JP2021004314A - 樹脂組成物 - Google Patents
樹脂組成物 Download PDFInfo
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- JP2021004314A JP2021004314A JP2019118952A JP2019118952A JP2021004314A JP 2021004314 A JP2021004314 A JP 2021004314A JP 2019118952 A JP2019118952 A JP 2019118952A JP 2019118952 A JP2019118952 A JP 2019118952A JP 2021004314 A JP2021004314 A JP 2021004314A
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- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
- 229910000166 zirconium phosphate Inorganic materials 0.000 description 1
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 description 1
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Abstract
Description
[1] (A−1)エポキシ当量が400g/eq.より大きく、1500g/eq.以下であるエポキシ樹脂、
(B)無機充填剤、及び
(C)硬化剤、を含む樹脂組成物であって、
(A−1)成分の含有量が、樹脂組成物中の不揮発成分を100質量%としたとき、0.2質量%以上3質量%未満であり、
(B)成分の含有量が、樹脂組成物中の不揮発成分を100質量%としたとき、70質量%以上である、樹脂組成物。
[2] (A−1)成分が、フルオレン骨格、ブタジエン骨格、イソプレン骨格、アルキレンオキシ骨格、シロキサン骨格、及びビスフェノール骨格からなる群より選択される1種以上の骨格を含む、[1]に記載の樹脂組成物。
[3] さらに、(A−2)エポキシ当量が400g/eq.以下のエポキシ樹脂、又はエポキシ当量が1500g/eq.より大きいエポキシ樹脂を含む、[1]又は[2]に記載の樹脂組成物。
[4] (C)成分が、酸無水物系硬化剤を含む、[1]〜[3]のいずれかに記載の樹脂組成物。
[5] 樹脂組成物が、液状である、[1]〜[4]のいずれかに記載の樹脂組成物。
[6] 封止用又は絶縁用の樹脂組成物である、[1]〜[5]のいずれかに記載の樹脂組成物。
[7] [1]〜[6]のいずれかに記載の樹脂組成物の硬化物により形成された絶縁層を含む、回路基板。
[8] [7]に記載の回路基板と、前記回路基板に搭載された半導体チップとを含む、半導体チップパッケージ。
[9] 半導体チップと、前記半導体チップを封止する[1]〜[6]のいずれかに記載の樹脂組成物の硬化物とを含む、半導体チップパッケージ。
本発明の樹脂組成物は、(A−1)エポキシ当量が400g/eq.より大きく、1500g/eq.以下であるエポキシ樹脂、(B)無機充填剤、及び(C)硬化剤、を含む樹脂組成物であって、(A−1)成分の含有量が、樹脂組成物中の不揮発成分を100質量%としたとき、0.2質量%以上3質量%未満であり、(B)成分の含有量が、樹脂組成物中の不揮発成分を100質量%としたとき、70質量%以上である。(A−1)成分、(B)成分及び(C)成分を組み合わせて含み、且つ、(A−1)成分及び(B)成分の含有量を所定の範囲内とすることにより、樹脂組成物は、密着性に優れ、反り、モールド成形後のフローマークの発生、及びポストキュア後の樹脂表面のムラの発生を抑制された硬化物を得られるという、本発明の所望の効果を得ることができる。
樹脂組成物は、(A−1)成分として、(A−1)エポキシ当量が400g/eq.より大きく、1500g/eq.以下であるエポキシ樹脂を含有する。(A−1)成分は、エポキシ当量が400g/eq.より大きく1500g/eq.以下であるため、架橋密度が特定の適切な範囲にある硬化物が得られる。このため、(A−1)成分を含有する樹脂組成物の硬化物は靱性が向上し、その結果、密着性が向上すると考えられる。また、(A−1)成分を樹脂組成物に含有させることで、樹脂組成物が硬化する際の硬化収縮の発生が抑制される。その結果、反り量が抑制されると考えられる。
