JP4875386B2 - 低応力導電性接着材 - Google Patents

低応力導電性接着材 Download PDF

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JP4875386B2
JP4875386B2 JP2006057140A JP2006057140A JP4875386B2 JP 4875386 B2 JP4875386 B2 JP 4875386B2 JP 2006057140 A JP2006057140 A JP 2006057140A JP 2006057140 A JP2006057140 A JP 2006057140A JP 4875386 B2 JP4875386 B2 JP 4875386B2
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conductive
silver
epoxy
present
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JP2006249426A (ja
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チー−ミン・チェン
アンドリュー・コリンス
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ヘンケル・アーゲー・アンド・カンパニー・カーゲーアーアー
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    • H01BCABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20Conductive material dispersed in non-conductive organic material
    • H01B1/22Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01CPLANTING; SOWING; FERTILISING
    • A01C1/00Apparatus, or methods of use thereof, for testing or treating seed, roots, or the like, prior to sowing or planting
    • A01C1/02Germinating apparatus; Determining germination capacity of seeds or the like
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01GHORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
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Description

発明の詳細な説明
発明の分野
本発明は、電気的に安定な相互接続を与えるために超小型電子デバイス又は半導体パッケージにおいて導電性材料として使用されるのに適した組成物に関する。
発明の背景
超小型電子デバイス及び半導体パッケージの作製及び組立において、導電性組成物が様々な目的に使用されている。例えば、導電性接着材は、集積回路チップを基板に接着するために(ダイ取り付け用接着材)又は回路アセンブリを印刷配線基板に接着するために(表面実装導電性接着材)使用される。
基板に部品をソルダー処理するために電子産業で使用される先端技術においては、63重量%の錫と37重量%の鉛を含む所謂共晶ソルダーである金属ソルダー合金が使用される。それは回路基板にペースト又はソルダープリフォームとして施され、その溶融温度(183℃)以上に加熱され、ソルダーペーストを溶融させ、接合部を形成する。あるいは、基板を溶融ソルダーの波の上を通過させ、電子部品を回路基板に接着するための接合部を形成する。別の場合、フラックス材料を使用して、金属表面が表面酸化されることを排除し、溶融ソルダーが表面に強固に結合することを可能にし、耐衝撃性に優れた信頼できるソルダー接合部を形成する。ソルダー技術は数十年にわたって存在してきたが、それは一方でいくつかの問題点を有する。合金中の鉛は環境に優しいとは言えない。電子産業用ソルダーにおける鉛の使用を課税し、制限し、あるいは禁止するために、多くの環境に関する規制が提案されている。第二に、高いプロセス温度によってより高価な熱安定性基板を使用することが必要であるが、この高いプロセス温度は電子産業においてより一般的に使用されるようになっているフレキシブル基板に適合しない。別の問題点は、リフロープロセス後にフラックス材料からの残さを洗浄するための余分な工程が必要であるが、これが高価で効率の悪いプロセスとなっている。
導電性接着材は、無鉛、低プロセス温度、及びソルダーフラックス及びそれに伴うフラックスの洗浄工程を必要としない簡単な組立プロセスに起因して従来のソルダーアセンブリを超えるいくつかの利点を与える。導電性接着材の望ましい性質の中に、室温での長い可使時間、比較的低い硬化温度及び比較的短い硬化時間、スクリーン印刷に良好なレオロジー、硬化後に電流を流すために十分な導電性、硬化後に基板に対する許容できる接着力、高温及び高湿度で長時間にわたり安定な電気抵抗、並びに良好な耐衝撃性がある。導電性接着材は様々なマイクロ波用途に意図される大面積アセンブリに特に有用である。その用途では、FR4又はセラミック回路基板をアルミニウム又は銅のコアを有する金属基板に接着することが必要である。そのような用途において、導電性接着材は電気的インテグリティ、ボンド−ラインコンシステンシー及び改善された熱散逸を提供し、それは規制上の要件に対応し、損失を最小にし、高周波デジタル信号の歪みを最小にし、グランドプレーンに対する低インピーダンスを維持する。
二つのタイプの導電性接着材、フィルム及びペーストが一般に利用される。フィルム接着材はソルダーに対する低温度プロセスの代替物として利用され、電気回路基板及び金属支持体の間に堅固なグランドパスを形成する。フィルム導電性接着材はボンドライン厚さにおけるコンシステンシー、低流動性、複雑なダイ切断部分としての利用可能性に起因して大面積アセンブリに好適である。フィルム接着材は、所望のPCBの寸法に予備切断され、B段階処理(B-stage)条件においてエンドアセンブラーによって受け取られる。キャリア基材(通常MYLAR)がフィルムから除去され、そのフィルムが接着のために基板の間に置かれ、そして、高温高圧条件下でパッケージと共に接着される。さらに、フィルム接着材はペースト接着材よりも非常に高い粘度を有するので、そのフィルムを長時間室温で保管するときも、フィラーのセッティングが問題にならない。
フィルム接着材を取り巻く一つの問題はフレキシビリティである。高い強度を有するフィルム接着材は一般に制限されたフレキシビリティを有する高モジュラス接着材である。そのような高モジュラス及び高架橋密度を有するフィルムは、硬化後に基板と金属ヒートシンクとの間の熱膨張係数の非常に大きな違いに起因して高応力条件を生成する。高応力によって最終アセンブリにおいて高度のそりがもたらされる。低応力を与えるフィルム接着材は典型的には低モジュラスであり、接着強度も低い。結果として、市販のフレキシブルフィルムは非フレキシブルフィルムよりも接着強度が低い。
