JP2004174713A - Optical film sheet and display element using the same - Google Patents
Optical film sheet and display element using the same Download PDFInfo
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- JP2004174713A JP2004174713A JP2002338408A JP2002338408A JP2004174713A JP 2004174713 A JP2004174713 A JP 2004174713A JP 2002338408 A JP2002338408 A JP 2002338408A JP 2002338408 A JP2002338408 A JP 2002338408A JP 2004174713 A JP2004174713 A JP 2004174713A
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- 239000012788 optical film Substances 0.000 title claims abstract description 69
- 239000010408 film Substances 0.000 claims abstract description 123
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- 229910052753 mercury Inorganic materials 0.000 description 7
- 238000004544 sputter deposition Methods 0.000 description 7
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 6
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- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 6
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
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- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 4
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- TVIVIEFSHFOWTE-UHFFFAOYSA-K tri(quinolin-8-yloxy)alumane Chemical compound [Al+3].C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1 TVIVIEFSHFOWTE-UHFFFAOYSA-K 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000003848 UV Light-Curing Methods 0.000 description 2
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- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
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- 229920000728 polyester Polymers 0.000 description 2
- SYENVBKSVVOOPS-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butyl prop-2-enoate Chemical compound CCC(CO)(CO)COC(=O)C=C SYENVBKSVVOOPS-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
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- 229920010524 Syndiotactic polystyrene Polymers 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- ZCZFEIZSYJAXKS-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] prop-2-enoate Chemical compound OCC(CO)(CO)COC(=O)C=C ZCZFEIZSYJAXKS-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
【０００１】
【発明の属する技術分野】
本発明は、表面平滑性に優れた光学フィルムシートおよびこれを用いた表示素子に関する。
【０００２】
【従来の技術】
従来、表示素子用基板にはガラス基板が採用されてきたが、ガラス基板を用いた表示素子においては、ガラス基板自体が厚いため表示素子自体の薄型化が困難であると共に、軽量化しにくいという欠点があり、更に耐衝撃性の点で問題があった。
【０００３】
このガラス基板型表示素子のもつ欠点を改善する方法として、光学用高分子シートを用いて液晶表示素子を作製することにより、軽量化、耐衝撃性の向上が検討されている。
ガラス基板の代わりに導電性酸化金属物質を蒸着した長尺のポリエステルフィルムを用いて液晶表示素子を連続して製造することが示されている（例えば、特許文献１，２参照。）。しかしながら、研磨により極めて良好な平滑性が得られるガラス基板と異なり、高分子シートの場合には表面の平滑性に優れているとは言い難いものであった。特に、高精細な表示を目的としたＳＴＮ（Super Twisted Nematic）型液晶表示素子とした場合には、間隔を0.1μm単位で制御された基板間の液晶の複屈折性を利用して表示を行うために前記の高分子シートの表面平滑性が極めて重大である。また、自発光で高速駆動、高精細な表示を目的としたエレクトロルミネッセンス（ＥＬ）表示素子等の場合には、発光層が0.1μｍ単位の厚みで制御されるため、基板表面の突起欠陥または穴状欠陥が起因となる素子構造不良による表示欠陥（ダークスポット）が発生することや、基板表面の突起欠陥または穴状欠陥によりガスバリア膜に欠陥が生じるために、ＥＬ素子内部に水分子が透過して発光層もしくは仕事関数の小さい陰極材料を劣化させることがあり表示欠陥部分の成長といった問題があった（例えば、非特許文献１参照。）。また、表示素子は素子駆動のために電極パターンを加工することが必要であり、基板が搬送されるウエットプロセスでの基板上積層膜の層間密着性が高く、耐水性・耐薬品性に優れることが使用する基板には望まれている。更には、表示素子の信頼性を評価する上で、高温高湿度環境における加速試験においても基板上積層膜の層間密着性に優れることが使用する基板には望まれている。
【０００４】
【特許文献１】
特開昭５３−６８０９９号公報
【特許文献２】
特開昭５４−１２６５５９号公報
【非特許文献１】
「ＯＰＴＲＯＮＩＣＳ」，No.3，p122-123（２００１）記事
【０００５】
【発明が解決しようとする課題】
本発明の目的とするところは、表示素子、特にバリア欠陥低減による表示欠陥の低減されたＥＬ素子用途に適用可能な優れた表面平滑特性を持つ光学フィルムシートおよびこれを用いた表示素子を提供することにある。
【０００６】
【課題を解決するための手段】
すなわち本発明は
（１） 高分子材料からなる基材の少なくとも片面に、アクリレートモノマーを主成分とする紫外線硬化性樹脂組成物を積層し、乾燥後、硬化させたフィルムシートであって、紫外線硬化性樹脂組成物硬化層の表面粗さ算術平均値（Ｒａ）がＲａ＜１０ｎｍ、最大高さ（Ｒｙ）がＲｙ＜０．３μｍであり、且つ平均線からの深さが１０nm以上で穴深さと穴直径のアスペクト比（穴深さ／穴直径）が０．２よりも大きい穴の無いことを特徴とする光学フィルムシート。
（２） 高分子材料からなる基材の少なくとも片面に、アクリレートモノマーを主成分とする紫外線硬化性樹脂組成物を積層し、乾燥後、硬化させたフィルムシートであって、紫外線硬化性樹脂組成物硬化層の表面粗さ算術平均値（Ｒａ）がＲａ＜１０ｎｍ、最大高さ（Ｒｙ）がＲｙ＜０．３μｍであり、紫外線硬化性樹脂組成物硬化層の表面に最大高さと幅の最小値のアスペクト比（最大高さ／幅最小値）が０．２よりも大きい局所的な突起が無いことを特徴とする光学フィルムシート。
（３） 高分子材料からなる基材の少なくとも片面に、アクリレートモノマーを主成分とする紫外線硬化性樹脂組成物を積層し、乾燥後、硬化させたフィルムシートであって、紫外線硬化性樹脂組成物硬化層の表面粗さ算術平均値（Ｒａ）がＲａ＜１０ｎｍ、最大高さ（Ｒｙ）がＲｙ＜０．３μｍであり、且つ平均線からの深さが１０nm以上で穴深さと穴直径のアスペクト比（穴深さ／穴直径）が０．２よりも大きい穴の無く、紫外線硬化性樹脂組成物硬化層の表面に最大高さと幅の最小値のアスペクト比（最大高さ／幅最小値）が０．２よりも大きい局所的な突起も無いことを特徴とする光学フィルムシート。
（４） 前記アクリレートモノマーがイソシアヌール酸ＥＯ変性トリアクリレートを含む（１）〜（３）の光学フィルムシート。
（５） 前記アクリレートモノマーが、エポキシアクリレートモノマーを含むことを特徴とする（１）〜（４）の光学フィルムシート。
（６） 前記アクリレートモノマーがビスフェノールA型エポキシジアクリレートを含む（１）〜（５）の光学フィルムシート。
（７） 前記アクリレートモノマーが４臭素化ビスフェノールA型ジエポキシジアクリレートを含む（１）〜（６）の光学フィルムシート。
（８） 前記アクリレートモノマーがノボラック型エポキシアクリレートを含む（１）〜（７）の光学フィルムシート。
（９） 前記紫外線硬化性樹脂組成物硬化層の厚みが、０．３〜６μｍである（１）〜（８）の光学フィルムシート。
（１０） 前記紫外線硬化性樹脂組成物が硬化前の状態で紫外線硬化する際の環境下で流動性を示す液体であり、前記高分子材料からなる基板上での前記紫外線硬化性樹脂組成物の溶融接触角が１０°より小さいことを特徴とする（１）〜（９）の光学フィルムシート。