樹脂組成物は、(A−2)として、エポキシ当量が400g/eq.以下のエポキシ樹脂、又はエポキシ当量が1500g/eq.より大きいエポキシ樹脂を含有していてもよい。(A−2)成分を樹脂組成物に含有させることで、本発明の効果を顕著に得ることができる。
樹脂組成物は、(B)成分として無機充填材を含有する。(B)無機充填材を用いることにより、樹脂組成物の硬化物の絶縁性能を向上させることができる。
樹脂組成物は、(C)成分として、硬化剤を含有する。(C)硬化剤は、通常、(A)成分と反応して樹脂組成物を硬化させる機能を有する。(C)硬化剤は、1種類単独で用いてもよく、2種類以上を任意の比率で組み合わせて用いてもよい。
樹脂組成物は、任意の成分として(D)硬化促進剤を含有していてもよい。硬化促進剤としては、例えば、リン系硬化促進剤、アミン系硬化促進剤、イミダゾール系硬化促進剤、グアニジン系硬化促進剤、金属系硬化促進剤等が挙げられ、アミン系硬化促進剤、イミダゾール系硬化促進剤が好ましく、アミン系硬化促進剤がより好ましい。硬化促進剤は、1種単独で用いてもよく、2種以上を組み合わせて用いてもよい。
樹脂組成物は、上述した成分以外に、任意の成分として、更にその他の添加剤を含んでいてもよい。このような添加剤としては、例えば、熱可塑性樹脂;難燃剤;有機充填材;有機銅化合物、有機亜鉛化合物及び有機コバルト化合物等の有機金属化合物;増粘剤;消泡剤;レベリング剤;密着性付与剤;着色剤;顔料等の樹脂添加剤が挙げられる。これらの添加剤は、1種類を単独で用いてもよく、2種類以上を任意の比率で組み合わせて用いてもよい。それぞれの含有量は当業者であれば適宜設定できる。
上述した樹脂組成物によれば、反りの抑制が可能な硬化物の層を得ることができる。したがって、この樹脂組成物を用いることにより、回路基板及び半導体チップパッケージの反りの抑制が可能な封止層及び絶縁層を得ることができる。例えば、上述した樹脂組成物を用いて、実施例に記載の方法によって、12インチシリコンウエハ上に、180℃で90分加熱した樹脂組成物の硬化物層を形成して、試料基板を作製する。この場合、25℃での実施例に記載の方法で測定される反り量を、通常5mm未満、好ましくは4mm未満にできる。下限は特に限定されないが、0.01mm以上等とし得る。
RE80型粘度計(東機産業社製)にて測定対象の樹脂組成物0.2〜0.3mlをシリンジにて量り取る。測定の際には、粘度計の測定室を外部循環型恒温槽にて25.0℃に温度管理する。ローターの回転数を1rpmに設定し、120秒後の粘度を計測する。
本発明の樹脂シートは、支持体と、該支持体上に設けられた樹脂組成物層と、を有する。樹脂組成物層は、本発明の樹脂組成物を含む層であり、通常は、樹脂組成物で形成されている。
本発明で用いられる回路基板は、例えば、下記の工程(1)及び工程(2)を含む製造方法によって、製造できる。上述した樹脂組成物の硬化物は、後述するように回路基板上の半導体チップなどの封止層として用いられる以外に、回路基板に含まれる絶縁層を樹脂組成物の硬化物により形成してもよい。但し、絶縁層は、上述した樹脂組成物の硬化物以外の材料によって形成されていてもよい。
(1)基材上に、樹脂組成物層を形成する工程。
(2)樹脂組成物層を熱硬化して、絶縁層を形成する工程。
例えば、樹脂シートを用いて回路基板を製造した場合、回路基板の製造方法は、樹脂シートの支持体を剥離する工程を含んでいてもよい。支持体は、樹脂組成物層の熱硬化の前に剥離してもよく、樹脂組成物層の熱硬化の後に剥離してもよい。
本発明の第一実施形態に係る半導体チップパッケージは、上述した回路基板と、この回路基板に搭載された半導体チップとを含む。この半導体チップパッケージは、回路基板に半導体チップを接合することにより、製造することができる。
(A)基材に仮固定フィルムを積層する工程、
(B)半導体チップを、仮固定フィルム上に仮固定する工程、
(C)本発明の樹脂シートの樹脂組成物層を、半導体チップ上に積層、又は本発明の樹脂組成物を半導体チップ上に塗布し、熱硬化させて封止層を形成する工程、
(D)基材及び仮固定フィルムを半導体チップから剥離する工程、
(E)半導体チップの基材及び仮固定フィルムを剥離した面に再配線形成層(絶縁層)を形成する工程、
(F)再配線形成層(絶縁層)上に導体層(再配線層)を形成する工程、及び
(G)導体層上にソルダーレジスト層を形成する工程、を含む。また、半導体チップパッケージの製造方法は、(H)複数の半導体チップパッケージを個々の半導体チップパッケージにダイシングし、個片化する工程を含み得る。
