JP2004130709A - Transparent sheet - Google Patents
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- JP2004130709A JP2004130709A JP2002298658A JP2002298658A JP2004130709A JP 2004130709 A JP2004130709 A JP 2004130709A JP 2002298658 A JP2002298658 A JP 2002298658A JP 2002298658 A JP2002298658 A JP 2002298658A JP 2004130709 A JP2004130709 A JP 2004130709A
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Abstract
Description
【０００１】
【発明の属する技術分野】
本発明は、液晶表示素子用基板、有機ＥＬ表示素子用基板、太陽電池基板等に好適に利用できる透明なシートに関する。
【０００２】
【従来の技術】
一般に、液晶表示素子用基板、有機ＥＬ表示素子用基板、太陽電池基板等には、ガラス板が多く用いられている。しかし、割れ易い、曲げられない、比重が大きく軽量化に不向き等の問題から、近年、ガラス板の代わりにプラスチックを用いる試みが数多く行われるようになってきた。例えば、脂環式構造、芳香族等を持つ特定のビス（メタ）アクリレートを含む組成物を活性エネルギー線等により硬化させ成形した透明基板を用いてなる液晶表示素子が検討されている。（例えば、特許文献１参照。）
しかしながら、プラスチックは、ガラス板に比べ線膨張係数が大きいため、表示素子用基板の中でも、特にアクティブマトリックス表示素子用基板に用いた場合、その製造時の加熱工程おいて、金属やシリコン及びそれらの酸化物などの無機薄膜にクラックが発生したり、剥離する等の不具合が生じる場合があり問題となっている。したがって、軽く、曲げることができ、軽いと同時に線膨張係数の小さいシートが望まれている。
【０００３】
一方、ガラス基板を出来る限り薄くすることで、軽く、曲げることができるようにすることも検討されている。このような場合、割れやすさを回避するために樹脂を塗布することなどが提案されている。（例えば、非特許文献１参照。）しかし、ガラス基板を薄くすることは５０μｍ程度が下限であり、プラスチックほどの軽量化は困難であるとともに、このような薄いガラスは、より厚いガラスを研磨やエッチングすることで得るために高コストになってしまう。
従来、ガスバリア層として樹脂フィルムに透明無機薄膜を成膜することが行われている。（例えば、特許文献２，３参照。）しかし、これらは線膨張係数を下げる目的で発明されたものではなく、片面に樹脂層が無い場合にも割れない厚さである０．０１〜０．１μｍという薄い厚さで用いられるため線膨張係数を下げるには有効ではない。また、線膨張係数が低い樹脂フィルムとしては、ポリイミドやポリエチレンナフタレート（ＰＥＮ）が知られているが、前者は一般に可視光でも短波長域に吸収を持ち黄色〜褐色であり光学用途には好ましくなく、後者は大きな位相差を持つために光学等方性が必要な用途には好ましくない。
【０００４】
【特許文献１】
特開平１０−９０６６７号公報（第２−３頁）
【非特許文献１】
Ａ．Ｗｅｂｅｒ， Ｔｈｉｎ Ｇｌａｓｓ−Ｐｏｌｙｍｅｒ Ｓｙｓｔｅｍ ａｓ Ｆｌｅｘｉｂｌｅ Ｓｕｂｓｔｒａｔｅ ｆｏｒ Ｄｉｓｐｌａｙｓ， ＳＩＤ ＩＮＴＥＲＮＡＴＩＯＮＡＬ ＳＹＭＰＯＳＩＵＭ ＤＩＧＥＳＴ ＯＦＴＥＣＨＮＩＣＡＬ ＰＡＰＥＲＳ ２００２ Ｖｏｌ．ＸＸＸＩＩＩ， Ｎｏ．１ Ｐ．５３−５５
【特許文献２】
特開平９−３９１５１号公報（第１−３頁）
【特許文献３】
特開平１０−３２９２５４号公報（第２−３頁）
【０００５】
【発明が解決しようとする課題】
本発明は、線膨張係数が低く、液晶表示素子用基板、有機ＥＬ表示素子用基板、太陽電池基板等に好適に利用できる透明シートを提供することを目的とするものである。