（１１） 前記紫外線硬化性樹脂組成物を沸点の異なる２種以上の溶剤に溶解させることを特徴とする、（１）〜（１０）の光学フィルムシート。
（１２） 前記乾燥の方法が、異なる乾燥温度を２段階以上経由して乾燥するものであり、乾燥温度の最低値が最も沸点の低い溶剤の沸点より低く、乾燥温度の最高値が最も沸点の高い溶剤の沸点より低い温度条件で、硬化前に残留溶剤量を１ｗｔ％以下まで乾燥することを特徴とする（１１）の光学フィルムシート。
（１３） 前記紫外線硬化性樹脂組成物硬化層上にバリア膜が積層されていることを特徴とする（１）〜（１２）の光学フィルムシート。
（１４） 前記バリア膜がSi、Al、In、Sn、Zn、Ti、Cu、Ce、Mg、La、Cr、Ca、Zr、Taから選ばれる１種以上を含む酸化物または窒化物または酸化窒化物またはハロゲン化物を主成分とする（１）〜（１３）の光学フィルムシート。
（１５） ウエットプロセスにおけるTMAH水溶液60分浸漬処理において、前記紫外線硬化性樹脂組成物硬化層と前記バリア膜との層間剥離が起こらないことを特徴とする（１３）、（１４）記載の光学フィルムシート。
（１６）４０℃、湿度９０％の環境下に、24時間暴露しても、前記紫外線硬化性樹脂組成物硬化層と前記バリア膜との層間剥離が起こらないことを特徴とする（１３）〜（１５）の光学フィルムシート。
（１７） 前記基材のガラス転移温度が160℃以上である（１）〜（１６）の光学フィルムシート。
（１８） 前記基材がノルボルネン系樹脂、シクロオレフィン系樹脂、またはポリエーテルスルホン樹脂から選ばれる一種類以上の樹脂を主成分とする（１）〜（１７）の光学フィルムシート。
（１９） （１）〜（１８）の光学フィルムシートを用いた表示素子。
（２０） （１）〜（１９）の光学フィルムシートを用いたエレクトロルミネッセンス表示素子。
である。
【０００７】
【発明の実施の形態】
本発明は、高分子材料からなる基板との濡れ性の優れたアクリレートモノマーを主成分とする紫外線硬化性樹脂組成物を基板上に積層することで得られた、有機ＥＬ表示素子にも適用可能な表面性を有する光学フィルムシートであり、これを用いた表示素子である。
【０００８】
本発明の光学フィルムシートは、少なくとも紫外線硬化性樹脂組成物を積層した面の表面粗さ算術平均値（Ｒａ）がＲａ＜１０ｎｍ、最大高さ（Ｒｙ）がＲｙ＜０．３μｍであり、且つ平均線からの深さ１０nm以上で穴深さと穴直径のアスペクト比（穴深さ／穴直径）が０．２よりも大きい穴が無い、および／または紫外線硬化性樹脂組成物の表面に最大高さと幅の最小値のアスペクト比（最大高さ／幅最小値）が０．２よりも大きい局所的な突起が無い表面であり、用いられる紫外線硬化性樹脂組成物はアクリレートモノマーを主成分とするものである。
【０００９】
表面粗さ算術平均値（Ｒａ）が１０ｎｍ以上の場合は、表示素子において表示の不均一性が発生すると言った問題がある。また、表面粗さ算術平均値（Ｒａ）が１０ｎｍよりも小さい場合でも、表面粗さにおける最大高さ（Ｒｙ）が０．３μｍ以上の凸状形状が存在すること、または、穴状欠陥が存在しその穴形状が表面粗さの平均線からの深さが１０nm以上で、穴深さと穴直径のアスペクト比（穴深さ／穴直径）が０．２よりも大きい場合は、表示素子の不均一性を引き起こすばかりでなく、積層するバリア膜にクラックや穴状欠陥が発生し易くなり、フィルムシート自体のバリア性能を低下させると言った問題が起こる。その結果、液晶表示素子では素子内部での気泡発生、エレクトロルミネッセンス素子では表示欠陥の発生及び表示欠陥部分の成長拡大と言った、表示素子自体の信頼性を大きく低下させる問題が発生する。
【００１０】
更に、表面粗さ算術平均値（Ｒａ）が１０ｎｍよりも小さい場合でも、表面粗さにおける最大高さ（Ｒｙ）が０．３μｍ以上の凸状形状が存在すること、また、その突起の最大高さと幅の最小値のアスペクト比（最大高さ／幅最小値）が０．２よりも大きい場合は、表示素子の不均一性を引き起こすばかりでなく、積層するバリア膜にクラックや膜厚不均一が発生し易くなりフィルムシート自体のバリア性能を低下させると言った問題が起こる。その結果、液晶表示素子では素子内部での気泡発生や基板間ギャップの不均一による表示不良、エレクトロルミネッセンス素子では非点灯欠陥の発生及び非点灯欠陥部分の成長拡大と言った、表示素子自体の信頼性を大きく低下させる問題が発生する。紫外線硬化性樹脂組成物表面の突起形状を表現する、最大高さと幅の最小値のアスペクト比（最大高さ／幅最小値）における最大高さとは、樹脂表面粗さの平均線からの突起の最大高さを示す。また、幅の最小値とは、局所的な突起を樹脂表面粗さの平均線で２次元に切り出した場合の突起のすそのに対応する面形状の最小距離を示す。つまり、突起の表面粗さ平均線における面形状が扁平していた場合に、最も急峻なアスペクト比を算出することができる。
【００１１】
紫外線硬化性樹脂組成物の厚みは０．３〜６μｍの範囲が好ましい。紫外線硬化性樹脂組成物の厚みは用いるベースフィルムシートの平滑性、特に最大高さ（Ｒｙ）に依存するが、０．３μｍ以下の場合は、ベースフィルムの凹凸を平坦化する効果に乏しい。また、厚みが６μｍ以上の場合は、厚みの均一性が低下する問題や、紫外線硬化性樹脂組成物によっては、ベースフィルムシートの柔軟性に追従できず破壊劣化を起こすと言った問題が生じる恐れがある。
【００１２】
前記の平滑性を有する紫外線硬化性樹脂組成物を積層した光学フィルムシートの作製方法としては、キスコート法、バーコート法、グラビアコート法、マイクログラビアコート法等を用いて、紫外線硬化性樹脂を溶剤に溶解し塗布成膜した後に紫外線硬化する湿式塗布方法や、紫外線硬化性樹脂組成物の表面に研磨されたガラス等の固体基板を接触させながら硬化成膜する転写法等を挙げることができる。生産性等を考慮すると湿式塗布法が好ましいが、本発明の光学フィルムシートを得る方法としては成膜方法に何ら制限はない。
【００１３】
また、湿式塗布法においては、用いるアクリレートモノマーを主成分とする紫外線硬化性樹脂組成物とベースフィルムとの濡れ性を良好にすることが好ましく、本検討を進める中で用いるアクリレートモノマーを主成分とする紫外線硬化性樹脂組成物の紫外線硬化前の樹脂組成物とベースフィルムとの溶融接触角が１０°より小さい場合に上記の平滑性が得られることが見出された。本検討の溶融接触角とは、紫外線硬化性樹脂組成物を積層するベースフィルムが紫外線硬化前に曝される雰囲気温度の上限温度での、ベースフィルムと硬化前紫外線樹脂組成物の接触角である。
【００１４】
また、本検討に用いるアクリレートモノマーを主成分とする紫外線硬化性樹脂組成物を少なくとも沸点の異なる２種以上の溶剤に溶解させた後に、ベースフィルム上に塗布し、溶剤が十分乾燥した後に紫外線硬化させることも好ましい。紫外線樹脂組成物を溶解する溶剤の種類が単一組成であると、ベースフィルム上の紫外線樹脂組成物ドープ溶剤液の濃度が、溶剤乾燥時において急激に変化し、紫外線樹脂組成物表面の凹凸発生が顕著になる。また、紫外線硬化性樹脂組成物と溶剤の組成比は２０：８０〜６０：４０であることが好ましい。組成比が溶剤リッチの場合は、塗布後の外観が悪くなるばかりでなく、揮発する溶剤の相対量が多くなるため、紫外線硬化後の表面凹凸が改善され難く、組成比が樹脂組成物リッチの場合は局所的な表面凹凸は改善されるものの、長周期的な表面うねりが発生することがあり、外観不良が発生しやすくなる。
【００１５】
用いる溶剤を乾燥させる雰囲気温度は、異なる温度雰囲気を２段階以上経由して溶剤乾燥するステップ乾燥が好ましく、更には、用いる溶剤が２種以上であり、乾燥温度の最低値が最も沸点の低い溶剤の沸点より低く、乾燥温度の最高値が最も沸点の高い溶剤の沸点より低い温度条件で、硬化前に残留溶剤量を１ｗｔ％以下まで乾燥することがより好ましい。溶剤間の沸点の差が、ステップ乾燥に用いる温度雰囲気差よりも小さい場合は、乾燥時の急激な温度差により、溶剤の揮発速度が大きくなるため、樹脂組成物の表面平滑性が低下する恐れがある。
【００１６】
本発明のアクリレートモノマーは特に限定はしないが、エポキシアクリレート、ウレタンアクリレート、イソシアヌール酸ＥＯ変性アクリレート、ペンタエリスリトールアクリレート、トリメチロールプロパンアクリレート、エチレングリコールアクリレート、ポリエステルアクリレート、ノルボルネンアクリレートなどのうち、２官能以上のアクリロイル基を有するモノマーを主成分とすることが好ましい。これらの２官能以上のアクリロイル基を有するモノマーは２種類以上を混合して用いる方法、また１官能のアクリレートを混合して用いる方法は硬化収縮を小さく抑える点でより好ましい。また、特に架橋度が高く、ガラス転移温度が200℃以上である、イソシアヌール酸ＥＯ変性トリアクリレートを主成分とすることが好ましく、更に、アクリレートモノマーから成る紫外線硬化性樹脂組成物の表面にバリア膜のような無機膜を積層する場合は、紫外線硬化性樹脂組成物と無機膜との層間密着性に優れることからエポキシアクリレートを含むことが好ましく、中でもビスフェノールＡ型エポキシジアクリレート、４臭素化ビスフェノールA型ジエポキシジアクリレート、ノボラック型エポキシアクリレートがより好ましい。これらのアクリレートモノマーは、単独で用いても複数種を混合して用いても良い。
また、本発明の紫外線硬化性樹脂組成物には、シリコン系、フッ素系のレベリング材、シリコン系、チタネート系、メルカプト系のシランカップリング材等を添加しても良い。
【００１７】
本発明の光学フィルムシートは、バリア膜が積層されていても良く、そのバリア膜に関して何ら制限はないが、バリア膜は水蒸気バリア性および／または酸素バリア性を有することが好ましい。また、その材質についても特に制限はしないが、バリア特性に温度湿度依存性が少ない無機物質を主構成とするバリア膜が好ましい。例えばSi、Al、In、Sn、Zn、Ti、Cu、Ce 、Mg、La、Cr、Ca、Zr、Ta等の１種以上を含む酸化物もしくは窒化物もしくは酸化窒化物もしくはハロゲン化合物などを用いることができる。無機物層は厚すぎると曲げ応力によるクラックの恐れがあり、薄すぎると膜が島状に分布するため、いずれもガスバリア性が悪くなる。上記のことより、それぞれの無機物層の厚みは5nm〜500nmの範囲が好ましいが、特に限定はしない。また、それぞれの無機物層は同じ組成でも別の組成でも良く制限はない。ガスバリア性と高透明性を両立させるには無機層として珪素酸化物や珪素酸化窒化物を使うのが好ましい。また、無機膜の成膜方法としては抵抗加熱蒸着法、電子線蒸着法、イオンプレーティング法、ＣＶＤ法、スパッタリング法、常圧ＣＶＤ法等が適用でき、目的の無機酸化物、無機窒化物、無機窒化酸化物、無機ハロゲン化合物が得られる方法であれば制限はない。
【００１８】