上述した半導体チップパッケージが実装される半導体装置としては、例えば、電気製品(例えば、コンピューター、携帯電話、スマートフォン、タブレット型デバイス、ウェラブルデバイス、デジタルカメラ、医療機器、及びテレビ等)及び乗物(例えば、自動二輪車、自動車、電車、船舶及び航空機等)等に供される各種半導体装置が挙げられる。
平均粒径7μm、比表面積3.4m2/gの球状シリカを、KBM―573(信越化学工業製)で表面処理をしたことにより、球状のシリカAを得た。
液状エポキシ樹脂(新日鉄住金化学社製「ZX1059」、ビスフェノールA型エポキシ樹脂とビスフェノールF型エポキシ樹脂との1:1混合品(質量比)、エポキシ当量:169g/eq.)5部、グリシジルアミン型エポキシ樹脂(三菱ケミカル社製「630」、エポキシ当量95g/eq.)7部、フルオレン骨格含有エポキシ樹脂(大阪ガスケミカル社製「EG−280」、エポキシ当量460g/eq.)2部、酸無水物系硬化剤(新日本理化社製「MH−700」、4−メチルヘキサヒドロ無水フタル酸/ヘキサヒドロ無水フタル酸=70/30)8部、シリカA 140部、硬化促進剤(四国化成工業社製「1B2PZ」)0.1部を、ミキサーを用いて均一に分散して、樹脂組成物1を得た。
実施例1において、フルオレン骨格含有エポキシ樹脂(大阪ガスケミカル社製「EG−280」、エポキシ当量460g/eq.)2部を、液状アルキレンオキシ骨格及びブタジエン骨格含有エポキシ樹脂(ナガセケムテックス社製「EX−991L」、エポキシ当量450g/eq.)2部に代えた。以上の事項以外は実施例1と同様にして樹脂組成物2を得た。
実施例1において、フルオレン骨格含有エポキシ樹脂(大阪ガスケミカル社製「EG−280」、エポキシ当量460g/eq.)2部を、液状アルキレンオキシ骨格含有エポキシ樹脂(阪本薬品工業社製「SR−PTMG」、エポキシ当量420g/eq.)2部に代えた。以上の事項以外は実施例1と同様にして樹脂組成物3を得た。
実施例1において、フルオレン骨格含有エポキシ樹脂(大阪ガスケミカル社製「EG−280」、エポキシ当量460g/eq.)2部を、液状シロキサン骨格含有エポキシ樹脂(信越化学工業製「KF−105」、エポキシ当量490g/eq.)2部に代えた。以上の事項以外は実施例1と同様にして樹脂組成物4を得た。
実施例1において、フルオレン骨格含有エポキシ樹脂(大阪ガスケミカル社製「EG−280」、エポキシ当量460g/eq.)2部を、ビスフェノールA型骨格含有液状エポキシ樹脂(DIC社製「EXA−4816」、エポキシ当量403g/eq.)2部に代えた。以上の事項以外は実施例1と同様にして樹脂組成物5を得た。
実施例1において、フルオレン骨格含有エポキシ樹脂(大阪ガスケミカル社製「EG−280」、エポキシ当量460g/eq.)の量を、2部から1部に代えた。以上の事項以外は実施例1と同様にして樹脂組成物6を得た。
実施例1において、フルオレン骨格含有エポキシ樹脂(大阪ガスケミカル社製「EG−280」、エポキシ当量460g/eq.)2部を、液状エポキシ樹脂(阪本薬品工業社製「SR−14BJ」、エポキシ当量102g/eq.)2部に代えた。以上の事項以外は実施例1と同様にして樹脂組成物7を得た。
実施例1において、フルオレン骨格含有エポキシ樹脂(大阪ガスケミカル社製「EG−280」、エポキシ当量460g/eq.)2部を、液状エポキシ樹脂(阪本薬品工業社製「SR−16BJ」、エポキシ当量120g/eq.)2部に代えた。以上の事項以外は実施例1と同様にして樹脂組成物8を得た。
実施例1において、フルオレン骨格含有エポキシ樹脂(大阪ガスケミカル社製「EG−280」、エポキシ当量460g/eq.)2部を、液状エポキシ樹脂(信越化学工業社製「X−22−163B」、エポキシ当量1800g/eq.)2部に代えた。以上の事項以外は実施例1と同様にして樹脂組成物9を得た。
実施例4において、液状エポキシ樹脂(信越化学工業製「KF−105」、エポキシ当量490g/eq.)の量を2部から5部に代えた。以上の事項以外は実施例4と同様にして樹脂組成物10を得た。
実施例2においてシリカAの量を140部から55部に代えた。以上の事項以外は実施例2と同様にして樹脂組成物11を得た。