【０００６】
【課題を解決するための手段】
本発明者らは、上記課題を達成すべく鋭意検討した結果、少なくとも厚さ０．６μｍ以上１０μｍ以下の透明無機層及びそれを挟む透明樹脂層を有するシートが液晶表示素子用基板や有機ＥＬ表示素子用基板、特にアクティブマトリックス表示素子用基板に好適に用いられることを見出し、本発明に至った。
すなわち本発明は、
（１） 少なくとも厚さ０．６μｍ以上５０μｍ未満の透明無機層及びこれを挟む透明樹脂層１並びに透明樹脂層２を有し、３０℃から１００℃における面内方向の線膨張係数が４０ｐｐｍ／℃以下であり、位相差が１０ｎｍ以下であり、波長４００ｎｍにおける光線透過率が８０％以上である透明シート。
（２） 前記透明無機層が物理気相成長法および／または化学気相成長法により成膜される（１）の透明シート、
（３） 前記物理気相成長法が真空蒸着法またはイオンプレーティング法である（２）の透明シート、
（４） 前記化学気相成長法が大気圧下で行なわれる（２）の透明シート、
（５） 前記透明樹脂層１上に透明無機層および透明樹脂層２をロールツーロール方式で積層した（１）〜（４）の透明シート、
である。
【０００７】
【発明の実施の形態】
以下、本発明を詳細に説明する。
本発明中の透明無機層の例としては、酸化珪素，酸化窒化珪素などの可視光の透過性を有する珪素化合物や、酸化アルミニウム，酸化鉛，酸化亜鉛，酸化チタン，酸化タンタルなどの可視光の透過性を有する金属酸化物などが挙げられる。これらは、単層で用いても２層以上を用いても良い。
透明無機層の成膜は、真空蒸着，イオンプレーティング，スパッタリングなどの物理気相成長法、真空中でのプラズマＣＶＤ，触媒ＣＶＤ，大気圧下でのＣＶＤなどの化学気相成長法、ゾル−ゲル法等の湿式塗布法により行うことができる。これらのうち、物理気相成長法，化学気相成長法は低温で緻密な膜を得られやすく好ましい。更に、物理気相成長法の中でも真空蒸着とイオンプレーティングは成膜速度が速く、０．２μｍ以上５０μｍ未満の膜を連続的に成膜する際に好ましい。また、化学気相成長法では、大気圧下でこれを行う方法が、真空工程を必要とせずタクトタイムを短くできる点から好ましい。
【０００８】
本発明中の透明樹脂層１および透明樹脂層２に用いる透明樹脂とは、可視光線の透過性を有する樹脂を示す。本発明の透明樹脂の透明性は、シートにした際の５５０ｎｍでの光線透過率が８０％以上のものが好ましく、より好ましくは８５％以上、最も好ましくは９０％以上である。表示素子用基板として用いる場合には、８５％以上が好ましい。
本発明の透明樹脂のガラス転移温度は、１２０℃以上であることが好ましく、より好ましくは１８０℃以上、さらに好ましくは２００℃以上である。ガラス転移温度が１２０℃未満の樹脂を用いた場合、例えば液晶表示素子基板に適用すると、配向膜形成や基板はり合わせなどの加熱工程で変形やうねりが生じる恐れがある。更に透明性や位相差が小さいことから、本発明中の透明樹脂層に用いる透明樹脂は非晶質であることが好ましい。位相差が１０ｎｍを超える場合、偏光を利用する表示素子の場合にコントラストの低下や色ムラが発生する場合があるため、透明シートの位相差は１０ｎｍ以下である必要がある。
【０００９】
本発明の透明樹脂の例としては、ポリカーボネート、ポリアリレート、ポリスルホン、ポリエーテルスルホン、シクロオレフィンポリマーなどの熱可塑性樹脂、エポキシ樹脂などの熱硬化性樹脂、アクリレートなどの反応性モノマーを活性エネルギー線で架橋させた樹脂などがあげられ、耐溶剤性に優れていることからアクリレートやエポキシ樹脂などの反応性モノマーを活性エネルギー線および／または熱によって架橋させた樹脂が好ましい。反応性モノマーとしては、熱や活性エネルギー線で架橋させることができるものであれば特に制限されないが、透明性や耐熱性の面から２つ以上の官能基を有する（メタ）アクリレートや２つ以上の官能基を有するエポキシ樹脂が好ましく、特に２つ以上の官能基を有する（メタ）アクリレートが好ましい。これら樹脂は、単独で用いても２種以上を併用しても良い。さらに各透明樹脂層は、２層以上の多層構成であってもかまわない。また、透明樹脂層１と透明樹脂層２とは、同一の樹脂構成であっても、異なるものでも良い。