また、無機物質を主構成とするバリア膜としては、異なる種類の無機酸化物、無機窒化物もしくは無機酸化窒化物を多数積層する構造や無機層／有機層／無機層を交互に積層する層構成のバリア膜がある。バリアの信頼性を考えると単層の無機バリア膜よりも前記に示す多層構造バリア膜が好ましく、無機層／有機層／無機層を交互に積層するバリア膜がより好ましい。前記多層膜の有機層としては、本発明に用いるアクリレートモノマーを主成分とする紫外線硬化性樹脂組成物が好ましいが、特に限定はされない。
【００１９】
本発明の光学フィルム及びシートに用いるベースフィルムは、表示素子の製造環境温度に耐えうる必要があり、そのガラス転移温度は１６０℃以上であることが望ましい。例として、ポリエステル、ポリカーボネイト、ポリノルボルネン、ポリエーテルイミド、ポリアリレート、ポリエーテルスルホン、ポリエーテルケトン、ポリフェニレンスルフィド、シンジオタクチックポリスチレン、シクロポリオレフィン及びそのコポリマー、イミド変性ポリメチルメタクリレート等のイミド変性した高分子等によるフィルムシート等があげられるが、特に限定はしない。また、本発明のベースフィルムは各層の形成に先立ち、積層する各層との密着力を高めるために脱ガス処理、コロナ放電処理、火炎処理ＵＶオゾン処理、エキシマＵＶ処理等の表面処理が施されていてもよい。上記ベースフィルムは、押出成形およびキャスティング等の方法でシート化することができ、本発明の光学フィルム及びシートは、成形したベースフィルムの上にキャスティング、コーティングあるいは各種印刷手法、積層手法等により、紫外線硬化性樹脂組成物を積層した構造である。
【００２０】
本発明の紫外線硬化性樹脂組成物を硬化させるための紫外線照射に関しては、必要な波長の光を選択的に照射してもよい。具体的には、照射部に選択透過フィルターをもうけるか、フィルムの塗膜が形成される側とは反対面から照射する方法などが挙げられる。また大気中の酸素によって紫外線効果樹脂の硬化反応が阻害させる場合には、窒素など不活性ガス雰囲気化で照射を行っても良い。紫外線照射量は、３６５ｎｍまたは２５４ｎｍの波長か、ある波長を選択的に照射する場合は、紫外線領域で最大照射量となる波長域での照射量を、紫外線照度計によって測定するとよい。
【００２１】
【実施例】
以下本発明を実施例によって説明するが、本発明は実施例により何ら限定されるものではない。
【００２２】
なお、各フィルムの表面平滑性については目視観察及び超深度レーザー顕微鏡または原子間力顕微鏡（AFM）にて評価した。超深度レーザー顕微鏡は1mm x 1.4mmの領域を測定し、AFMは20μｍ×20μｍ角の領域を測定した。
【００２３】
バリア性については、モコン社製のパーメトランを用いて水蒸気バリア性をJIS−K7129−B法にて評価した。
バリア膜と紫外線硬化性樹脂組成物の密着性は、透明電極パターン加工性および水蒸気バリア性評価後のバリア膜を碁盤目剥離試験することで評価した。
【００２４】
＜実施例１＞
厚さ２００μｍ、最大高さ（Ｒｙ）が１．０μｍポリエーテルスルホン（ＰＥＳ）をベースフィルムとした。紫外線硬化性樹脂組成物としてイソシアヌール酸ＥＯ変性トリアクリレート（東亞合成製 Ｍ−３１５）３０重量部、エポキシアクリレート（昭和高分子社製 VR-60LAV）４．５重量部、ウレタンアクリレート（大日本インキ社製 ユニテ゛ィック17-806）３重量部、光開始剤（チハ゛カ゛イキ゛ー社製 IRG-907）１．５重量部、・`ルセロソルフ゛アセテート（沸点＝145℃）１２重量部、酢酸ブチル（沸点＝126℃）４０重量部，ブチルセロソルブ（沸点＝170℃）７．０重量部にて撹拌、溶解してＲＣ＝３６ｗｔ％の均一な溶液としたものをバーコーターコーターにて塗布し、加熱乾燥機中９０℃で２分間続いて１２０℃で３分間加熱して溶媒を除去した。溶媒除去後の紫外線硬化性樹脂組成物はペースト状の軟化状態であり、ＰＥＳと硬化前の樹脂組成物の120℃での溶融接触角は２．２°であった。乾燥後の樹脂組成物に、高圧水銀灯にて350ｍＪ／cm2の紫外線を照射させ硬化樹脂組成物をフィルム上に作製した。
【００２５】
作製した紫外線硬化性樹脂組成物積層フィルムの表面平滑性をAFMにて評価した。作製した基板はＲａ＝０．４ｎｍ、Ｒｙ＝0．1μｍ、深さ１０nm以上の穴欠点が無く、目視外観の良好な非常に平滑性の高いフィルムであった。
【００２６】
＜実施例２＞
厚さ２００μｍ、最大高さ（Ｒｙ）が１．０μｍポリエーテルスルホン（ＰＥＳ）をベースフィルムとした。紫外線硬化性樹脂組成物としてイソシアヌール酸ＥＯ変性トリアクリレート（東亞合成製 Ｍ−３１５）４０重量部、光開始剤（チハ゛カ゛イキ゛ー社製 IRG-907）２．５重量部、・`ルセロソルフ゛アセテート（沸点＝145℃）８．５重量部、乳酸エチル（沸点＝155℃）３０重量部，ブチルセロソルブ（沸点＝170℃）６．０重量部にて撹拌、溶解してＲＣ＝４８．８ｗｔ％の均一な溶液としたものをバーコーターコーターにて塗布し、加熱乾燥機中９０℃で５分間続いて１２０℃で２分間加熱して溶媒を除去した。溶媒除去後の紫外線硬化性樹脂組成物はペースト状の軟化状態であり、ＰＥＳと硬化前の樹脂組成物の120℃での溶融接触角は１．０°であった。乾燥後の樹脂組成物に、高圧水銀灯にて350ｍＪ／cm2の紫外線を照射させ硬化樹脂組成物をフィルム上に作製した。
【００２７】
作製した紫外線硬化性樹脂組成物積層フィルムの表面平滑性をAFMにて評価した。作製した基板はＲａ＝０．３ｎｍ、Ｒｙ＝0．０３μｍ、深さ１０nm以上の穴欠点が無く、目視外観の良好な非常に平滑性の高いフィルムであった。
【００２８】
＜実施例３＞
厚さ２００μｍ、最大高さ（Ｒｙ）が１．０μｍポリエーテルスルホン（ＰＥＳ）をベースフィルムとした。紫外線硬化性樹脂組成物としてエポキシアクリレート（昭和高分子社製 VR-60LAV）２０重量部、ウレタンアクリレート（大日本インキ社製 ユニテ゛ィック17-806）１４重量部、光開始剤（チハ゛カ゛イキ゛ー社製 IRG-907）１．２重量部、・`ルセロソルフ゛アセテート（沸点＝145℃）１５重量部、酢酸ブチル（沸点＝126℃）４０重量部，ブチルセロソルブ（沸点＝170℃）６．０重量部にて撹拌、溶解してＲＣ＝２６．４ｗｔ％の均一な溶液としたものをバーコーターコーターにて塗布し加熱乾燥機中９０℃で２分間続いて１２０℃で３分間加熱して溶媒を除去した。溶媒除去後の紫外線硬化性樹脂組成物はペースト状の軟化状態であり、ＰＥＳと硬化前の樹脂組成物の120℃での溶融接触角は１８°であった。乾燥後の樹脂組成物の表面にＲａ＝0.3nm、Ry=5nmのシリコンウエハーを接触転写させながら、光学フィルムシートを通して高圧水銀灯にて450ｍＪ／cm2の紫外線を照射させ硬化させた。紫外線硬化後の樹脂表面からシリコンウエハーを取り除くことで紫外線硬化性樹脂組成物付き光学フィルムシートを作製した。
【００２９】
作製した紫外線硬化性樹脂組成物積層フィルムの表面平滑性をAFMにて評価した。作製した基板はＲａ＝０．４ｎｍ、Ｒｙ＝０．０１μｍ、深さ１０nm以上の穴欠点が無く、目視外観の良好な非常に平滑性の高いフィルムであった。
【００３０】
＜実施例４＞
厚さ２００μｍ、最大高さ（Ｒｙ）が１．０μｍポリエーテルスルホン（ＰＥＳ）をベースフィルムとした。紫外線硬化性樹脂組成物としてイソシアヌール酸ＥＯ変性トリアクリレート（東亞合成製 Ｍ−３１５）３０重量部、エポキシアクリレート（東亞合成社製 M-211B）７．５重量部、光開始剤（チハ゛カ゛イキ゛ー社製IRG-907）１．１重量部、・`ルセロソルフ゛アセテート １０．８重量部、酢酸ブチル ３６重量部，ブチルセロソルブ ６．３重量部にて撹拌、溶解してＲＣ＝４２ｗｔ％の均一な溶液としたものをバーコーターコーターにて塗布し、加熱乾燥機中９０℃で２分間続いて１２０℃で３分間加熱して溶媒を除去した。溶媒除去後の紫外線硬化性樹脂組成物は粘調な液体状態であった。乾燥後の樹脂組成物に、高圧水銀灯にて350ｍＪ／cm2の紫外線を照射させ４μｍ厚の硬化樹脂組成物をフィルム上に作製した。
【００３１】
作製した紫外線硬化性樹脂組成物積層フィルムの表面平滑性をAFMにて評価した。作製した基板はＲａ＝０．５ｎｍ、Ｒｙ＝0．２μｍ、深さ１０nm以上の穴欠点が無く、20μｍ×20μｍ角の領域における局所的な突起形状の最大高さと幅の最小値のアスペクト比（最大高さ／幅最小値）の最大値は０．１５であり、目視外観の良好な非常に平滑性の高いフィルムであった。
【００３２】
＜実施例５＞
厚さ２００μｍ、最大高さ（Ｒｙ）が１．０μｍポリエーテルスルホン（ＰＥＳ）をベースフィルムとした。紫外線硬化性樹脂組成物としてイソシアヌール酸ＥＯ変性トリアクリレート（東亞合成製 Ｍ−３１５）３０重量部、ノルボレネンジアクリレート（日本化薬社製 KAYARAD R-684）１０重量部、光開始剤（チハ゛カ゛イキ゛ー社製 IRG-907）２．０重量部、・`ルセロソルフ゛アセテート ９．０重量部、酢酸ブチル ３０重量部，ブチルセロソルブ ６．０重量部にて撹拌、溶解してＲＣ＝４８．３ｗｔ％の均一な溶液としたものをバーコーターコーターにて塗布し、加熱乾燥機中９０℃で２分間続いて１２０℃で３分間加熱して溶媒を除去した。溶媒除去後の紫外線硬化性樹脂組成物は粘調な液体状態であった。乾燥後の樹脂組成物に、高圧水銀灯にて350ｍＪ／cm2の紫外線を照射させ４μｍ厚の硬化樹脂組成物をフィルム上に作製した。
【００３３】
作製した紫外線硬化性樹脂組成物積層フィルムの表面平滑性をAFMにて評価した。作製した基板はＲａ＝０．３ｎｍ、Ｒｙ＝０．０３μｍ、深さ１０nm以上の穴欠点が無く、20μｍ×20μｍ角の領域における局所的な突起形状の最大高さと幅の最小値のアスペクト比（最大高さ／幅最小値）の最大値は０．０８であり、目視外観の良好な非常に平滑性の高いフィルムであった。
【００３４】
＜実施例６＞
厚さ２００μｍ、最大高さ（Ｒｙ）が１．０μｍポリエーテルスルホン（ＰＥＳ）をベースフィルムとした。紫外線硬化性樹脂組成物としてイソシアヌール酸ＥＯ変性トリアクリレート（東亞合成製 Ｍ−３１５）３０重量部、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 VR-７７）１０重量部、光開始剤（チハ゛カ゛イキ゛ー社製 IRG-907）２．０重量部、・`ルセロソルフ゛アセテート ９．０重量部、酢酸ブチル ３０重量部，ブチルセロソルブ ６．０重量部にて撹拌、溶解してＲＣ＝４８．３ｗｔ％の均一な溶液としたものをバーコーターコーターにて塗布し、加熱乾燥機中９０℃で２分間続いて１２０℃で３分間加熱して溶媒を除去した。溶媒除去後の紫外線硬化性樹脂組成物は粘調な液体状態であった。乾燥後の樹脂組成物に、高圧水銀灯にて350ｍＪ／cm2の紫外線を照射させ４μｍ厚の硬化樹脂組成物をフィルム上に作製した。
