JP6766417B2 - 硬化性樹脂シート、可撓性電気回路体及び半導体装置 - Google Patents
硬化性樹脂シート、可撓性電気回路体及び半導体装置 Download PDFInfo
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- JP6766417B2 JP6766417B2 JP2016075666A JP2016075666A JP6766417B2 JP 6766417 B2 JP6766417 B2 JP 6766417B2 JP 2016075666 A JP2016075666 A JP 2016075666A JP 2016075666 A JP2016075666 A JP 2016075666A JP 6766417 B2 JP6766417 B2 JP 6766417B2
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Description
まず、可撓性基材11上に電気回路12を形成する。電気回路の形成方法としては特に限定されないが、エッチング、めっき、印刷、転写等の方法が挙げられる。
次に、可撓性基材11及び電気回路12を、硬化性樹脂シート2で被覆する。例えば、図2の積層フィルムから保護フィルム3を剥離し、露出した硬化性樹脂シート2を可撓性基材11及び電気回路12上にラミネートしてもよい。ラミネートは、加熱プレス、ロールラミネート、真空ラミネート等によって行うことができる。この中でも、電気回路をボイドなく埋め込むためには、減圧下でのラミネート(真空ラミネート等)が好ましい。ラミネートの際、硬化性樹脂シートを50〜170℃に加熱することが好ましく、圧着圧力は、0.1〜150MPa程度(1〜1500kgf/cm2程度)が好ましい。これらの条件には特に制限はない。
次に、硬化性樹脂シート2を硬化させることにより可撓性を有する保護層13を形成させる。加熱による熱硬化、又は、露光による光硬化によって硬化性樹脂シートを硬化させることができる。工程の簡易化のためには、熱硬化であれば低温で硬化する硬化性樹脂シートが好ましい。室温で硬化できる観点から、光硬化する硬化性樹脂シートが好ましい。
最後に基材フィルム1を剥がして除去することで、図3に示される電気回路体200が得られる。
[樹脂ワニスVA11の調合]
(A)成分として水素添加型スチレンブタジエンゴム(スチレン系エラストマ、JSR(株)「ダイナロン2324P」)80質量部、(B)成分としてブタンジオールジアクリレート(日立化成(株)製「ファンクリルFA−124AS」)20質量部、(C)成分としてビス(2,4,6−トリメチルベンゾイル)フェニルホスフィンオキシド(BASF社製「イルガキュア819」)1.5質量部、及び溶剤としてトルエン125質量部を攪拌しながら混合し樹脂ワニスVA11を得た。
基材フィルムとして離型処理ポリエチレンテレフタレート(PET)フィルム(帝人デュポンフィルム(株)製「ピューレックスA31」、厚み25μm)を準備した。このPETフィルムの離型処理面上にナイフコータ((株)康井精機製「SNC−350」を用いて樹脂ワニスVA11を塗布した。塗膜を乾燥機((株)二葉科学製「MSO−80TPS」)中100℃で20分乾燥して、硬化性樹脂シートを形成させた。形成された硬化性樹脂シートに、基材フィルムと同じ離型処理PETフィルムを、離型処理面が硬化性樹脂シート側になる向きで保護フィルムとして貼付けて、積層フィルムFA11を得た。硬化後の硬化性樹脂シート(可撓性基材)の厚さが100μmとなるように塗工機のギャップを調節した。
実施例1と同様の方法で、表1に示す配合比に従って樹脂ワニスを調合し、積層フィルムFA12〜FA17を作製した。比較例2としてシリコーンゴム製のシート状フィルムFS18(厚さ100μm)を準備した。
各硬化性樹脂シートに、紫外線露光機(ミカサ(株)「ML−320FSAT」)によって紫外線(波長365nm)を5000mJ/cm2照射して、シート状の硬化物を形成させた。その後、長さ40mm、幅10mmの大きさに積層フィルムを切り出し、保護フィルム及び基材フィルムを除去して、硬化物の測定用サンプルを得た。測定用サンプルの応力−ひずみ曲線を、オートグラフ((株)島津製作所「EZ−S」)を用いて測定し、その応力−ひずみ曲線から弾性率及び伸び率を求めた。測定時のチャック間距離は20mm、引っ張り速度は50mm/minとした。荷重0.5から1.0Nにおける応力とひずみの関係から弾性率を求めた。サンプルが破断した際の時点のひずみから求められる伸び率を破断伸び率とした。
各硬化性樹脂シートに、紫外線露光機(ミカサ(株)「ML−320FSAT」)によって紫外線(波長365nm)を5000mJ/cm2照射して、シート状の硬化物を形成させた。その後、長さ70mm、幅5mmの大きさに積層フィルムを切り出し、保護フィルム及び基材フィルムを除去して、硬化物の測定用サンプルを得た。測定用サンプルの回復率を、マイクロフォース試験機(Illinois Tool Works Inc「Instron 5948」)を用いて測定した。
積層フィルムから保護フィルムを除去し、硬化性樹脂シートを、スライドガラス(松浪硝子工業(株)「S1111」)上に真空加圧式ラミネータ(ニチゴー・モートン(株)「V130」)を用いて、圧力0.5MPa、温度60℃及び加圧時間60秒の条件でラミネートした。ラミネートされた硬化性樹脂シートに、前記紫外線露光機にて紫外線(波長365nm)を5000mJ/cm2照射して、シート状の硬化物を形成させた。その後、基材フィルムを剥がし、硬化物の全光線透過率、YI及びヘイズを分光ヘイズメータ(日本電色工業(株)「SH7000」)を用いて測定した。