12インチシリコンウエハ上に、実施例及び比較例で製造した各樹脂組成物を、コンプレッションモールド装置(金型温度:130℃、圧力:6MPa、キュアタイム:10分)を用いて圧縮成型して、厚さ300μmの樹脂組成物層を形成した。その後、180℃で90分加熱して、樹脂組成物層を熱硬化させた。これにより、シリコンウエハと樹脂組成物の硬化物層とを含む試料基板を得た。シャドウモアレ測定装置(Akorometrix社製「ThermoireAXP」)を用いて、前記の試料基板を25℃での反り量を測定した。測定は、電子情報技術産業協会規格のJEITA EDX−7311−24に準拠して行った。具体的には、測定領域の基板面の全データの最小二乗法によって算出した仮想平面を基準面として、その基準面から垂直方向の最小値と最大値との差を反り量として求め、以下の基準で評価した。
○:反り量が4mm未満
△:反り量が4mm以上5mm未満
×:反り量が5mm以上
12インチシリコンウエハ上に、実施例及び比較例で調製した樹脂組成物を、コンプレッションモールド装置(金型温度:130℃、圧力:6MPa、キュアタイム:10分)を用いて圧縮成型して、厚さ300μmの樹脂組成物層を形成した。その後、180℃で90分加熱して、樹脂組成物層を熱硬化させた。これにより、シリコンウエハと樹脂組成物の硬化物層とを含む試料基板を得た。続いて、130℃85%RH96時間の条件で高温高湿環境試験(HAST)を実施した。HAST実施後の硬化物層を、#180のサンドペーパーを使用して硬化物層が厚さ50μmになるまで研磨した。研磨後のサンプルを幅1cm角の試験片に切断し、硬化物層に対して垂直にφ2.7mmの接着剤付きstud pinを立てて150℃で60分加熱し、stud pinと硬化物層とが接着した試験片を作製した。
得られたstud pin付き試験片をQUAD GROUP社製垂直引張型試験機「ROMULUS」を使用して、試験スピード0.1Kg/secで垂直引っ張り試験の測定を行った。5個の試験片について測定を行い、平均値を算出し、以下の基準で評価した。
○:密着強度が500kgf/cm2を超える。
×:500kgf/cm2未満。
12インチシリコンウエハ上に、実施例及び比較例で調製した樹脂組成物を、コンプレッションモールド装置(金型温度:130℃、圧力:6MPa、キュアタイム:10分)を用いて圧縮成型して、厚さ300μmの樹脂組成物層を形成し(この時の樹脂組成物層の面積は、14.6cm×14.6×3.14=45.844cm2)、樹脂組成物層の外観を観察した。樹脂組成物層表面全体のうち、フローマークの占める面積が20%未満のものを「〇」、20%を超えるものを「×」とした。
12インチシリコンウエハ上に、実施例及び比較例で調製した樹脂組成物を、コンプレッションモールド装置(金型温度:130℃、圧力:6MPa、キュアタイム:10分)を用いて圧縮成型して、厚さ300μmの樹脂組成物層を形成した(この時の樹脂組成物層の面積は、14.6cm×14.6×3.14=45.844cm2)。その後、180℃で90分加熱して、樹脂組成物層を熱硬化し硬化物層の外観を観察した。硬化物層表面が均一で色ムラがないものを「〇」、硬化物層表面が樹脂の分離等により色むらが発生し均一でないものを「×」とした。
Claims (9)
- (A−1)エポキシ当量が400g/eq.より大きく、1500g/eq.以下であるエポキシ樹脂、
(B)無機充填剤、及び
(C)硬化剤、を含む樹脂組成物であって、
(A−1)成分の含有量が、樹脂組成物中の不揮発成分を100質量%としたとき、0.2質量%以上3質量%未満であり、
(B)成分の含有量が、樹脂組成物中の不揮発成分を100質量%としたとき、70質量%以上である、樹脂組成物。 - (A−1)成分が、フルオレン骨格、ブタジエン骨格、イソプレン骨格、アルキレンオキシ骨格、シロキサン骨格、及びビスフェノール骨格からなる群より選択される1種以上の骨格を含む、請求項1に記載の樹脂組成物。
- さらに、(A−2)エポキシ当量が400g/eq.以下のエポキシ樹脂、又はエポキシ当量が1500g/eq.より大きいエポキシ樹脂を含む、請求項1又は2に記載の樹脂組成物。
- (C)成分が、酸無水物系硬化剤を含む、請求項1〜3のいずれか1項に記載の樹脂組成物。
- 樹脂組成物が、液状である、請求項1〜4のいずれか1項に記載の樹脂組成物。
- 封止用又は絶縁用の樹脂組成物である、請求項1〜5のいずれか1項に記載の樹脂組成物。
- 請求項1〜6のいずれか1項に記載の樹脂組成物の硬化物により形成された絶縁層を含む、回路基板。
- 請求項7に記載の回路基板と、前記回路基板に搭載された半導体チップとを含む、半導体チップパッケージ。
- 半導体チップと、前記半導体チップを封止する請求項1〜6のいずれか1項に記載の樹脂組成物の硬化物とを含む、半導体チップパッケージ。
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