【００３５】
作製した紫外線硬化性樹脂組成物積層フィルムの表面平滑性をAFMにて評価した。作製した基板はＲａ＝０．４ｎｍ、Ｒｙ＝０．０６μｍ、深さ１０nm以上の穴欠点が無く、20μｍ×20μｍ角の領域における局所的な突起形状の最大高さと幅の最小値のアスペクト比（最大高さ／幅最小値）の最大値は０．０９であり、目視外観の良好な非常に平滑性の高いフィルムであった。
【００３６】
＜比較１＞
ポリエーテルスルホン（住友化学社製ＶＩＣＴＲＥＸＰＥＳー４１００P Ｔｇ：２２３℃）を５０ｍｍφ押出実験機でシリンダー温度３５０℃の条件にて溶融混練し、Ｔダイによりシート状に成形し、周速度１．９０ｍ／分の外径３００ｍｍφの２５０℃に保たれたハードクロムメッキ冷却ロールを用いて２００μで６８０ｍｍ幅のフィルムを製造した。
【００３７】
作製した光学フィルムシートの表面平滑性をAFMにて評価した。作製した基板はＲａ＝０．４ｎｍ、深さ１０nm以上の穴欠点は無かったが、超深度レーザー顕微鏡による評価ではＲｙ＝１．６μｍであり、1mm x 1.4mmの領域の局所的な突起形状の最大高さと幅の最小値のアスペクト比（最大高さ／幅最小値）の最大値は０．５３であり、目視外観評価でも部分的に凸状形状が確認された。
【００３８】
＜比較例２＞
厚さ２００μｍ、最大高さ（Ｒｙ）が１．０μｍポリエーテルスルホン（ＰＥＳ）をベースフィルムとした。紫外線硬化性樹脂組成物としてエポキシアクリレート（昭和高分子社製 VR-60LAV）２０重量部、ウレタンアクリレート（大日本インキ社製 ユニテ゛ィック17-806）１４重量部、光開始剤（チハ゛カ゛イキ゛ー社製 IRG-907）１．２重量部、・`ルセロソルフ゛アセテート（沸点＝145℃）１５重量部、酢酸ブチル（沸点＝126℃）４０重量部，ブチルセロソルブ（沸点＝170℃）６．０重量部にて撹拌、溶解してＲＣ＝２６．４ｗｔ％の均一な溶液としたものをバーコーターコーターにて塗布し、加熱乾燥機中９０℃で２分間続いて１２０℃で３分間加熱して溶媒を除去した。溶媒除去後の紫外線硬化性樹脂組成物はペースト状の軟化状態であり、ＰＥＳと硬化前の樹脂組成物の120℃での溶融接触角は１８°であった。乾燥後の樹脂組成物に、高圧水銀灯にて350ｍＪ／cm2の紫外線を照射させ硬化樹脂組成物をフィルム上に作製した。
【００３９】
作製した紫外線硬化性樹脂組成物積層フィルムの表面平滑性をAFMにて評価した。作製した基板はＲａ＝０．８ｎｍ、Ｒｙ＝０．５μｍ、深さ１０nm以上の穴欠点が２０μｍ□サイス゛に５点確認された。
【００４０】
＜実施例７＞
実施例２で作製した基板上に、パルスＤＣマグネトロン法により、初期真空度３×１０−４Ｐａの状態から酸素／アルゴンガス９％の混合ガスを導入して３×１０−１Ｐａの条件下においてシリコンターゲットにてスパッタリングを行い１０００Å厚のバリアＳｉＯｘ膜を得た。得られたバリア膜付き光学フィルムシートの水蒸気透過率は測定限界以下の値（＜0.1g/m2/day）を示し、バリア性が良好であった。
【００４１】
バリア膜上に続いて、透明導電膜として、パルスＤＣマグネトロン法により初期真空度３×１０−４Ｐａの状態から酸素／アルゴンガス４％の混合ガスを導入して１×１０−１Ｐａの条件下においてＩＴＯターゲットにてスパッタリングを行いＩｎ／Ｉｎ＋Ｓｎの原子比が０．９８である酸化インジウム錫（ＩＴＯ）からなる透明導電膜を得た。測定の結果、膜厚は１０００Å、比抵抗は４×１０-4Ω−ｃｍであった。
【００４２】
得られた透明電極／バリア膜／紫外線硬化性樹脂組成物層／ＰＥＳ基板を用いて、有機ＥＬ素子を作製した。ＩＴＯ陽極の上に正孔輸送層としてＴＰＤを４０ｎｍ蒸着し、ついで電子輸送層兼発光層としてＡｌｑ３を７０ｎｍ蒸着後、陰極としてＡｇ／Ｍｇ（１０：１）の陰極を２００ｎｍ蒸着し有機ＥＬ素子を作製した。陰極側を紫外線硬化性樹脂組成物をシール材とした接着剤を用いてガラス基板で封止した。
【００４３】
作製した有機ＥＬ素子を室温（２３℃、４５％ＲＨ）に２週間保管した素子を評価した結果、発光部分に素子劣化は見られず、初期発光特性同等の良好な素子特性を示した。
【００４４】
＜実施例８＞
実施例５で作製した基板上に、パルスＤＣマグネトロン法により、初期真空度３×１０−４Ｐａの状態から酸素／アルゴンガス９％の混合ガスを導入して３×１０−１Ｐａの条件下においてシリコンターゲットにてスパッタリングを行い１０００Å厚のバリアＳｉＯｘ膜を得た。得られたバリア膜付き光学フィルムシートの水蒸気透過率は測定限界以下の値（＜0.1g/m2/day）を示し、バリア性が良好であった。
【００４５】
バリア膜上に続いて、透明導電膜として、パルスＤＣマグネトロン法により初期真空度３×１０−４Ｐａの状態から酸素／アルゴンガス４％の混合ガスを導入して１×１０−１Ｐａの条件下においてＩＴＯターゲットにてスパッタリングを行いＩｎ／Ｉｎ＋Ｓｎの原子比が０．９８である酸化インジウム錫（ＩＴＯ）からなる透明導電膜を得た。測定の結果、膜厚は１０００Å、比抵抗は４×１０-4Ω−ｃｍであった。
【００４６】
得られた透明電極／バリア膜／紫外線硬化性樹脂組成物層／ＰＥＳ基板を用いて、有機ＥＬ素子を作製した。ＩＴＯ陽極の上に正孔輸送層としてＴＰＤを４０ｎｍ蒸着し、ついで電子輸送層兼発光層としてＡｌｑ３を７０ｎｍ蒸着後、陰極としてＡｇ／Ｍｇ（１０：１）の陰極を２００ｎｍ厚に共蒸着し有機ＥＬ素子を作製した。紫外線硬化性樹脂組成物のシール材を接着剤として用いて陰極側をガラス基板で封止した。
【００４７】
作製した有機ＥＬ素子を室温（２３℃、４５％ＲＨ）に２週間保管した素子を評価した結果、発光部分に素子劣化は見られず、初期発光特性同等の良好な素子特性を示した。
【００４８】
＜実施例９＞
実施例６で作製した基板上に、パルスＤＣマグネトロン法により、初期真空度３×１０−４Ｐａの状態から酸素／アルゴンガス９％の混合ガスを導入して３×１０−１Ｐａの条件下においてシリコンターゲットにてスパッタリングを行い１０００Å厚のバリアＳｉＯｘ膜を得た。得られたバリア膜付き光学フィルムシートの水蒸気透過率は測定限界以下の値（＜0.1g/m2/day）を示し、バリア性が良好であった。また、バリア性評価（４０℃９０％２４時間）後のＳｉＯｘ膜面を碁盤目にカットして密着性を評価した結果、碁盤目の剥離及びカットしたエッジの欠けは見られず、耐湿層間密着性が良好であった。
【００４９】
バリア膜上に続いて、透明導電膜として、パルスＤＣマグネトロン法により初期真空度３×１０−４Ｐａの状態から酸素／アルゴンガス４％の混合ガスを導入して１×１０−１Ｐａの条件下においてＩＴＯターゲットにてスパッタリングを行いＩｎ／Ｉｎ＋Ｓｎの原子比が０．９８である酸化インジウム錫（ＩＴＯ）からなる透明導電膜を得た。測定の結果、膜厚は１０００Å、比抵抗は４×１０-4Ω−ｃｍであった。
【００５０】
得られた透明電極／バリア膜／紫外線硬化性樹脂組成物層／ＰＥＳ基板を用いて、有機ＥＬ素子を作製するため、ＩＴＯを電極幅１００μｍ／電極間５０μｍにパターニングした。ＩＴＯパターニングのため、ＩＴＯにフォトレジスト(東京応化社製：PMER P-LA900PM)を塗布し、パターンを露光した。次にTMAH水溶液に６０分間浸漬し不要な感光剤を除去し、ITOをエッチング（塩化第二鉄水溶液）により除去した。パターニング後の基板は、バリア膜のクラックや層間剥離の欠陥が見られず、耐薬品性および層間密着性が良好であった。パターニングの後、ＩＴＯ陽極の上に正孔輸送層としてＴＰＤを４０ｎｍ蒸着し、ついで電子輸送層兼発光層としてＡｌｑ３を７０ｎｍ蒸着後、陰極としてＡｇ／Ｍｇ（１０：１）を用い、メタルマスクにより１００μｍ電極幅、２００ｎｍ厚に共蒸着し有機ＥＬ素子を作製した。紫外線硬化性樹脂組成物のシール材を接着剤として用いて陰極側をガラス基板で封止した。
【００５１】
作製した有機ＥＬ素子を室温（２３℃、４５％ＲＨ）に２週間保管した素子を評価した結果、発光部分に素子劣化は見られず、初期発光特性同等の良好な素子特性を示した。
【００５２】
＜比較例３＞
比較例１で作製した光学フィルムシート上に、実施例７と同様な手法にてバリア膜を成膜した後に、透明電極、正孔輸送層、電子輸送層、陰極を順じ成膜し、有機ＥＬ素子を作製した。用いたバリア膜付き光学フィルムシートの水蒸気透過率は１．３g/m2/dayであり、水蒸気の透過が多い傾向が確認された。
【００５３】
作製した有機ＥＬ素子を室温（２３℃、４５％ＲＨ）に２週間保管した素子を評価した結果、作製初期から非発光部が確認され、保管後確認したところ素子全面に劣化が進行し、ほとんど発光部分が観察出来なかった。
【００５４】
＜比較例４＞
比較例２で作製した光学フィルムシート上に、実施例４と同様な手法にてバリア膜を成膜した後に、透明電極、正孔輸送層、電子輸送層、陰極を順じ成膜し、有機ＥＬ素子を作製した。用いたバリア膜付き光学フィルムシートの水蒸気透過率は0.２g/m2/dayであり、水蒸気の透過が多い傾向が確認された。
【００５５】
作製した有機ＥＬ素子を室温（２３℃、４５％ＲＨ）に２週間保管した素子を評価した結果、作製初期では非発光部が確認されなかったが、保管後確認したところ非発光部が素子内部に確認された。
【００５６】
＜比較例５＞
比較例１で作製した光学フィルムシート上に、実施例９と同様な手法にてバリア膜を成膜した。バリア膜付き光学フィルムシートの水蒸気透過率は１．３g/m2/dayであり、水蒸気の透過が多い傾向が確認され、更に、バリア性評価（４０℃９０％２４時間）後の碁盤目剥離試験において基板と無機膜の界面において剥離があり、層間密着性も乏しいことが確認された。
【００５７】
バリア膜成膜後に透明導電膜を成膜し、透明電極／バリア膜／ＰＥＳ基板を用いて、有機ＥＬ素子を作製するため、ＩＴＯをパターニングした。パターニングのため、ＩＴＯにフォトレジスト(東京応化社製：PMER P-LA900PM)を塗布し、パターンを露光した。次にTMAH水溶液に６０分間浸漬し不要な感光剤を除去したが、ＰＥＳ基板とバリア膜の間で層間剥離が発生し、層間密着性に乏しいことが確認された。
【００５８】
【発明の効果】
本発明によれば平滑性に優れた光学フィルムシートが作製でき、従来ではプラスチック基板の適用が難しかったＥＬ表示素子もプラスチック化が可能になる。更に、本発明は、ロールトゥロールの生産方式の適用も可能であるため、生産性高く光学フィルムシートを提供できるため、産業上極めて有用である。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to an optical film sheet having excellent surface smoothness and a display device using the same.
