET離型フィルムを除去する。その後、接着テープ(Nitto社)を、1.5mmの幅でガラス上に仮圧着した異方性導電フィルムより5cm長く準備して前記接着テープをガラス上に仮圧着した異方性導電フィルム上に置いてゴムローラを2回移動させ接着テープと異方性導電フィルムをくっつける。
≪多層構造の異方性導電フィルムの製造≫
実施例1
<導電性接着層の反応性モノマー含量が絶縁性接着層の反応性モノマー含量より高い異方性導電フィルムの製造>
(1)導電性接着層
バインダー樹脂として、NBR系樹脂(N−34、日本ゼオン)5質量%、ポリウレタンバインダー(NPC7007T、NANUX社)24質量%、アクリルバインダー(AOF−7003、AEKYUNG化学)28質量%、及びウレタンアクリレート(NPC7007、NANUX社)12質量%;反応性モノマーとして、2−メタクリロイルオキシエチルホスフェート1質量%、ペンタエリスリトールトリ(メタ)アクリレート12質量%、及び、2−ヒドロキシエチル(メタ)アクリレート12質量%;熱硬化型開始剤として、ラウリルパーオキサイド3質量%;及び、導電粒子として、3μmの大きさ(平均粒径)の導電粒子(Sekisui社)3質量%を使用しこれを混合することにより、4μm厚さの導電性接着層を製造した。
バインダー樹脂として、NBR系樹脂(N−34、日本ゼオン)5質量%、ポリウレタンバインダー(NPC7007T、NANUX社)29質量%、アクリルバインダー(AOF−7003、AEKYUNG化学)30質量%、及び、ウレタンアクリレート(NPC7007、NANUX社)12質量%;反応性モノマーとして、2−メタクリロイルオキシエチルホスフェート1質量%、ペンタエリスリトールトリ(メタ)アクリレート10質量%、及び、2−ヒドロキシエチル(メタ)アクリレート10質量%;及び、熱硬化型開始剤として、ラウリルパーオキサイド3質量%を使用しこれらを混合することにより、10μm厚さの絶縁性接着層を製造した。
<導電性接着層の反応性モノマー含量が絶縁性接着層の反応性モノマー含量より高い異方性導電フィルムの製造>
(1)導電性接着層
前記実施例1の(1)において、ポリウレタンバインダー(NPC7007T、NANUX社)を20質量%、アクリルバインダー(AOF−7003、AEKYUNG化学)を22質量%、ペンタエリスリトールトリ(メタ)アクリレートを17質量%、2−ヒドロキシエチル(メタ)アクリレートを17質量%として含量を変えて使用したこと以外は、前記実施例1の(1)と同一方法で製造した。
前記実施例1の(2)において、ポリウレタンバインダー(NPC7007T、NANUX社)を27質量%、アクリルバインダー(AOF−7003、AEKYUNG化学)を28質量%、ペンタエリスリトールトリ(メタ)アクリレートを12質量%、2−ヒドロキシエチル(メタ)アクリレートを12質量%として含量を変えて使用したこと以外は、前記実施例1の(2)と同一方法で製造した。
<絶縁性接着層の反応性モノマー含量が導電性接着層の反応性モノマー含量より高い異方性導電フィルムの製造>
(1)導電性接着層
前記実施例1の(1)において、アクリルバインダー(AOF−7003、AEKYUNG化学)を40質量%、ペンタエリスリトールトリ(メタ)アクリレートを6質量%、2−ヒドロキシエチル(メタ)アクリレートを6質量%として含量を変えて使用したこと以外は、前記実施例1の(1)と同一方法で製造した。
前記実施例1の(2)と同一方法で製造した。
<絶縁性接着層の反応性モノマー含量が導電性接着層の反応性モノマー含量より高い異方性導電フィルムの製造>
(1)導電性接着層
前記実施例1の(1)において、ポリウレタンバインダー(NPC7007T、NANUX社)を31質量%、アクリルバインダー(AOF−7003、AEKYUNG化学)を38質量%、ペンタエリスリトールトリ(メタ)アクリレートを3質量%、2−ヒドロキシエチル(メタ)アクリレートを4質量%として含量を変えて使用したこと以外は、前記実施例1の(1)と同一方法で製造した。
前記実施例1の(2)において、ポリウレタンバインダー(NPC7007T、NANUX社)を17質量%、アクリルバインダー(AOF−7003、AEKYUNG化学)を18質量%、ペンタエリスリトールトリ(メタ)アクリレートを22質量%、2−ヒドロキシエチル(メタ)アクリレートを22質量%として含量を変えて使用したこと以外は、前記実施例1の(2)と同一方法で製造した。
<仮圧着性測定−ピール強度の測定>
前記実施例1、2及び比較例1、2の多層異方性導電フィルムにおいて、導電性接着層及び絶縁性接着層のピール強度を各々測定した。
<接着力の信頼性の評価>
前記実施例1、2及び比較例1、2の多層異方性導電フィルムの各々をメタル電極ガラス(Mo/Al/Mo構造、サムスン電子)とCOF(Chip on Film)(サムスン電子)を利用して実測温度70℃で1秒の仮圧着条件と、180℃、5秒、4.5MPaの本圧着条件で接続して、前記の各々の試片を10個ずつ準備して、これら各々の初期接着力を測定して平均値を計算した。
<接続抵抗の信頼性の評価>
前記実施例1、2及び比較例1、2の多層異方性導電フィルム各々を常温(25℃)で1時間放置した後、ITO層を1000Åで被膜した、パターン無しのガラスに4端子測定可能なパターンを形成したCOF(サムスン電子)を利用して実測温度70℃で1秒の仮圧着条件と、180℃、5秒、4.5MPaの本圧着条件で接続して前記の各々の試片を10個ずつ準備し、これらの各々を4端子測定方法で初期接続抵抗を測定(ASTM F43−64Tの方法に準する)して平均値を計算した。