ペースト導電性接着材もまた、特に基板上に接着材がスクリーン印刷される場合に、大面積で接着されるために使用できる。スクリーン印刷は高体積の製造を可能にし、廃棄物を制限する。ペースト導電性接着材もまたB段階処理可能であり、その結果、それらはフィルムと同様に予め部品に施すことができ、保管し、そして最終的な接着のために加熱することができる。ペースト接着材のレオロジーは回路基板上に接着材を正確に配置することを保証するために監視する必要がある。同様に、ペーストのレオロジーはB段階処理又は硬化プロセスの際のブリードアウト又はスランピング(slumping)を回避するために監視する必要がある。
それゆえ、半導体パッケージング操作において使用するための電気的に安定したアセンブリを形成するために、低応力及び高接着力を与える導電性のフィルム及びペースト接着材を与えることが有利である。有利には、その接着材は一般のフレキシブルフィルム接着材よりも優れた接着力と、一般の高強度フィルム接着材と比較してより優れた応力低減との組み合わせを有する。
発明の概要
本発明は低応力、等方性、導電性のフィルム又はペースト接着材に関し、その接着材はa)1以上の官能性アクリルコポリマー又はターポリマー;b)エポキシ樹脂;及びc)導電性フィラーを含む。接着促進剤、硬化剤、導電性向上剤等の追加の成分も利用できる。本発明の導電性フィルム接着材は従来のフレキシブル導電性フィルム接着材よりも高い接着強度を与え、現存する高接着強度導電性フィルムよりも被接着部品間の低い応力を与える。
発明の詳細な記述
本発明の導電性接着材は、a)1以上の官能性アクリルコポリマー又はターポリマー;b)エポキシ樹脂;及びc)導電性フィラーを含む。好ましい態様において、1以上の接着促進剤、硬化剤及び導電率添加剤も含むことができる。ここで、官能性アクリルコポリマーに関して言及される場合、官能性アクリルコポリマーはターポリマーを含んでもよいと理解される。
本発明の官能性アクリルコポリマーはコーティング溶媒に溶解でき、低応力、高強度フィルム形成性又はペースト状接着材を可能にする。好適なアクリルコポリマーは飽和ポリマーであり、それゆえカルボキシル末端ブタジエンニトリルゴムなどの典型的なゴム強化樹脂よりも酸化、老化及び劣化に対して耐性がある。コポリマーの組成物は、好ましくはブチルアクリレート−エチルアクリロニトリル又はブチルアクリレート−コ−エチルアクリロニトリル又はエチルアクリレート−アクリロニトリルであり、高分子量の重合を与える。コポリマーは、好ましくは、ヒドロキシル、カルボン酸、イソシアネート又はエポキシ官能基を有し、溶媒及びエポキシ樹脂との適合性を向上させる。コポリマーの分子量は高く、好ましくは、約200,000〜約900,000の範囲内である。コポリマーのガラス転移温度(Tg)は室温に比べて低く、好ましくは約30℃〜約−40℃の範囲内である。様々な官能性アクリルコポリマーが利用できる一方、好ましい官能性アクリルコポリマーはTEISAN RESIN SG80H(Nagase ChemteX Corporation(日本国、大阪)から商業的に入手可能)である。
本発明で使用する好適なエポキシ樹脂としては、例えば、ビスフェノールA及びビスフェノールFの単官能性及び多官能性グリシジルエーテル類、脂肪族及び芳香族エポキシ類、飽和及び不飽和エポキシ類、脂環族エポキシ樹脂、これらの組合せ等が挙げられる。最も好ましいエポキシ樹脂はビスフェノールAタイプ樹脂である。これら樹脂は一般に1モルのビスフェノールA樹脂と2モルのエピクロロヒドリンとの反応によって調製される。エポキシ樹脂のさらに好ましいタイプはエポキシノボラック樹脂である。エポキシノボラック樹脂は一般にフェノール樹脂とエピクロロヒドリンとの反応によって調製される。ジシクロペンタジエン−フェノールエポキシ樹脂、ナフタレン樹脂、エポキシ官能性ブタジエンアクリロニトリルコポリマー、エポキシ官能性ポリジメチルシロキサン、エポキシ官能性コポリマー及びそれらの混合物は、採用してもよいエポキシ樹脂の追加のタイプである。商業的に入手できるビスフェノールFタイプ樹脂はCVC Specialty Chemicals, Maple Shade, New Jerseyからの8230E、Resolution Performance Products Ltd.からのRSL1739である。ビスフェノールAタイプのエポキシ樹脂はResolution Performance Products Ltd.からEPON 828として商業的に入手できる。ビスフェノールA及びビスフェノールFのブレンド物はNippon Chemical CompanyからZX-1059として入手できる。
導電性材料は、導電性フィラーを含んでもよい。導電性フィラーとしては、例えば、銀、銅、金、パラジウム、白金、カーボンブラック、カーボンファイバー、グラファイト、アルミニウム、インジウム錫酸化物、銀コートされた銅、銀コートされたアルミニウム、ビスマス、錫、ビスマス−錫合金、金属コートされたガラス球、銀コートされたファイバー、銀コートされた球、アンチモンドープされた錫酸化物、カーボンナノチューブ、導電性ナノフィラー、導電性酸化物、それらの混合物などが挙げられる。
場合によって、適切な流動添加剤、接着促進剤、導電率添加剤、硬化剤及びレオロジー改質剤を所望により加えることができる。場合によって採用される流動添加剤としては、例えば、シリコンポリマー、エチルアクリレート/2−エチルヘキシルアクリレートコポリマー、酸のアルキロールアンモニウム塩、ケトキシムのリン酸エステル、これらの混合物などが挙げられる。好適な接着促進剤としては、例えば、シランの様々な形のもの等が挙げられる。好適なレオロジー改質剤としては、例えば、熱可塑性樹脂、好ましくはポリビニルアセタール等が挙げられる。好適な導電率添加剤としては、例えば、無水物、グルタール酸、クエン酸、リン酸、他の酸触媒などが挙げられる。好適な硬化剤としては、例えば、ルイス酸、無水物、アミン類、イミダゾール類、ジシアンジアミド類、これらの混合物などが挙げられるが、これらに限定されない。
本発明のこの態様の等方性導電性接着材組成物は、合計100重量%に対して、約4〜19重量%までの官能性アクリルコポリマー、約60〜95重量%の導電性フィラー、約1〜10重量%のエポキシ樹脂、約0〜10重量%の硬化剤、約0〜5重量%の導電率添加剤、及び約0〜5重量%の接着促進剤、流動添加剤、レオロジー改質剤又は他の添加剤を含む。好ましくは、官能性アクリルコポリマーは約12〜18重量%の範囲内で存在し、導電性フィラーは約70〜90重量%の範囲内で存在し、エポキシ樹脂は約2〜8重量%の範囲内で存在し、硬化剤は約0.1〜3重量%の範囲内で存在し、導電率添加剤は約0.01〜1重量%の範囲内で存在し、その他の添加剤は約0〜約5重量%の範囲内で存在する。
本発明はさらに以下の実施例により説明されることができる。
実施例
本発明の官能性アクリルコポリマーは表1中の成分で配合処方された。
Figure 0004875386
SG80H DR(Nagase Chemtexから)
RSL-1462 DGEGA epoxy(Resolution Performance Productsから商業的に入手可能)
Dicyanex 1400B(Air Productsから)
導電性促進剤及び銀充填剤は専売材料(proprietary materials)である。