[0002]
[Prior art]
Conventionally, a glass substrate has been adopted as a substrate for a display element. However, in a display element using a glass substrate, it is difficult to reduce the thickness of the display element itself because the glass substrate itself is thick, and it is difficult to reduce the weight. And there was a problem in terms of impact resistance.
[0003]
As a method of improving the disadvantages of the glass substrate type display element, reduction in weight and improvement in impact resistance by manufacturing a liquid crystal display element using an optical polymer sheet have been studied.
It is disclosed that a liquid crystal display element is continuously manufactured using a long polyester film on which a conductive metal oxide material is deposited instead of a glass substrate (for example, see Patent Documents 1 and 2). However, unlike a glass substrate, which can obtain extremely good smoothness by polishing, a polymer sheet cannot be said to have excellent surface smoothness. In particular, in the case of an STN (Super Twisted Nematic) type liquid crystal display element for high-definition display, display is performed by utilizing the birefringence of the liquid crystal between the substrates whose interval is controlled in units of 0.1 μm. Therefore, the surface smoothness of the polymer sheet is extremely important. Further, in the case of an electroluminescence (EL) display element or the like for high-speed driving and high-definition display by self-luminous light, the light emitting layer is controlled in a unit of 0.1 μm, so that a protrusion defect or a hole on the substrate surface is formed. Since a display defect (dark spot) due to a device structure defect due to a shape defect or a gas barrier film due to a projection defect or a hole-like defect on the substrate surface, water molecules permeate into the EL device. As a result, the light emitting layer or the cathode material having a small work function may be deteriorated, and there is a problem that a display defect portion grows (for example, see Non-Patent Document 1). In addition, the display element requires electrode pattern processing to drive the element, and the interlayer adhesion of the laminated film on the substrate in the wet process in which the substrate is transported is high, and the water resistance and chemical resistance are excellent. Is desired for a substrate to be used. Furthermore, in evaluating the reliability of a display element, it is desired for a substrate used to have excellent interlayer adhesion of a laminated film on the substrate even in an accelerated test in a high temperature and high humidity environment.
[0004]
[Patent Document 1]
JP-A-53-68099
[Patent Document 2]
JP-A-54-126559
[Non-patent document 1]
"OPTRONICS", No.3, p122-123 (2001) Article
[0005]
[Problems to be solved by the invention]
An object of the present invention is to provide an optical film sheet having excellent surface smoothness applicable to a display element, in particular, an EL element in which a display defect is reduced by reducing a barrier defect, and a display element using the same. It is in.
[0006]
[Means for Solving the Problems]
That is, the present invention
(1) A film sheet obtained by laminating an ultraviolet-curable resin composition containing an acrylate monomer as a main component on at least one surface of a polymer material, drying and curing the resin sheet, wherein the ultraviolet-curable resin composition is Arithmetic mean surface roughness (Ra) of the hardened layer is Ra <10 nm, maximum height (Ry) is Ry <0.3 μm, and the depth from the average line is 10 nm or more, and the aspect of hole depth and hole diameter is An optical film sheet characterized by having no holes having a ratio (hole depth / hole diameter) larger than 0.2.
(2) A film sheet obtained by laminating an ultraviolet-curable resin composition containing an acrylate monomer as a main component on at least one side of a base material made of a polymer material, drying and curing the resin sheet, the ultraviolet-curable resin composition The arithmetic average value (Ra) of the surface roughness of the cured layer is Ra <10 nm, the maximum height (Ry) is Ry <0.3 μm, and the minimum value of the maximum height and the width on the surface of the ultraviolet curable resin composition cured layer An optical film sheet characterized in that there is no local protrusion having an aspect ratio (maximum height / minimum width) of more than 0.2.
(3) A film sheet obtained by laminating an ultraviolet-curable resin composition containing an acrylate monomer as a main component on at least one surface of a base material made of a polymer material, drying and curing the resin sheet, wherein the ultraviolet-curable resin composition is Arithmetic mean surface roughness (Ra) of the hardened layer is Ra <10 nm, maximum height (Ry) is Ry <0.3 μm, and the depth from the average line is 10 nm or more, and the aspect of hole depth and hole diameter is There is no hole having a ratio (hole depth / hole diameter) larger than 0.2, and the aspect ratio (maximum height / minimum width) of the minimum height and width on the surface of the cured layer of the ultraviolet curable resin composition. An optical film sheet characterized by having no local protrusions larger than 0.2.
(4) The optical film sheet according to any one of (1) to (3), wherein the acrylate monomer contains an isocyanuric acid EO-modified triacrylate.
(5) The optical film sheet according to (1) to (4), wherein the acrylate monomer contains an epoxy acrylate monomer.
(6) The optical film sheet according to (1) to (5), wherein the acrylate monomer contains a bisphenol A type epoxy diacrylate.
(7) The optical film sheet according to any one of (1) to (6), wherein the acrylate monomer contains tetrabrominated bisphenol A type diepoxy diacrylate.
(8) The optical film sheet according to any one of (1) to (7), wherein the acrylate monomer contains a novolak epoxy acrylate.
(9) The optical film sheet according to (1) to (8), wherein the cured layer of the ultraviolet curable resin composition has a thickness of 0.3 to 6 μm.
(10) The ultraviolet-curable resin composition is a liquid that exhibits fluidity in an environment in which the ultraviolet-curable resin composition is cured by ultraviolet light before being cured, and is a liquid of the ultraviolet-curable resin composition on a substrate made of the polymer material. The optical film sheet according to any one of (1) to (9), wherein the melt contact angle is smaller than 10 °.
(11) The optical film sheet according to (1) to (10), wherein the ultraviolet curable resin composition is dissolved in two or more solvents having different boiling points.
(12) The method of drying, wherein drying is performed through two or more different drying temperatures, wherein the lowest value of the drying temperature is lower than the boiling point of the solvent having the lowest boiling point, and the highest value of the drying temperature is the highest value of the solvent having the highest boiling point. (11) The optical film sheet according to (11), wherein the residual solvent amount is dried to 1 wt% or less before curing under a temperature condition lower than the boiling point of the high solvent.
(13) The optical film sheet according to any one of (1) to (12), wherein a barrier film is laminated on the cured layer of the ultraviolet curable resin composition.
(14) The barrier film is an oxide, nitride or oxynitride containing at least one selected from Si, Al, In, Sn, Zn, Ti, Cu, Ce, Mg, La, Cr, Ca, Zr and Ta. The optical film sheet according to any one of (1) to (13), wherein the optical film sheet mainly comprises a substance or a halide.
(15) The optical film according to (13) or (14), wherein in the immersion treatment of the TMAH aqueous solution for 60 minutes in the wet process, delamination between the cured layer of the ultraviolet-curable resin composition and the barrier film does not occur. Sheet.
(16) Even when exposed to an environment of 40 ° C. and 90% humidity for 24 hours, delamination between the cured layer of the ultraviolet-curable resin composition and the barrier film does not occur (13) to (13). The optical film sheet according to (15).
(17) The optical film sheet according to any one of (1) to (16), wherein the glass transition temperature of the substrate is 160 ° C. or higher.
(18) The optical film sheet according to any one of (1) to (17), wherein the base material is mainly composed of at least one resin selected from a norbornene-based resin, a cycloolefin-based resin, and a polyethersulfone resin.
(19) A display element using the optical film sheet of (1) to (18).
(20) An electroluminescent display device using the optical film sheet according to any one of (1) to (19).
It is.
[0007]
BEST MODE FOR CARRYING OUT THE INVENTION
INDUSTRIAL APPLICABILITY The present invention can be applied to an organic EL display device obtained by laminating an ultraviolet-curable resin composition containing an acrylate monomer having excellent wettability with a substrate made of a polymer material as a main component on the substrate. An optical film sheet having excellent surface properties, and a display element using the same.
[0008]
The optical film sheet of the present invention has a surface roughness arithmetic average value (Ra) of at least Ra <10 nm, a maximum height (Ry) of Ry <0.3 μm, and a surface on which the ultraviolet curable resin composition is laminated, and There is no hole having an aspect ratio (hole depth / hole diameter) of hole depth to hole diameter of more than 0.2 at a depth of 10 nm or more from the average line and / or the maximum height on the surface of the ultraviolet curable resin composition. A surface having no local protrusions having an aspect ratio (maximum height / minimum width) of the minimum value of width and width greater than 0.2, and the ultraviolet-curable resin composition to be used has an acrylate monomer as a main component. Things.
[0009]
When the surface roughness arithmetic average value (Ra) is 10 nm or more, there is a problem that display non-uniformity occurs in the display element. Further, even when the arithmetic average value (Ra) of the surface roughness is smaller than 10 nm, a convex shape having a maximum height (Ry) of 0.3 μm or more in the surface roughness exists, or a hole-like defect exists. If the depth of the hole from the average line of the surface roughness is 10 nm or more and the aspect ratio between the hole depth and the hole diameter (hole depth / hole diameter) is larger than 0.2, the display element is not defective. In addition to causing uniformity, cracks and hole-like defects are liable to occur in the laminated barrier film, causing a problem that the barrier performance of the film sheet itself is reduced. As a result, there arises a problem that the reliability of the display element itself is greatly reduced, such as generation of bubbles inside the liquid crystal display element and generation of a display defect and expansion of a display defect portion in the electroluminescence element.
[0010]
Furthermore, even when the arithmetic mean value (Ra) of the surface roughness is smaller than 10 nm, there is a convex shape having a maximum height (Ry) of 0.3 μm or more in the surface roughness, and the maximum height of the projections When the aspect ratio (maximum height / minimum width) of the minimum value of the height and the width is larger than 0.2, not only non-uniformity of the display element is caused, but also cracks and non-uniformity of the thickness of the laminated barrier film are caused. And the problem that the barrier performance of the film sheet itself is lowered occurs. As a result, the reliability of the display element itself was reduced, such as the occurrence of air bubbles inside the element and uneven display of the gap between the substrates in the liquid crystal display element, and the occurrence of non-lighting defects and the growth of non-lighting defects in electroluminescent elements. A problem that greatly reduces the performance occurs. The maximum height in the aspect ratio (maximum height / minimum width) of the minimum value of the maximum height and the width, which expresses the shape of the projections on the surface of the ultraviolet-curable resin composition, is the height of the projections from the average line of the resin surface roughness. Indicates the maximum height. The minimum value of the width indicates the minimum distance of the surface shape corresponding to the bottom of the projection when the local projection is cut out two-dimensionally by the average line of the resin surface roughness. In other words, the steepest aspect ratio can be calculated when the surface shape of the projection on the average surface roughness line is flat.
[0011]
The thickness of the ultraviolet curable resin composition is preferably in the range of 0.3 to 6 μm. The thickness of the ultraviolet curable resin composition depends on the smoothness of the base film sheet to be used, particularly the maximum height (Ry). When the thickness is 0.3 μm or less, the effect of flattening the unevenness of the base film is poor. Further, when the thickness is 6 μm or more, there may be a problem that the uniformity of the thickness is reduced, and a problem that, depending on the ultraviolet-curable resin composition, it is impossible to follow the flexibility of the base film sheet and causes destructive deterioration. There is.
