JP7000652B2 - フレキシブルディスプレイ製造用積層体及びそれを用いたフレキシブルディスプレイの製造方法 - Google Patents
フレキシブルディスプレイ製造用積層体及びそれを用いたフレキシブルディスプレイの製造方法 Download PDFInfo
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Description
一実施例によれば、前記デボンディング層の厚さが、50nm以上1μm以下である。
PDA:phenylene diamine
PMDA:pyromellitic dianhydride
TFMB:2,2'-bis(trifluoromethyl)benzidine
図3Aと図3Bとを参照すれば、キャリア基板上にデボンディング層が形成され、この際、デボンディング層の面積を第1面積と称する。前記デボンディング層上に可撓性基板層が形成されるが、可撓性基板層は、前記デボンディング層の第1面積よりも広い第2面積に形成される。すなわち、前記可撓性基板層は、デボンディング層を完全に覆う形態に形成されることにより、前記キャリア基板と前記可撓性基板層とが直接接する領域(A)が存在する。
化学式3aから化学式3kにおいて、*は、連結部位を示す。
化学式4aから化学式4kにおいて、*は、連結部位を示す。
窒素気流が流れる攪拌機内に有機溶媒NMP(N-メチル-2-ピロリドン)100gを満たした後、反応器の温度を25℃に保持した状態でパラフェニレンジアミン(p-PDA)6.243g(57.726mmol)を溶解させた。前記p-PDA溶液に3,3',4,4'-ビフェニルカルボン酸二無水物(s-BPDA)16.797g(57.091mmol)とNMP 56.96gとを同じ温度で添加し、一定時間溶解しながら撹拌して、ポリアミド酸を重合することにより、ポリイミド前駆体を製造した。
窒素気流が流れる攪拌機内に有機溶媒NMP(N-メチル-2-ピロリドン)100gを満たした後、反応器の温度を25℃に保持した状態でパラフェニレンジアミン(p-PDA)6.364g(58.849mmol)を溶解させた。前記p-PDA溶液に3,3',4,4'-ビフェニルカルボン酸二無水物(s-BPDA)15.393g(52.316mmol)、ピロメリット酸二無水物(PMDA)1.289g(5.885mmol)とNMP 56.96gとを同じ温度で添加し、一定時間溶解しながら撹拌して、ポリアミド酸を重合することにより、ポリイミド前駆体を製造した。
窒素気流が流れる攪拌機内に有機溶媒NMP(N-メチル-2-ピロリドン)100gを満たした後、反応器の温度を25℃に保持した状態でパラフェニレンジアミン(p-PDA)5.335g(49.332mmol)とビストリフルオロメチルベンジジン(TFMB)1.775g(5.481mmol)とを溶解させた。前記p-PDAとTFMB溶液に3,3',4,4'-ビフェニルカルボン酸二無水物(s-BPDA)15.950g(54.221mmol)とNMP 56.96gとを同じ温度で添加し、一定時間溶解しながら撹拌して、ポリアミド酸を重合することにより、ポリイミド前駆体を製造した。
窒素気流が流れる攪拌機内に有機溶媒NMP(N-メチル-2-ピロリドン)100gを満たした後、反応器の温度を25℃に保持した状態でパラフェニレンジアミン(p-PDA)6.142g(56.800mmol)を溶解させた。前記p-PDA溶液に3,3',4,4'-ビフェニルカルボン酸二無水物(s-BPDA)16.898g(57.432mmol)とNMP 56.96gとを同じ温度で添加して、一定時間溶解しながら撹拌して、ポリアミド酸を重合することにより、ポリイミド前駆体を製造した。
窒素気流が流れる攪拌機内に有機溶媒NMP(N-メチル-2-ピロリドン)100gを満たした後、反応器の温度を25℃に保持した状態でパラフェニレンジアミン(p-PDA)6.192g(57.259mmol)を溶解させた。前記p-PDA溶液に3,3',4,4'-ビフェニルカルボン酸二無水物(s-BPDA)16.661g(56.629mmol)とNMP 56.96gとを同じ温度で添加して、一定時間溶解しながら撹拌して、ポリアミド酸を重合することにより、ポリイミド前駆体を製造した。以後、前記ポリアミド酸溶液に無水フタル酸(PA)0.187g(1.260mmol)を投入し、一定時間撹拌して、ポリイミド前駆体を製造した。
BPDA-PMDA-pPDAのmol比を変化させて、二無水物が当量比よりも過量になるようにしたことを除いては、製造例2と同じ方法でポリイミド前駆体溶液を製造した。
BPDA-pPDA-TFMBのmol比を変化させて、二無水物が当量比よりも過量になるようにしたことを除いては、製造例3と同じ方法でポリイミド前駆体溶液を製造した。
製造例1から製造例7から製造されたそれぞれのポリイミド前駆体溶液をガラス基板にスピンコーティングした。ポリイミド前駆体溶液が塗布されたガラス基板をオーブンに入れ、6℃/minの速度で加熱し、400℃で10分を保持して硬化工程を進行した。硬化工程完了後に、ガラス基板を水に浸してガラス基板上に形成されたフィルムを取り外した後、オーブンで100℃に乾燥して、厚さが6μmであるポリイミドのフィルムを製造した。