<電気的短絡発生の測定>
前記実施例1、2及び比較例1、2の多層異方性導電フィルムの各々に対する電気的短絡発生は、100回測定した時短絡による問題発生の比率を測定した。
<伸び率の測定>
前記実施例1、2及び比較例1、2の異方性導電フィルムを1.5mmの幅でスリーティングして3cmの長さで準備した。前記フィルムの2cmを離型フィルムから除去した後UTM(万能試験機(引張強度試験機ないし剥離強度試験装置))に置いて他方の片側(離型フィルムが除去されてない部分)をUTM(万能試験機(引張強度試験機ないし剥離強度試験装置))の反対側に置いた後、5Nのロードセルを使用して50mm/分の速度で引張り、切れるまでの伸び率を測定した。
Claims (9)
- 導電性接着層及び絶縁性接着層が積層された異方性導電フィルムにおいて、前記導電性接着層の反応性モノマー含量が前記絶縁性接着層の反応性モノマー含量より多い、異方性導電フィルム。
- 前記導電性接着層の総質量を基準として、前記導電性接着層の反応性モノマー含量が25ないし50質量%で、前記絶縁性接着層の総質量を基準として前記絶縁性接着層の反応性モノマー含量が20ないし40質量%である、請求項1に記載の異方性導電フィルム。
- 前記導電性接着層の反応性モノマー含量が、前記絶縁性接着層の反応性モノマー含量の1倍超過ないし2倍以下である、請求項1または2に記載の異方性導電フィルム。
- 前記導電性接着層、前記絶縁性接着層、又は前記導電性接着層及び前記絶縁性接着層の反応性モノマーは、2−メタクリロイルオキシエチルホスフェート、ペンタエリスリトールトリ(メタ)アクリレート、及び2−ヒドロキシエチル(メタ)アクリレートからなる群より選ばれる1種以上である、請求項1ないし3の何れか一つに記載の異方性導電フィルム。
- 異方性導電フィルムの総質量を基準として、反応性モノマー20ないし45質量%、及びバインダー樹脂55ないし80質量%を含み、各々のピール強度が異なる二つ以上の層を有する、請求項1ないし4の何れか一つに記載の異方性導電フィルム。
- 前記反応性モノマーは、2−メタクリロイルオキシエチルホスフェート、ペンタエリスリトールトリ(メタ)アクリレート、及び2−ヒドロキシエチル(メタ)アクリレートからなる群より選ばれる1種以上である、請求項5に記載の異方性導電フィルム。
- 異方性導電フィルムの総質量を基準として、熱可塑性樹脂45ないし75質量%、導電粒子1ないし10質量%、及び反応性モノマー20ないし45質量%を含み、伸び率が400ないし800%である、請求項1ないし6の何れか一つに記載の異方性導電フィルム。
- 前記反応性モノマーは、2−メタクリロイルオキシエチルホスフェート、ペンタエリスリトールトリ(メタ)アクリレート、及び2−ヒドロキシエチル(メタ)アクリレートからなる群より選ばれる1種以上である、請求項7に記載の異方性導電フィルム。
- 配線基板;
前記配線基板のチップ搭載面に接着されている異方性導電フィルム;及び、
前記フィルム上に搭載された半導体チップを含む半導体装置において、
前記異方性導電フィルムは、請求項1〜8の何れか一つに記載のフィルムである、半導体装置。
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JP2011159486A (ja) * | 2010-02-01 | 2011-08-18 | Sony Chemical & Information Device Corp | 異方性導電フィルム、接合体及び接続方法 |
JP2012140589A (ja) * | 2010-12-29 | 2012-07-26 | Cheil Industries Inc | 異方導電性フィルム、これに含まれる異方導電性フィルム組成物およびこれを含む装置 |
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JP2015124321A (ja) * | 2013-12-27 | 2015-07-06 | リンテック株式会社 | 導電性粘着剤組成物、導電性粘着シートおよび導電性粘着シートの製造方法 |
WO2022102573A1 (ja) * | 2020-11-10 | 2022-05-19 | 昭和電工マテリアルズ株式会社 | 回路接続用接着剤フィルム及びその製造方法、並びに回路接続構造体及びその製造方法 |
WO2023106400A1 (ja) * | 2021-12-10 | 2023-06-15 | 株式会社レゾナック | 回路接続用接着剤フィルム、並びに回路接続構造体及びその製造方法 |
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US8896117B2 (en) | 2014-11-25 |
KR20130055388A (ko) | 2013-05-28 |
US20130127038A1 (en) | 2013-05-23 |
JP6169347B2 (ja) | 2017-07-26 |
CN103122221B (zh) | 2015-11-11 |
KR101479658B1 (ko) | 2015-01-06 |
TWI626288B (zh) | 2018-06-11 |
TW201329189A (zh) | 2013-07-16 |
CN103122221A (zh) | 2013-05-29 |
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