[0012]
As a method for producing an optical film sheet on which the ultraviolet curable resin composition having the above-mentioned smoothness is laminated, a kiss coat method, a bar coat method, a gravure coat method, a microgravure coat method, or the like is used. And a UV coating method, followed by a wet coating method of forming a film, and a transfer method of curing and forming a film while bringing a solid substrate such as polished glass into contact with the surface of the UV-curable resin composition. The wet coating method is preferable in consideration of productivity and the like, but the method for obtaining the optical film sheet of the present invention is not limited to a film forming method.
[0013]
In the wet coating method, it is preferable to improve the wettability between the base film and the ultraviolet-curable resin composition containing an acrylate monomer as a main component. It has been found that the above-mentioned smoothness can be obtained when the melting contact angle between the base film and the resin composition before UV curing of the UV-curable resin composition is smaller than 10 °. The melt contact angle in the present study is the contact angle between the base film and the pre-cured ultraviolet resin composition at the upper limit temperature of the ambient temperature at which the base film for laminating the ultraviolet-curable resin composition is exposed before the ultraviolet curing. .
[0014]
In addition, after dissolving the UV-curable resin composition containing an acrylate monomer as a main component used in this study in at least two or more solvents having different boiling points, it is applied on a base film, and after the solvent is sufficiently dried, UV-curing is performed. It is also preferable to make it. When the type of the solvent that dissolves the ultraviolet resin composition is a single composition, the concentration of the ultraviolet resin composition dope solvent solution on the base film rapidly changes during drying of the solvent, and irregularities on the surface of the ultraviolet resin composition occur. Becomes noticeable. Further, the composition ratio of the ultraviolet curable resin composition and the solvent is preferably from 20:80 to 60:40. When the composition ratio is solvent-rich, not only the appearance after coating is deteriorated, but also the relative amount of the volatile solvent increases, so that the surface unevenness after ultraviolet curing is hardly improved, and the composition ratio is high in the resin composition rich. In such a case, although local surface irregularities are improved, long-period surface waviness may occur, and appearance defects are likely to occur.
[0015]
The atmosphere temperature at which the solvent to be used is dried is preferably step drying in which the solvent is dried through two or more different temperature atmospheres, and furthermore, the solvent to be used is two or more, and the lowest value of the drying temperature is the solvent having the lowest boiling point. It is more preferable to dry the resin to a residual solvent amount of 1 wt% or less before curing under a temperature condition lower than the boiling point of the solvent and having the highest drying temperature lower than the boiling point of the solvent having the highest boiling point. If the difference in boiling point between the solvents is smaller than the difference in the temperature and atmosphere used for step drying, the rapid temperature difference during drying increases the evaporation rate of the solvent, and the surface smoothness of the resin composition may decrease. There is.
[0016]
The acrylate monomer of the present invention is not particularly limited, but is bifunctional or more among epoxy acrylate, urethane acrylate, isocyanuric acid EO-modified acrylate, pentaerythritol acrylate, trimethylolpropane acrylate, ethylene glycol acrylate, polyester acrylate, norbornene acrylate, and the like. It is preferable to use a monomer having an acryloyl group as a main component. A method in which two or more of these monomers having a bifunctional or higher acryloyl group are mixed and used, and a method in which a monofunctional acrylate is mixed and used, are more preferable in that curing shrinkage is suppressed to a small value. In addition, it is preferable that the isocyanuric acid EO-modified triacrylate having a high degree of cross-linking and a glass transition temperature of 200 ° C. or more is a main component, and furthermore, a barrier is provided on the surface of the ultraviolet-curable resin composition comprising an acrylate monomer. When laminating an inorganic film such as a film, it is preferable to include epoxy acrylate because of excellent interlayer adhesion between the ultraviolet-curable resin composition and the inorganic film, and among them, bisphenol A type epoxy diacrylate and 4-brominated bisphenol are particularly preferable. A type diepoxy diacrylate and novolak type epoxy acrylate are more preferable. These acrylate monomers may be used alone or in combination of two or more.
In addition, a silicon-based or fluorine-based leveling material, a silicon-based, titanate-based, mercapto-based silane coupling material, or the like may be added to the ultraviolet-curable resin composition of the present invention.
[0017]
The optical film sheet of the present invention may be laminated with a barrier film, and there is no particular limitation on the barrier film, but the barrier film preferably has a water vapor barrier property and / or an oxygen barrier property. Further, the material is not particularly limited, but a barrier film mainly composed of an inorganic substance having low temperature-humidity dependence in barrier characteristics is preferable. For example, oxides, nitrides, oxynitrides, or halogen compounds containing at least one of Si, Al, In, Sn, Zn, Ti, Cu, Ce, Mg, La, Cr, Ca, Zr, and Ta are used. be able to. If the inorganic layer is too thick, there is a risk of cracking due to bending stress, and if it is too thin, the film is distributed in an island shape, and in any case, the gas barrier properties deteriorate. From the above, the thickness of each inorganic layer is preferably in the range of 5 nm to 500 nm, but is not particularly limited. Further, the respective inorganic layers may have the same composition or different compositions, and there is no limitation. To achieve both gas barrier properties and high transparency, it is preferable to use silicon oxide or silicon oxynitride as the inorganic layer. In addition, as a method for forming an inorganic film, a resistance heating evaporation method, an electron beam evaporation method, an ion plating method, a CVD method, a sputtering method, a normal pressure CVD method, or the like can be applied, and a target inorganic oxide, inorganic nitride, There is no particular limitation as long as an inorganic nitride oxide or an inorganic halogen compound can be obtained.
[0018]
Further, as the barrier film mainly composed of an inorganic material, a structure in which many different types of inorganic oxides, inorganic nitrides, or inorganic oxynitrides are laminated, or a layer configuration in which inorganic layers / organic layers / inorganic layers are alternately laminated. There is a barrier film. Considering the reliability of the barrier, a multilayer barrier film described above is preferable to a single-layer inorganic barrier film, and a barrier film in which an inorganic layer / organic layer / inorganic layer is alternately laminated is more preferable. As the organic layer of the multilayer film, an ultraviolet-curable resin composition mainly containing an acrylate monomer used in the present invention is preferable, but not particularly limited.
[0019]
The base film used for the optical film and sheet of the present invention needs to be able to withstand the environmental temperature of the display element, and its glass transition temperature is desirably 160 ° C. or higher. Examples include imide-modified high polymers such as polyester, polycarbonate, polynorbornene, polyetherimide, polyarylate, polyethersulfone, polyetherketone, polyphenylene sulfide, syndiotactic polystyrene, cyclopolyolefin and copolymers thereof, and imide-modified polymethyl methacrylate. Examples thereof include a film sheet made of molecules and the like, but are not particularly limited. Prior to the formation of each layer, the base film of the present invention is subjected to a surface treatment such as a degassing treatment, a corona discharge treatment, a flame treatment UV ozone treatment, and an excimer UV treatment in order to increase the adhesion to each layer to be laminated. May be. The base film can be formed into a sheet by a method such as extrusion molding and casting, and the optical film and sheet of the present invention are formed on the formed base film by casting, coating or various printing methods, laminating method, etc. It has a structure in which a curable resin composition is laminated.
[0020]
Regarding the ultraviolet irradiation for curing the ultraviolet curable resin composition of the present invention, light having a necessary wavelength may be selectively irradiated. Specific examples include a method of providing a selective transmission filter in the irradiating portion, and a method of irradiating from the surface opposite to the side on which the coating film of the film is formed. When the curing reaction of the ultraviolet-ray effect resin is inhibited by oxygen in the atmosphere, the irradiation may be performed in an atmosphere of an inert gas such as nitrogen. When selectively irradiating a wavelength of 365 nm or 254 nm, or a certain wavelength, the amount of ultraviolet irradiation may be measured by an ultraviolet illuminometer in an ultraviolet region where the irradiation amount is the maximum in the ultraviolet region.
[0021]
【Example】
Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to the examples.
[0022]
The surface smoothness of each film was evaluated by visual observation and an ultra-depth laser microscope or an atomic force microscope (AFM). The ultra-depth laser microscope measured an area of 1 mm × 1.4 mm, and the AFM measured an area of 20 μm × 20 μm square.
[0023]
As for the barrier property, the water vapor barrier property was evaluated by JIS-K7129-B method using Permetran manufactured by Mocon.
The adhesion between the barrier film and the ultraviolet-curable resin composition was evaluated by performing a cross-cut peel test on the barrier film after the evaluation of the processability of the transparent electrode pattern and the water vapor barrier property.
[0024]
<Example 1>
Polyethersulfone (PES) having a thickness of 200 μm and a maximum height (Ry) of 1.0 μm was used as a base film. 30 parts by weight of isocyanuric acid EO-modified triacrylate (M-315, manufactured by Toagosei Co., Ltd.), 4.5 parts by weight of epoxy acrylate (VR-60LAV, manufactured by Showa Polymer Co., Ltd.), urethane acrylate (Dainippon Ink) Unitic 17-806, 3 parts by weight, photoinitiator (IGR-907, Chika Ikey Co., Ltd.) 1.5 parts by weight, 12 parts by weight of lucerosol acetate (boiling point = 145 ° C.), butyl acetate (boiling point = 126) Stirring and dissolving with 40 parts by weight and 7.0 parts by weight of butyl cellosolve (boiling point = 170 ° C.) into a uniform solution having an RC = 36 wt% was applied with a bar coater coater, and the solution was heated and dried in a drier. The solvent was removed by heating at 120 ° C for 2 minutes followed by heating at 120 ° C for 3 minutes. After the solvent was removed, the ultraviolet-curable resin composition was in a paste-like softened state, and the melt contact angle at 120 ° C. between PES and the resin composition before curing was 2.2 °. The dried resin composition is applied with a high-pressure mercury lamp at 350 mJ / cm. Two Was irradiated to produce a cured resin composition on the film.
[0025]
The surface smoothness of the produced ultraviolet curable resin composition laminated film was evaluated by AFM. The produced substrate was a film having a Ra = 0.4 nm, Ry = 0.1 μm, a hole having a depth of 10 nm or more, and a very smooth film having a good visual appearance and a good visual appearance.
[0026]
<Example 2>
Polyethersulfone (PES) having a thickness of 200 μm and a maximum height (Ry) of 1.0 μm was used as a base film. 40 parts by weight of isocyanuric acid EO-modified triacrylate (M-315, manufactured by Toagosei Co., Ltd.), 2.5 parts by weight of a photoinitiator (IRG-907, manufactured by Chiyaka Ikki Co., Ltd.) as a UV-curable resin composition, 2.5 parts by weight of lucellosol acetate (boiling point) 8.5 parts by weight), 30 parts by weight of ethyl lactate (boiling point = 155 ° C.), and 6.0 parts by weight of butyl cellosolve (boiling point = 170 ° C.). The solution was applied with a bar coater coater, and heated at 90 ° C. for 5 minutes and then at 120 ° C. for 2 minutes in a heat dryer to remove the solvent. After the solvent was removed, the ultraviolet-curable resin composition was in a paste-like softened state, and the melt contact angle at 120 ° C. between PES and the resin composition before curing was 1.0 °. The dried resin composition is applied with a high-pressure mercury lamp at 350 mJ / cm. Two Was irradiated to produce a cured resin composition on the film.