表1の配合物Aの性能は商業的に入手できる高接着強度エポキシ樹脂及び低応力エポキシ樹脂の性能と共に試験した。試験された高接着強度エポキシ樹脂(比較例A)はCF3350(Emerson & Cumingから商業的に入手可能)であり、試験された低応力エポキシ樹脂(比較例B)は845OWL(AI Technologiesから商業的に入手可能)であった。これら試験の結果を表2に示す。
ダイせん断接着力は、Dage instrumentを使用して部品を別個に押して測定した。そりは、マイクロメータによって端から中心までの湾曲の差として測定した(なお、LTCCは低温焼成セラミック(low temperature cofired ceramic)を表す。)。Sonoscan microscopeから発生したアコースティックイメージでボンド−ラインインテグリティを表示した。
Figure 0004875386
表2に示されるように、官能性アクリルコポリマーを含む試料は、比較例Bと比べて優れた強度及び優れたボンドラインインテグリティを示した。アセンブリをリフロープロセス温度に曝露した後の接着強度の保持性が表2に示されている。強度の保持性は、これら接着材をアンポピュレーテッド(un-populated)な基板を接着するために利用する場合に必要である。部品を有する回路基板のポピュレーションはソルダープロセスで行われ、従って接着強度の保持性はボンド−ラインインテグリティにとってクリティカルである。比較例Bはリフロー温度に曝露する際に良好な性能を示さなかった。このことから、曝露後に接着強度の低下及びボンドラインインテグリティの変化があったことが明らかである。試験配合物はまた比較例Aと比べて曲率(応力:stress)の有意な低下を示した。この応力の低下は、リフロープロセス曝露後の接着インテグリティの損失無しで達成された。
当業者に明らかであるように、本発明の多くの変更及び変形をその精神及び範囲から逸脱することなく行うことができる。本明細書に記載された特定の態様は一例として提供されたに過ぎず、本発明は添付の特許請求の範囲の記載並びにそのような特許請求の範囲に付与される均等物の全範囲によってのみ制限される。

