JP7126129B2 - アンダーフィル用熱硬化性組成物及び半導体装置 - Google Patents
アンダーフィル用熱硬化性組成物及び半導体装置 Download PDFInfo
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- JP7126129B2 JP7126129B2 JP2019504490A JP2019504490A JP7126129B2 JP 7126129 B2 JP7126129 B2 JP 7126129B2 JP 2019504490 A JP2019504490 A JP 2019504490A JP 2019504490 A JP2019504490 A JP 2019504490A JP 7126129 B2 JP7126129 B2 JP 7126129B2
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Images
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Description
表1の組成の欄に示す成分を混合して、組成物を調製した。成分の詳細は次のとおりである。
・エポキシ化合物1:3官能グリシジルアミン型エポキシ樹脂、エポキシ当量95g/eq。
・エポキシ化合物2:1,6-ナフタレンジオールジグリシジルエーテル。
・硬化剤1:3-メチル-ヘキサヒドロ無水フタル酸。
・硬化剤2:トリアルキルテトラヒドロ無水フタル酸。
・硬化促進剤:2-フェニル-4-メチルイミダゾール。
・アクリル化合物1:エトキシ化ビスフェノールAジメタクリレート。
・アクリル化合物2;ビスフェノールA型エポキシアクリレート、昭和高分子社製、品番VR-77。
・アクリル化合物3:トリシクロデカンジメタノールジメタクリレート、新中村化学工業株式会社、品番DCP。
・架橋助剤1:エトキシ化イソシアヌル酸トリアクリレート新中村化学工業製、品番A-9300。
・架橋助剤2:トリアリルイソシアヌレート。
・熱ラジカル重合開始剤:ジクミルパーオキサイド、日油製、品名パークミルD。
・エラストマー1:1,2-ビニル基を有する無水マレイン酸変性ポリブタジエン、Cray Valley社製、品番Ricobond1756。
・エラストマー2:1,2-ビニル基を有さない液状ブタジエンゴム、クラレ製、品番LBR307。
・エラストマー3:1,2-ビニル基を有さない液状ポリブタジエン、エボニック社製、品番Polyvest 110。
・エラストマー4:1,2-ビニル基を有するブタジエンスチレンコポリマー、Cray Valley社製、品番Ricon100。
・カップリング剤:3-アクリロキシプロピルトリメトキシシラン、信越化学工業製、品番KBM-5103。
・無機フィラー1:球状シリカ、平均粒径1.0μm。
・無機フィラー2:中空シリカ、平均粒径15μm、中空率70%、比重0.6。
・無機フィラー3:球状シリカ、平均粒径1.5μm。
組成物に対して、次の評価試験を実施した。その結果は表1の評価の欄に示す。
Brookfield社製のB型粘度測定装置(型番DV-II)を用い、ローター直径8.74mm、温度25℃、回転速度50rpmの条件で、組成物の粘度を測定した。
Brookfield社製のB型粘度測定装置(型番DV-II)を用い、ローター直径8.74mm、温度25℃、回転速度5rpm及び50rpmの条件で、組成物の粘度を測定した。回転速度5rpmの場合の粘度測定値μ5と、回転速度50rpmの場合の粘度測定値μ50との比の値μ5/μ50を、チクソトロピーインデックスとした。
組成物をシリコーン製の型内に流し入れ、150℃で1時間加熱することで、20mm×40mm×3mmの寸法の硬化物を作製した。
上記ガラス転移温度測定と同じ条件で硬化物の熱機械分析を行い、30℃からガラス転移温度よりも15℃低い温度までの温度範囲の測定結果から、線膨張係数を算出した。
上記ガラス転移温度測定と同じ条件で硬化物の熱機械分析を行い、ガラス転移温度よりも15℃高い温度から300℃までの温度範囲の測定結果から、線膨張係数を算出した。
組成物をシリコーン製の型内に流し入れ、室温から30分かけて100℃まで加熱し、この温度に60分間維持してから、15分かけて150℃まで加熱し、この温度に60分間維持してから、30分かけて室温まで冷却した。これにより、2mm×2mm×50mmの寸法の四角柱形状を有する硬化物を作製した。
組成物を用い、次のようにして半導体装置を作製した。
Claims (7)
- 2官能以下のアクリル化合物、熱ラジカル重合開始剤、シリカ及び1,2-ビニル基を有するエラストマーを含有し、
前記2官能以下のアクリル化合物が、架橋多環構造を有する(メタ)アクリレートと、ビスフェノール骨格にアルキレンオキサイドが付加された構造を有するジ(メタ)アクリレートと、エポキシ(メタ)アクリレートとを含有し、
前記架橋多環構造を有する(メタ)アクリレートがトリシクロデカンジメタノールジメタクリレートを含有し、前記ビスフェノール骨格にアルキレンオキサイドが付加された構造を有するジ(メタ)アクリレートがエトキシ化ビスフェノールAジメタクリレートを含有し、前記エポキシ(メタ)アクリレートがビスフェノールA型エポキシアクリレートを含有し、
前記2官能以下のアクリル化合物全体に対して、前記架橋多環構造を有する(メタ)アクリレートが62.0~82.1質量%、前記ビスフェノール骨格にアルキレンオキサイドが付加された構造を有するジ(メタ)アクリレートが11.9~25.2質量%、前記エポキシ(メタ)アクリレートが6.0~12.8質量%であり、
前記シリカが球状シリカを含有し、
前記シリカの割合が組成物全量に対して59.2~64.5質量%であり、
前記1,2-ビニル基を有するエラストマーが1,2-ビニル基を有する無水マレイン酸変性ポリブタジエンと1,2-ビニル基を有するブタジエンスチレンコポリマーとのうち少なくとも一方を含有し、
前記1,2-ビニル基を有するエラストマーの割合が組成物全量に対して4.8~8.2質量%であり、
液状であり、
熱硬化すると3.2以下の25℃での比誘電率と、0.013以下の25℃での誘電正接とを有する硬化物になる性質を有する、
アンダーフィル用熱硬化性組成物。 - 1分子中に3個以上のラジカル重合性官能基を有する架橋助剤を更に含有する、
請求項1に記載のアンダーフィル用熱硬化性組成物。 - 25℃での粘度が100Pa・s以下である、
請求項1又は2に記載のアンダーフィル用熱硬化性組成物。 - 前記硬化物は100℃以上のガラス転移温度を有する、
請求項1から3のいずれか一項に記載のアンダーフィル用熱硬化性組成物。 - 前記硬化物は、50ppm/℃以下の、ガラス転移温度以下での線膨張係数を有する、
請求項1から4のいずれか一項に記載のアンダーフィル用熱硬化性組成物。 - 前記硬化物は、120ppm/℃以下の、ガラス転移温度以上での線膨張係数を有する、
請求項1から5のいずれか一項に記載のアンダーフィル用熱硬化性組成物。 - 基材と、前記基材にフェイスダウンで実装されている半導体チップと、前記基材と前記半導体チップとの間の隙間を封止する封止材とを備え、前記封止材が請求項1から6のいずれか一項に記載のアンダーフィル用熱硬化性組成物の硬化物である、
半導体装置。
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