[0027]
The surface smoothness of the produced ultraviolet curable resin composition laminated film was evaluated by AFM. The produced substrate was a film having a Ra of 0.3 nm, a Ry of 0.03 μm, a hole having a depth of 10 nm or more, and having a good visual appearance and a very high smoothness.
[0028]
<Example 3>
Polyethersulfone (PES) having a thickness of 200 μm and a maximum height (Ry) of 1.0 μm was used as a base film. 20 parts by weight of epoxy acrylate (VR-60LAV manufactured by Showa Polymer Co., Ltd.), 14 parts by weight of urethane acrylate (Unitic 17-806 manufactured by Dainippon Ink Co., Ltd.), and a photoinitiator (IRG- manufactured by Chihwa Ikki Co., Ltd.) 907) 1.2 parts by weight, 15 parts by weight of lucerosol acetate (boiling point = 145 ° C.), 40 parts by weight of butyl acetate (boiling point = 126 ° C.), and 6.0 parts by weight of butyl cellosolve (boiling point = 170 ° C.) Then, a solution having a uniform concentration of RC = 26.4 wt% was dissolved and applied with a bar coater coater, followed by heating at 90 ° C. for 2 minutes and then at 120 ° C. for 3 minutes in a heat dryer to remove the solvent. After the solvent was removed, the ultraviolet-curable resin composition was in a paste-like softened state, and the melt contact angle at 120 ° C. between PES and the resin composition before curing was 18 °. While contact-transferring a silicon wafer of Ra = 0.3 nm and Ry = 5 nm onto the surface of the dried resin composition, 450 mJ / cm was passed through an optical film sheet using a high-pressure mercury lamp. Two Was irradiated and cured. An optical film sheet with an ultraviolet-curable resin composition was prepared by removing the silicon wafer from the resin surface after ultraviolet-curing.
[0029]
The surface smoothness of the produced ultraviolet curable resin composition laminated film was evaluated by AFM. The produced substrate was a film having a Ra of 0.4 nm, a Ry of 0.01 μm, and a hole having a depth of 10 nm or more and having a good visual appearance and a very high smoothness.
[0030]
<Example 4>
Polyethersulfone (PES) having a thickness of 200 μm and a maximum height (Ry) of 1.0 μm was used as a base film. 30 parts by weight of isocyanuric acid EO-modified triacrylate (M-315, manufactured by Toagosei Co., Ltd.), 7.5 parts by weight of epoxy acrylate (M-211B, manufactured by Toagosei Co., Ltd.), and a photoinitiator (manufactured by Chiyaka Ikki Co., Ltd.) IRG-907) 1.1 parts by weight, 10.8 parts by weight of `lucerosol acetate, 36 parts by weight of butyl acetate, and 6.3 parts by weight of butyl cellosolve, stirred and dissolved to form a uniform solution of RC = 42 wt%. The resultant was applied with a bar coater coater, and heated at 90 ° C. for 2 minutes and then at 120 ° C. for 3 minutes in a heating dryer to remove the solvent. After the solvent was removed, the ultraviolet curable resin composition was in a viscous liquid state. The dried resin composition is applied with a high-pressure mercury lamp at 350 mJ / cm. Two Was irradiated to produce a cured resin composition having a thickness of 4 μm on the film.
[0031]
The surface smoothness of the produced ultraviolet curable resin composition laminated film was evaluated by AFM. The prepared substrate had no hole defects of Ra = 0.5 nm, Ry = 0.2 μm, and a depth of 10 nm or more, and the aspect ratio of the minimum value of the maximum height and width of the local projection shape in the area of 20 μm × 20 μm square ( The maximum value of (maximum height / minimum width) was 0.15, and the film was very smooth with good visual appearance.
[0032]
<Example 5>
Polyethersulfone (PES) having a thickness of 200 μm and a maximum height (Ry) of 1.0 μm was used as a base film. 30 parts by weight of isocyanuric acid EO-modified triacrylate (M-315 manufactured by Toagosei Co., Ltd.), 10 parts by weight of norborenene diacrylate (KAYARAD R-684 manufactured by Nippon Kayaku Co., Ltd.), and a photoinitiator (Chihka Iki Co.) 2.0 parts by weight of IRG-907), 9.0 parts by weight of `lucerosol acetate, 30 parts by weight of butyl acetate, and 6.0 parts by weight of butyl cellosolve, stirred and dissolved to obtain a uniform RC = 48.3 wt%. The resulting solution was applied with a bar coater coater, and heated at 90 ° C. for 2 minutes and then at 120 ° C. for 3 minutes in a heat dryer to remove the solvent. After the solvent was removed, the ultraviolet curable resin composition was in a viscous liquid state. The dried resin composition is applied with a high-pressure mercury lamp at 350 mJ / cm. Two Was irradiated to produce a cured resin composition having a thickness of 4 μm on the film.
[0033]
The surface smoothness of the produced ultraviolet curable resin composition laminated film was evaluated by AFM. The prepared substrate had no hole defects of Ra = 0.3 nm, Ry = 0.03 μm, depth of 10 nm or more, and the aspect ratio of the maximum height and the minimum value of the local protrusion shape in the region of 20 μm × 20 μm square ( The maximum value of (maximum height / minimum width) was 0.08, and the film was very smooth with good visual appearance.
[0034]
<Example 6>
Polyethersulfone (PES) having a thickness of 200 μm and a maximum height (Ry) of 1.0 μm was used as a base film. 30 parts by weight of isocyanuric acid EO-modified triacrylate (M-315, manufactured by Toagosei Co., Ltd.), 10 parts by weight of a bisphenol A type epoxy acrylate (VR-77, manufactured by Showa Polymer Co., Ltd.), and a photoinitiator (Tihaka Iki Co., Ltd.) 2.0 parts by weight of IRG-907), 9.0 parts by weight of `lucerosol acetate, 30 parts by weight of butyl acetate, and 6.0 parts by weight of butyl cellosolve, stirred and dissolved to obtain a uniform RC = 48.3 wt%. The resulting solution was applied with a bar coater coater, and heated at 90 ° C. for 2 minutes and then at 120 ° C. for 3 minutes in a heat dryer to remove the solvent. After the solvent was removed, the ultraviolet curable resin composition was in a viscous liquid state. The dried resin composition is applied with a high-pressure mercury lamp at 350 mJ / cm. Two Was irradiated to produce a cured resin composition having a thickness of 4 μm on the film.
[0035]
The surface smoothness of the produced ultraviolet curable resin composition laminated film was evaluated by AFM. The fabricated substrate had no hole defects with Ra = 0.4 nm, Ry = 0.06 μm, and a depth of 10 nm or more, and the aspect ratio of the maximum height and the minimum value of the local projection shape in the region of 20 μm × 20 μm square ( The maximum value of (maximum height / minimum width) was 0.09, and the film was very smooth with good visual appearance.
[0036]
<Comparison 1>
Polyether sulfone (VICTREXPES-4100P Tg: 223 ° C, manufactured by Sumitomo Chemical Co., Ltd.) is melt-kneaded in a 50 mmφ extruder at a cylinder temperature of 350 ° C, formed into a sheet by a T-die, and has a peripheral speed of 1.90 m / min. Using a hard chrome plating cooling roll maintained at 250 ° C. and having an outer diameter of 300 mmφ, a 200 μm-wide 680 mm wide film was manufactured.
[0037]
The surface smoothness of the produced optical film sheet was evaluated by AFM. Although the prepared substrate did not have a hole defect of Ra = 0.4 nm and a depth of 10 nm or more, it was Ry = 1.6 μm as evaluated by an ultra-depth laser microscope, and had a local protrusion shape in a 1 mm × 1.4 mm area. The maximum value of the aspect ratio (maximum height / minimum width) of the minimum value of the maximum height and the width was 0.53, and a partially convex shape was also confirmed in the visual appearance evaluation.
[0038]
<Comparative Example 2>
Polyethersulfone (PES) having a thickness of 200 μm and a maximum height (Ry) of 1.0 μm was used as a base film. 20 parts by weight of epoxy acrylate (VR-60LAV manufactured by Showa Polymer Co., Ltd.), 14 parts by weight of urethane acrylate (Unitic 17-806 manufactured by Dai Nippon Ink Co., Ltd.), and a photoinitiator (IRG- manufactured by Chihwa Ikki Co., Ltd.) 907) 1.2 parts by weight, 15 parts by weight of lucerosol acetate (boiling point = 145 ° C.), 40 parts by weight of butyl acetate (boiling point = 126 ° C.), and 6.0 parts by weight of butyl cellosolve (boiling point = 170 ° C.) The resulting solution was dissolved into a uniform solution having an RC of 26.4 wt%, and the solution was applied using a bar coater coater, followed by heating at 90 ° C. for 2 minutes and then at 120 ° C. for 3 minutes in a heat dryer to remove the solvent. After the solvent was removed, the ultraviolet-curable resin composition was in a paste-like softened state, and the melt contact angle at 120 ° C. between PES and the resin composition before curing was 18 °. The dried resin composition is applied with a high-pressure mercury lamp at 350 mJ / cm. Two Was irradiated to produce a cured resin composition on the film.
[0039]
The surface smoothness of the produced ultraviolet curable resin composition laminated film was evaluated by AFM. In the prepared substrate, Ra = 0.8 nm, Ry = 0.5 μm, and a hole defect having a depth of 10 nm or more were confirmed at 5 points in 20 μm square.
[0040]
<Example 7>
An initial degree of vacuum of 3 × 10 was formed on the substrate prepared in Example 2 by a pulse DC magnetron method. -4 From the state of Pa, a mixed gas of 9% of oxygen / argon gas was introduced and 3 × 10 -1 Sputtering was performed with a silicon target under the condition of Pa to obtain a barrier SiOx film having a thickness of 1000 mm. The water vapor transmission rate of the obtained optical film sheet with a barrier film is below the measurement limit (<0.1 g / m Two / day), and the barrier properties were good.
[0041]
Subsequently on the barrier film, a transparent conductive film was formed at an initial vacuum of 3 × 10 3 by a pulse DC magnetron method. -4 From the state of Pa, a mixed gas of oxygen / argon gas 4% was introduced to obtain 1 × 10 -1 Sputtering was performed with an ITO target under the condition of Pa to obtain a transparent conductive film made of indium tin oxide (ITO) having an atomic ratio of In / In + Sn of 0.98. As a result of the measurement, the film thickness was 1000 ° and the specific resistance was 4 × 10 -Four Ω-cm.
[0042]
Using the obtained transparent electrode / barrier film / ultraviolet curable resin composition layer / PES substrate, an organic EL device was produced. On the ITO anode, TPD was deposited in a thickness of 40 nm as a hole transport layer, and then Alq3 was deposited in a thickness of 70 nm as an electron transport layer and a light emitting layer. Produced. The cathode side was sealed with a glass substrate using an adhesive using a UV-curable resin composition as a sealing material.