【００１０】
本発明の透明樹脂層１は、架橋させうる樹脂の場合は注型法，流延法などで、熱可塑性樹脂の場合は溶融押出法や溶液流延法などで成膜することができる。紫外線等の活性エネルギー線により架橋させて製造する場合は、樹脂組成物中にラジカルを発生する光重合開始剤を含有させることが好ましい。その際に用いる光重合開始剤としては、例えばベンゾフェノン、ベンゾインメチルエーテル、ベンゾインプロピルエーテル、ジエトキシアセトフェノン、１−ヒドロキシ−シクロヘキシル−フェニルケトン、２，６−ジメチルベンゾイルジフェニルホスフィンオキシド、２，４，６−トリメチルベンゾイルジフェニルホスフィンオキシドが挙げられる。これらの光重合開始剤は２種以上を併用しても良い。
【００１１】
本発明で、透明樹脂層１上に、透明無機層および透明樹脂層２を順次積層する場合は、製造工程中で透明無機層に傷や割れが発生することを防ぐことから、ベースとなるロール状の透明シート原反等である透明樹脂層１上に、ロールツーロール方式で透明無機層を成膜した後、連続してその上層に、やはりロールツーロール方式で透明樹脂層２を成膜することが好ましい。この場合、透明樹脂層２の成膜方法としては、透明無機層を物理気相成長法などにより真空チャンバー中で成膜する場合には蒸着重合法が、ゾル−ゲル法や大気圧下での化学気相成長法により成膜する場合にはグラビアコートやダイコート等の湿式塗布法を用いることができる。
【００１２】
本発明の透明樹脂層中には、必要に応じて、透明性、耐熱性等の特性を損なわない範囲で、酸化防止剤、紫外線吸収剤、染顔料を含んでいても良い。
【００１３】
本発明の透明シートの線膨張係数は４０ｐｐｍ／℃以下であることが必要である。従来の透明シートで得られているような５０ｐｐｍ／℃を超える線膨張係数の場合、表示素子の製造時の加熱工程おいて、金属やシリコン及びそれらの酸化物などの無機薄膜にクラックが発生したり、剥離する等の不具合が生じる場合がある。
【００１４】
【実施例】
以下、本発明の内容を実施例により詳細に説明するが、本発明は、その要旨を越えない限り以下の例に限定されるものではない。
（実施例１）
溶融押出法により幅６００ｍｍ厚さ１０μｍのポリカーボネートフィルムのロール品を作成した。このフィルム上に、グラビアコーターとＵＶ照射装置を有するロールツーロール方式の塗工機を用いて、ノルボルナンジメチロールジアクリレート９０重量部と平均分子量５００であるエポキシアクリレート１０重量部の混合物に光重合開始剤として１−ヒドロキシ−シクロヘキシル−フェニル−ケトン０．５重量部を加えた樹脂組成物をグラビアコーターにより膜厚１μｍで塗布した後、５００ｍＪ／ｃｍ２のＵＶ光を照射して硬化させ、透明樹脂層１を作製した。シートを３００ｍｍ×４００ｍｍの大きさに切断して板状治具に固定した後、パルスＤＣ式多層スパッタリング装置によりＡｌターゲットを用いた反応性スパッタリグでＡｌ２Ｏ３を膜厚０．６μｍにスパッタし、透明無機層を成膜した。治具に固定したシートをスパッタリング装置から取り出し、枚葉式ダイコーターを用いてノルボルナンジメチロールジアクリレート９０重量部と平均分子量５００であるエポキシアクリレート１０重量部の混合物に光重合開始剤として１−ヒドロキシ−シクロヘキシル−フェニル−ケトン０．５重量部を加えた樹脂組成物を膜厚３μｍに塗布し、ＵＶ照射装置により５００ｍＪ／ｃｍ２のＵＶ光を照射して硬化させ、枚葉の透明シートを得た。
【００１５】
（実施例２）