それぞれのポリイミドフィルムを5x20mmのサイズに準備した後、アクセサリーを用いてTA社のQ400装備に試料をローディングする。実際に測定されるフィルムの長さは、16mmに同様にした。フィルムを引っ張る力を0.02Nに設定し、100~460℃の温度範囲で4℃/minの昇温速度で1次昇温工程を進行した後、460~100℃の温度範囲で5℃/minの冷却速度で冷却させた。以後、前記冷却されたそれぞれのサンプルを100~460℃で4℃/minの昇温速度で加熱(heating)させながら、サンプルの熱膨張変化をTMAで測定した。前記加熱による温度変化によるサンプルの寸法変化の態様を図1Aに示し、前記温度範囲で測定された熱膨張係数を下記表1に示した。
TA instruments社のDiscovery TGAを用いて窒素雰囲気で重合体の重量減少率1%である時の温度を測定した。
製造例1から製造されたポリイミド前駆体溶液を固形分濃度3wt%になるように溶媒で希釈した後、ガラス基板の一部にスピンコーティングした。ポリイミド前駆体溶液が塗布されたガラス基板をオーブンに入れ、常温から6℃/minの速度で加熱し(200℃、350℃及び400℃)、最終硬化温度で10分を保持して、最終厚さ0.1μmであるデボンディング層を形成した。
製造例2及び製造例3で製造したポリイミド前駆体溶液でデボンディング層をそれぞれ形成したことを除いては、実施例1と同じ方法で積層体を製造した。
製造例4から製造例7で製造したポリイミド前駆体溶液でデボンディング層をそれぞれ形成したことを除いては、実施例1と同じ方法で積層体を製造した。
実施例及び比較例で製造した積層体に対して、デボンディング層を完全に覆っている可撓性基板層を幅10mm及び長さ100mmの長方形状にカッティング後、カッティングした可撓性基板の端部を握って50mm/minの速度で取り外す時に入る力をTexture Analyzer(TA、XT plus、Stable microsystems)を用いて測定した。
測定結果は、表2に示した。
Claims (13)
- キャリア基板と、
前記キャリア基板上に形成されており、350℃以上の温度で熱膨張係数(CTE)が負数値を有するポリイミドを含むデボンディング層と、
前記デボンディング層上に形成された可撓性基板層と、
を備え、
前記デボンディング層は、第1面積を有し、
前記可撓性基板層は、前記第1面積よりも大きな第2面積を有しながら、前記デボンディング層を完全に覆っており、
前記デボンディング層に含まれたポリイミドは、ジアミンと二無水物とが、二無水物に比べて、ジアミンが当量比よりも過量である条件で重合及び硬化された生成物を含む、
フレキシブルディスプレイ製造用積層体。 - 前記デボンディング層は、ビフェニルテトラカルボン酸二無水物(BPDA)を含む二無水物と、フェニレンジアミン(PDA)を含むジアミンとの重合及び硬化生成物を含む請求項1に記載のフレキシブルディスプレイ製造用積層体。
- 前記二無水物は、ピロメリット酸二無水物(PMDA)をさらに含むものであり、前記ジアミンは、2,2'-ビス(トリフルオロメチル)ベンジジン(TFMB)をさらに含む請求項2に記載のフレキシブルディスプレイ製造用積層体。
- 前記二無水物とジアミンとの組合わせは、BPDA-PDA、BPDA-PMDA-PDA及びBPDA-PDA-TFMBのうちから選択される請求項3に記載のフレキシブルディスプレイ製造用積層体。
- 前記二無水物とジアミンとの組合わせが、BPDA-PDA-TFMBであり、TFMBがジアミン全体のうち、5mol%以上である請求項4に記載のフレキシブルディスプレイ製造用積層体。
- 前記二無水物とジアミンとの組合わせが、BPDA-PMDA-PDAであり、PMDAが二無水物全体のうち、5mol%以上である請求項4に記載のフレキシブルディスプレイ製造用積層体。
- 前記デボンディング層の厚さが、50nm以上1μm以下である請求項1から6の何れか一項に記載のフレキシブルディスプレイ製造用積層体。
- 前記可撓性基板層が、350℃以上の温度でCTEが正数値を有するポリイミドを含む請求項1から7の何れか一項に記載のフレキシブルディスプレイ製造用積層体。
- 請求項1から請求項8のうち何れか一項に記載のフレキシブルディスプレイ製造用積層体に含まれた可撓性基板層上に素子を形成する段階と、
前記素子が形成された可撓性基板層をデボンディング層から剥離する段階と、
を含むフレキシブルディスプレイの製造方法。 - 前記デボンディング層は、第1面積を有するようにキャリア基板上に形成され、
前記可撓性基板層は、前記第1面積よりも大きな第2面積を有しながら、前記デボンディング層を完全に覆うように形成され、
前記素子は、前記デボンディング層と前記可撓性基板層とが重なる領域で前記可撓性基板層上に形成される請求項9に記載のフレキシブルディスプレイの製造方法。 - 前記可撓性基板層を剥離する段階は、前記デボンディング層と前記可撓性基板層とが重なる領域の内側縁部で前記キャリア基板に垂直方向に切断して、前記デボンディング層と前記可撓性基板層とが分離する請求項10に記載のフレキシブルディスプレイの製造方法。
- 前記剥離する段階において、可撓性基板層がデボンディング層から剥離される剥離強度が、0.05N/cm以下である請求項9から11の何れか一項に記載のフレキシブルディスプレイの製造方法。
- 前記剥離する段階において、前記デボンディング層と可撓性基板層との間に化学的または物理的変化を引き起こす工程を経ない請求項9から12の何れか一項に記載のフレキシブルディスプレイの製造方法。
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