[0043]
As a result of evaluating a device in which the produced organic EL device was stored at room temperature (23 ° C., 45% RH) for 2 weeks, no device deterioration was observed in a light emitting portion, and good device characteristics equivalent to initial light emitting characteristics were exhibited.
[0044]
Example 8
An initial degree of vacuum of 3 × 10 was formed on the substrate prepared in Example 5 by a pulse DC magnetron method. -4 From the state of Pa, a mixed gas of 9% of oxygen / argon gas was introduced and 3 × 10 -1 Sputtering was performed with a silicon target under the condition of Pa to obtain a barrier SiOx film having a thickness of 1000 mm. The water vapor transmission rate of the obtained optical film sheet with a barrier film is below the measurement limit (<0.1 g / m Two / day), and the barrier properties were good.
[0045]
Subsequently on the barrier film, a transparent conductive film was formed at an initial vacuum of 3 × 10 3 by a pulse DC magnetron method. -4 From the state of Pa, a mixed gas of oxygen / argon gas 4% was introduced to obtain 1 × 10 -1 Sputtering was performed with an ITO target under the condition of Pa to obtain a transparent conductive film made of indium tin oxide (ITO) having an atomic ratio of In / In + Sn of 0.98. As a result of the measurement, the film thickness was 1000 ° and the specific resistance was 4 × 10 -Four Ω-cm.
[0046]
Using the obtained transparent electrode / barrier film / ultraviolet curable resin composition layer / PES substrate, an organic EL device was produced. On the ITO anode, TPD was deposited to a thickness of 40 nm as a hole transporting layer, then Alq3 was deposited to a thickness of 70 nm as an electron transporting layer and a light emitting layer, and a 200 nm thick Ag / Mg (10: 1) cathode was co-deposited as a cathode. An EL device was manufactured. The cathode side was sealed with a glass substrate using a sealing material of an ultraviolet curable resin composition as an adhesive.
[0047]
As a result of evaluating a device in which the produced organic EL device was stored at room temperature (23 ° C., 45% RH) for 2 weeks, no device deterioration was observed in a light emitting portion, and good device characteristics equivalent to initial light emitting characteristics were exhibited.
[0048]
<Example 9>
An initial degree of vacuum of 3 × 10 was formed on the substrate prepared in Example 6 by a pulse DC magnetron method. -4 From the state of Pa, a mixed gas of 9% of oxygen / argon gas was introduced and 3 × 10 -1 Sputtering was performed with a silicon target under the condition of Pa to obtain a barrier SiOx film having a thickness of 1000 mm. The water vapor transmission rate of the obtained optical film sheet with a barrier film is below the measurement limit (<0.1 g / m Two / day), and the barrier properties were good. After the barrier property evaluation (40 ° C., 90% for 24 hours), the SiOx film surface was cut in a grid, and the adhesion was evaluated. As a result, no peeling of the grid and chipping of the cut edge were observed, and the moisture-resistant interlayer adhesion was not observed. The properties were good.
[0049]
Subsequently on the barrier film, a transparent conductive film was formed at an initial vacuum of 3 × 10 3 by a pulse DC magnetron method. -4 From the state of Pa, a mixed gas of oxygen / argon gas 4% was introduced to obtain 1 × 10 -1 Sputtering was performed with an ITO target under the condition of Pa to obtain a transparent conductive film made of indium tin oxide (ITO) having an atomic ratio of In / In + Sn of 0.98. As a result of the measurement, the film thickness was 1000 ° and the specific resistance was 4 × 10 -Four Ω-cm.
[0050]
Using the obtained transparent electrode / barrier film / ultraviolet curable resin composition layer / PES substrate, ITO was patterned to have an electrode width of 100 μm / interelectrode 50 μm in order to produce an organic EL device. For ITO patterning, a photoresist (PMER P-LA900PM, manufactured by Tokyo Ohkasha Co., Ltd.) was applied to ITO, and the pattern was exposed. Next, it was immersed in a TMAH aqueous solution for 60 minutes to remove unnecessary photosensitizer, and ITO was removed by etching (aqueous ferric chloride solution). The substrate after patterning did not show cracks in the barrier film or defects in delamination, and had good chemical resistance and interlayer adhesion. After patterning, TPD was deposited to a thickness of 40 nm as a hole transport layer on the ITO anode, Alq3 was deposited to a thickness of 70 nm as an electron transport layer and a light emitting layer, and then Ag / Mg (10: 1) was used as a cathode and a metal mask was used. An organic EL device was prepared by co-evaporation with a 100 μm electrode width and 200 nm thickness. The cathode side was sealed with a glass substrate using a sealing material of an ultraviolet curable resin composition as an adhesive.
[0051]
As a result of evaluating a device in which the produced organic EL device was stored at room temperature (23 ° C., 45% RH) for 2 weeks, no device deterioration was observed in a light emitting portion, and good device characteristics equivalent to initial light emitting characteristics were exhibited.
[0052]
<Comparative Example 3>
After forming a barrier film on the optical film sheet prepared in Comparative Example 1 by the same method as in Example 7, a transparent electrode, a hole transport layer, an electron transport layer, and a cathode were sequentially formed to form an organic layer. An EL device was manufactured. The water vapor transmission rate of the used optical film sheet with a barrier film was 1.3 g / m2 / day, confirming a tendency that water vapor transmission was high.
[0053]
As a result of evaluating a device in which the produced organic EL device was stored at room temperature (23 ° C., 45% RH) for 2 weeks, a non-light-emitting portion was confirmed from the initial stage of fabrication. No light emitting portion could be observed.
[0054]
<Comparative Example 4>
After forming a barrier film on the optical film sheet prepared in Comparative Example 2 in the same manner as in Example 4, a transparent electrode, a hole transport layer, an electron transport layer, and a cathode were sequentially formed to form an organic film. An EL device was manufactured. The water vapor transmission rate of the optical film sheet with a barrier film used is 0.2 g / m. Two / day, confirming the tendency of high water vapor transmission.
[0055]
As a result of evaluating a device in which the produced organic EL device was stored at room temperature (23 ° C., 45% RH) for 2 weeks, no non-light-emitting portion was confirmed in the initial stage of the production. Was confirmed.
[0056]
<Comparative Example 5>
A barrier film was formed on the optical film sheet prepared in Comparative Example 1 by the same method as in Example 9. Water vapor transmission rate of optical film sheet with barrier film is 1.3 g / m Two / day, which indicates that there is a tendency for a large amount of water vapor to permeate. Further, in a grid-cut peeling test after barrier property evaluation (40 ° C., 90%, 24 hours), there is peeling at the interface between the substrate and the inorganic film, and interlayer adhesion is also high It was confirmed that it was scarce.
[0057]
After forming the barrier film, a transparent conductive film was formed, and ITO was patterned using the transparent electrode / barrier film / PES substrate to manufacture an organic EL element. For patterning, a photoresist (PMER P-LA900PM, manufactured by Tokyo Ohkasha) was applied to ITO, and the pattern was exposed. Next, the unnecessary photosensitizer was removed by immersion in a TMAH aqueous solution for 60 minutes. However, delamination occurred between the PES substrate and the barrier film, and it was confirmed that interlayer adhesion was poor.
[0058]
【The invention's effect】
ADVANTAGE OF THE INVENTION According to this invention, the optical film sheet excellent in smoothness can be manufactured, and the plasticization of the EL display element which had been difficult to apply a plastic substrate conventionally becomes possible. Furthermore, the present invention can be applied to a roll-to-roll production system, and can provide an optical film sheet with high productivity, which is extremely useful in industry.
Claims (20)
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| JP2002338408A JP4145636B2 (en) | 2002-04-12 | 2002-11-21 | Optical film sheet and display element using the same |
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| JP2006015592A (en) * | 2004-07-01 | 2006-01-19 | Konica Minolta Opto Inc | Hard coat film, its production method, and reflection preventing film using it |
| JP2006083225A (en) * | 2004-09-14 | 2006-03-30 | Fuji Photo Film Co Ltd | Functional film |
| WO2007111098A1 (en) | 2006-03-24 | 2007-10-04 | Konica Minolta Medical & Graphic, Inc. | Transparent barrier sheet and method for producing same |
| JP2009012310A (en) * | 2007-07-05 | 2009-01-22 | Toppan Printing Co Ltd | Gas barrier film |
| EP2138533A1 (en) * | 2008-06-26 | 2009-12-30 | Fujifilm Corporation | Barrier laminate, gas barrier film and device using the same |
| EP2141190A1 (en) * | 2008-06-30 | 2010-01-06 | Fujifilm Corporation | Barrier laminate, gas barrier film, device and method for producing barrier laminate |
| JP2010201888A (en) * | 2009-03-06 | 2010-09-16 | Toppan Printing Co Ltd | Gas-barrier laminated film |
| JP2016100297A (en) * | 2014-11-26 | 2016-05-30 | 凸版印刷株式会社 | Transparent substrate for el element, organic el illumination, organic el light source, and organic el display device |
| JP2017107855A (en) * | 2011-04-08 | 2017-06-15 | サン−ゴバン パフォーマンス プラスティックス コーポレイション | Multilayer component for sealing element easily influenced |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006015592A (en) * | 2004-07-01 | 2006-01-19 | Konica Minolta Opto Inc | Hard coat film, its production method, and reflection preventing film using it |
| JP4649892B2 (en) * | 2004-07-01 | 2011-03-16 | コニカミノルタオプト株式会社 | Method for producing hard coat film |
| JP2006083225A (en) * | 2004-09-14 | 2006-03-30 | Fuji Photo Film Co Ltd | Functional film |
| WO2007111098A1 (en) | 2006-03-24 | 2007-10-04 | Konica Minolta Medical & Graphic, Inc. | Transparent barrier sheet and method for producing same |
| JP2009012310A (en) * | 2007-07-05 | 2009-01-22 | Toppan Printing Co Ltd | Gas barrier film |
| EP2138533A1 (en) * | 2008-06-26 | 2009-12-30 | Fujifilm Corporation | Barrier laminate, gas barrier film and device using the same |
| US8637147B2 (en) | 2008-06-26 | 2014-01-28 | Fujifilm Corporation | Barrier laminate, gas barrier film and device using the same |
| EP2141190A1 (en) * | 2008-06-30 | 2010-01-06 | Fujifilm Corporation | Barrier laminate, gas barrier film, device and method for producing barrier laminate |
| JP2010201888A (en) * | 2009-03-06 | 2010-09-16 | Toppan Printing Co Ltd | Gas-barrier laminated film |
| JP2017107855A (en) * | 2011-04-08 | 2017-06-15 | サン−ゴバン パフォーマンス プラスティックス コーポレイション | Multilayer component for sealing element easily influenced |
| US10036832B2 (en) | 2011-04-08 | 2018-07-31 | Saint-Gobain Performance Plastics Corporation | Multilayer component for the encapsulation of a sensitive element |
| JP2016100297A (en) * | 2014-11-26 | 2016-05-30 | 凸版印刷株式会社 | Transparent substrate for el element, organic el illumination, organic el light source, and organic el display device |
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