溶融押出法により幅６００ｍｍ厚さ１０μｍのポリエーテルスルホンフィルムのロール品を作成した。このフィルム上に、グラビアコーターとＵＶ照射装置を有するロールツーロール方式の塗工機を用いて、ノルボルナンジメチロールジアクリレート９０重量部と平均分子量５００であるエポキシアクリレート１０重量部の混合物に光重合開始剤として１−ヒドロキシ−シクロヘキシル−フェニル−ケトン０．５重量部を加えた樹脂組成物をグラビアコーターにより膜厚１μｍで塗布した後、５００ｍＪ／ｃｍ２のＵＶ光を照射して硬化させ、透明樹脂層１を作製した。続いて、ロールツーロール方式の真空蒸着装置を用いてＳｉＯ２を膜厚１μｍに蒸着し、透明無機層を成膜した。真空成膜から取り出した後、再度ロールツーロール方式の塗工機を用いて、ノルボルナンジメチロールジアクリレート９０重量部と平均分子量５００であるエポキシアクリレート１０重量部の混合物に光重合開始剤として１−ヒドロキシ−シクロヘキシル−フェニル−ケトン０．５重量部を加えた樹脂組成物を膜厚３μｍで塗布し、５００ｍＪ／ｃｍ２のＵＶ光を照射して硬化させ、ロール状で透明シートを得た。
【００１６】
（実施例３）
溶融押出法により幅６００ｍｍ厚さ１０μｍのポリエーテルスルホンフィルムのロール品を作成した。このフィルム上に、グラビアコーターとＵＶ照射装置を有するロールツーロール方式の塗工機を用いて、ジシクロペンタジエニルジアクリレート９０重量部と平均分子量５００であるエポキシアクリレート１０重量部の混合物に光重合開始剤として１−ヒドロキシ−シクロヘキシル−フェニル−ケトン０．５重量部を加えた樹脂組成物をグラビアコーターにより膜厚１μｍで塗布した後、５００ｍＪ／ｃｍ２のＵＶ光を照射して硬化させ、透明樹脂層１を作製した。ロールツーロール方式の、大気圧ＣＶＤ装置，グラビアコーター，ＵＶ照射装置を有する塗工機を用い、ＣＶＤによりテトラメトキシシランを原料ガスとして透明無機層であるＳｉＯ２を膜厚３μｍに成膜し、続いてジシクロペンタジエニルジアクリレート９０重量部と平均分子量５００であるエポキシアクリレート１０重量部の混合物に光重合開始剤として１−ヒドロキシ−シクロヘキシル−フェニル−ケトン０．５重量部を加えた樹脂組成物を膜厚５μｍにグラビアコーターで塗布し、５００ｍＪ／ｃｍ２のＵＶ光を照射して硬化させ、ロール状で透明シートを得た。
【００１７】
（実施例４）
グラビアコーターとＵＶ照射装置を有するロールツーロール方式の塗工機を用いて、離型処理した厚さ２５μｍのポリエステルフィルム上に、ジシクロペンタジエニルジアクリレート７０重量部と平均分子量５００であるエポキシアクリレート３０重量部の混合物に光重合開始剤として１−ヒドロキシ−シクロヘキシル−フェニル−ケトン０．５重量部を加えた樹脂組成物を膜厚１０μｍに塗布し、７５０ｍＪ／ｃｍ２のＵＶ光を照射して硬化させ、透明樹脂層１を得た。ロールツーロール方式のイオンプレーティング装置により透明無機層であるＳｉＯ２を厚さ２μｍに成膜した。イオンプレーティング装置から取り出した後、再度ロールツーロール方式の塗工機を用いて、ジシクロペンタジエニルジアクリレート９０重量部と平均分子量５００であるエポキシアクリレート１０重量部の混合物に光重合開始剤として１−ヒドロキシ−シクロヘキシル−フェニル−ケトン０．５重量部を加えた樹脂組成物を膜厚８μｍに塗布し、７５０ｍＪ／ｃｍ２のＵＶ光を照射して硬化させ、ポリエステルフィルムから剥離して透明シートを得た。
【００１８】
（比較例１）
ジシクロペンタジエニルジアクリレート７０重量部と平均分子量５００であるエポキシアクリレート３０重量部の混合物に光重合開始剤として１−ヒドロキシ−シクロヘキシル−フェニル−ケトンを０．５重量部を加えた樹脂組成物を、離型処理したガラス板に枚葉式ダイコーターで塗布し、両面から３００ｍＪ／ｃｍ２のＵＶ光を照射して硬化させた。さらに真空オーブン中で、約１００℃で３時間加熱後、さらに約２５０℃で３時間加熱し、厚さ２０μｍの透明シートを得た。
【００１９】
（比較例２）