Claims (14)

  1. 超小型電子デバイス用組成物であって、
    a)30℃〜−40℃の範囲内のTgを有する官能性アクリルコポリマー又はターポリマー;
    b)エポキシ樹脂
    c)導電性フィラー;及び
    d)前記組成物を熱硬化させるための硬化剤;
    を含み、
    (a)前記官能性アクリルコポリマー又はターポリマーが4〜19重量%の量で存在し;
    (b)前記エポキシ樹脂が1〜8重量%の量で存在し;
    (c)前記導電性フィラーが60〜95重量%の量で存在する;
    組成物
  2. 1以上の導電率添加剤をさらに含む請求項1の組成物。
  3. 1以上の導電率添加剤が0.01〜1重量%の量で存在する、請求項の組成物。
  4. 1以上の硬化剤をさらに含む請求項1の組成物。
  5. 1以上の硬化剤が0.1〜3重量%の量で存在する、請求項の組成物。
  6. 官能性アクリルコポリマー又はターポリマーがヒドロキシル、カルボン酸、イソシアネート又はエポキシ官能基を有する、請求項1の組成物。
  7. 官能性アクリルコポリマー又はターポリマーが200,000〜900,000の範囲内の分子量を有する、請求項1の組成物。
  8. 導電性フィラーが銀、銅、金、パラジウム、白金、カーボンブラック、カーボンファイバー、グラファイト、アルミニウム、インジウム錫酸化物、銀コートされた銅、銀コートされたアルミニウム、ビスマス、錫、ビスマス−錫合金、金属コートされたガラス球、銀コートされたファイバー、銀コートされた球、アンチモンドープされた錫酸化物、カーボンナノチューブ、導電性ナノフィラー、導電性酸化物、及びそれらの混合物からなる群から選ばれる、請求項1の組成物。
  9. エポキシ樹脂がビスフェノールA及びビスフェノールFの単官能性及び多官能性グリシジルエーテル類、脂肪族及び芳香族エポキシ類、飽和及び不飽和エポキシ類、脂環族エポキシ樹脂、エポキシ官能性ポリマー、コポリマー、ターポリマー又はこれらの混合物の群から選ばれる、請求項1の組成物。
  10. 流動添加剤、接着促進剤及びレオロジー改質剤からなる群の1以上をさらに含む請求項1の組成物。
  11. 組成物が低応力フィルム導電性接着材である、請求項1の組成物。
  12. 組成物が導電性の接着性ペーストであり、低応力フィルム導電性接着材にB段階処理できる、請求項1の組成物。
  13. 請求項1の組成物を使用して電子部品を接着する方法。
  14. 請求項1の組成物を使用して電子部品を接着するためのフレキシブルフィルム又はペーストを提供する方法。
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ATE465497T1 (de) 2010-05-15
TWI382076B (zh) 2013-01-11
JP2006249426A (ja) 2006-09-21
EP1701361A1 (en) 2006-09-13
KR20060097610A (ko) 2006-09-14
CN1831073B (zh) 2012-01-18
KR101325083B1 (ko) 2013-11-06
EP1701361B1 (en) 2010-04-21
TW200704743A (en) 2007-02-01
DE602006013734D1 (de) 2010-06-02

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