実施例3又は比較例2の硬化性樹脂シートから形成された硬化物について、JIS Z 0208 防湿包装材料の透湿度試験方法(カップ法)に準じて透湿度を測定した。試験温度は40℃、相対湿度は90%とした。
上記実施例及び比較例で作製した硬化性樹脂シートに関して、配線(電気回路)の埋め込みが可能か試験した。銅箔付きポリイミド(東レフィルム加工(株)製、商品名「メタロイヤル」)を加工し、ポリイミド基材上に厚さ18μm、幅100μmの銅回路パタン(電気回路)を形成した。積層フィルムから保護フィルムを剥がし、硬化性樹脂シートを、銅回路パタンの上に前記真空加圧式ラミネータを用いて、圧力0.8MPa、温度90℃及び加圧時間60秒の条件でラミネートした。次いで、前記紫外線露光機にて紫外線(波長365nm)を5000mJ/cm2照射して、硬化性樹脂シートを硬化させた。形成された保護層から基材フィルムを剥がした。その後、目視及び顕微鏡(倍率100倍)にて埋め込みの状態を観察し、ボイド等なく銅回路パタンが埋め込まれた場合は○、銅回路パタンが正常に埋め込まれなかった場合は×として評価した。
上記実施例及び比較例で作製した硬化性樹脂シートから形成される可撓性保護層のポリイミドフィルムに対する密着性を、90度ピール試験にて評価した。積層フィルムから保護フィルムを剥がし、硬化性樹脂シートを、前記真空加圧式ラミネータを用い、ポリイミドフィルム(東レ・デュポン(株)製「カプトン200EN」)上に圧力0.5MPa、温度60℃及び加圧時間60秒の条件でラミネートした。次いで、90度ピール試験時の補強を目的に、基材フィルムを剥がした後に、接着処理PETフィルム(東洋紡(株)製「コスモシャインA4100」、厚さ50μm)の易接着処理面を硬化性樹脂シート側にして、圧力0.8MPa、温度90℃及び加圧時間60秒の条件にてラミネートした。続いて、前記紫外線露光機にて紫外線(波長365nm)を5000mJ/cm2照射して、硬化性樹脂シートを硬化させた。その後、長さ100mm、幅10mmの大きさに硬化性樹脂シート及びポリイミドフィルムを切り出し、ピール強度測定用のサンプルを得た。サンプルを両面テープ(日立マクセル(株)製「スリオンテックNo.5579」にてSUS板に固定し、前記オートグラフを用い、引張り速度50mm/分の条件でピール試験を行って、ポリイミドフィルムと硬化性樹脂シートの硬化物(可撓性保護層)の間の密着強度を測定した。
2)シリコーンゴムシート、タイガースポリマー(株)「SR−50」
3)ゴム変性ポリアミド(日本化薬(株)「カヤフレックスBPAM−155」、重量平均分子量: 3.1×104
4)ブタンジオールジアクリレート(日立化成(株)「ファンクリルFA−124AS」)
5)ヘキサンジオールジアクリレート(日立化成(株)「ファンクリルFA−126AS」)
6)ノナンジオールジアクリレート(日立化成(株)「ファンクリルFA−129AS」)
7)ビス(2,4,6−トリメチルベンゾイル)フェニルホスフィンオキシド(BASFジャパン(株)「イルガキュア819」)
Claims (11)
- (A)スチレン系エラストマ、
(B)重合性モノマ、及び
(C)重合開始剤
を含有する、電気回路を保護する可撓性保護層を形成するために用いられる硬化性樹脂シートであって、
当該硬化性樹脂シートが硬化して形成される前記可撓性保護層の全光線透過率が80%以上である、硬化性樹脂シート。 - 当該硬化性樹脂シートが硬化して形成される前記可撓性保護層のヘイズが5.0%以下である、請求項1に記載の硬化性樹脂シート。
- 当該硬化性樹脂シートが硬化して形成される前記可撓性保護層の弾性率が0.1MPa以上1000MPa以下である、請求項1又は2に記載の硬化性樹脂シート。
- 可撓性基材上に形成された電気回路を当該硬化性樹脂シートで被覆し、次に当該硬化性樹脂シートを硬化させることにより前記電気回路を保護する可撓性保護層を形成するために用いられる、請求項1〜3のいずれか一項に記載の硬化性樹脂シート。
- 前記重合性モノマがエチレン性不飽和基を有する、請求項1〜4のいずれか一項に記載の硬化性樹脂シート。
- 前記重合開始剤が光ラジカル重合開始剤である、請求項1〜5のいずれか一項に記載の硬化性樹脂シート。
- 前記スチレン系エラストマの含有量が、前記スチレン系エラストマ及び前記重合性モノマの合計量に対して50〜90質量%であり、
前記重合性モノマの含有量が、前記スチレン系エラストマ及び前記重合性モノマの合計量に対して10〜50質量%であり、
前記重合開始剤の含有量が、前記スチレン系エラストマ及び前記重合性モノマの合計量100質量部に対して0.1〜10質量部である、請求項1〜6のいずれか一項に記載の硬化性樹脂シート。 - 前記重合性モノマが2官能又は多官能の(メタ)アクリレートである、請求項1〜7のいずれか一項に記載の硬化性樹脂シート。
- 前記スチレン系エラストマが、水素添加型スチレン系エラストマである、請求項1〜8のいずれか一項に記載の硬化性樹脂シート。
- 可撓性基材と、
前記可撓性基材上に形成された電気回路と、
前記電気回路を被覆し、請求項8又は9に記載の硬化性樹脂シートの硬化物である可撓性保護層と、
を備える可撓性電気回路体。 - 請求項10に記載の可撓性電気回路体と、
前記可撓性電気回路体に搭載された半導体素子と、
を具備する半導体装置。
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