溶融押出法により幅６００ｍｍ厚さ１０μｍのポリエーテルスルホンフィルムのロール品を作成した。このフィルム上に、グラビアコーターとＵＶ照射装置を有するロールツーロール方式の塗工機を用いて、ノルボルナンジメチロールジアクリレート９０重量部と平均分子量５００であるエポキシアクリレート１０重量部の混合物に光重合開始剤として１−ヒドロキシ−シクロヘキシル−フェニル−ケトン０．５重量部を加えた樹脂組成物をグラビアコーターにより膜厚１μｍで塗布した後、５００ｍＪ／ｃｍ２のＵＶ光を照射して硬化させ、透明樹脂層を成膜した。続いて、ロールツーロール方式のパルスＤＣ式スパッタリング装置によりＳｉターゲットを用いた反応性スパッタリグでガスバリア層であるＳｉＯｘ（１．５＜ｘ＜２．０）を膜厚０．１μｍに蒸着し、透明無機層を成膜した。真空成膜から取り出した後、再度ロールツーロール方式の塗工機を用いて、ノルボルナンジメチロールジアクリレート９０重量部と平均分子量５００であるエポキシアクリレート１０重量部の混合物に光重合開始剤として１−ヒドロキシ−シクロヘキシル−フェニル−ケトン０．５重量部を加えた樹脂組成物を膜厚３μｍで塗布し、５００ｍＪ／ｃｍ２のＵＶ光を照射して硬化させ、ロール状で透明シートを得た。
【００２０】
以上のようにして作製した光学シートについて、下記に示す評価方法により、各種特性を測定した。
ａ）線膨張係数
セイコー電子（株）製ＴＭＡ／ＳＳ１２０Ｃ型熱応力歪測定装置を用いて、窒素雰囲気下、１分間に５℃の割合で温度を３０℃から１５０℃まで上昇させた後、一旦０℃まで冷却し、再び１分間に５℃の割合で温度を上昇させて３０℃〜１００℃の時の値を測定して求めた。荷重を５ｇにし、引張モードで測定を行った。測定は、独自に設計した石英引張チャック（材質：石英，線膨張係数０．５ｐｐｍ／℃）を用いた。一般に使われているインコネル製のチャックは、それ自体の線膨張が高いことやサンプルの支持形態に不具合があり、測定ばらつきが大きくなる問題があった。したがって、石英引張チャックを独自に設計し、それを用いて線膨張係数を測定することにした。この引張チャックを用いることにより、圧縮モードで測定した場合とほぼ同様の値で測定できることを確認している。
ｂ）耐熱性（ガラス転移温度）
セイコー電子（株）製ＤＭＳ―２１０型粘弾性測定装置で測定し、１Ｈｚでのｔａｎδの最大値をガラス転移温度（Ｔｇ）とした。
ｃ）光線透過率
分光光度計Ｕ３２００（日立製作所製）で５５０ｎｍの光線透過率を測定した。
ｄ）位相差
王子計測器（株）製自動複屈折計ＫＯＢＲＡ−２１を用いて入社角度０度の値を測定した。
評価結果を表１に示す。
【００２１】
【表１】
実施例１〜４は低線膨張係数、高耐熱性、高透明性（高光線透過率）、低位相差であり、良好な特性を示した。
比較例１では透明無機層を有しないために線膨張係数が大きな値となってしまった。
比較例２では、透明無機層を有するものの、ガスバリア層として形成された厚さ０．６μｍ未満の層であるために線膨張係数が４０ｐｐｍ／℃を超えた大きな値となってしまった。
【発明の効果】
本発明の光学シートは、低線膨張係数、透明性、耐熱性に優れるため、アクティブマトリックスタイプの液晶表示素子用基板や有機ＥＬ素子用基板に好適に利用できる。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a transparent sheet that can be suitably used for a liquid crystal display element substrate, an organic EL display element substrate, a solar cell substrate, and the like.
[0002]
[Prior art]
In general, glass plates are often used for substrates for liquid crystal display elements, substrates for organic EL display elements, solar cell substrates, and the like. However, in recent years, many attempts have been made to use plastic instead of a glass plate because of problems such as being easily broken, being not bendable, having a large specific gravity, and being unsuitable for weight reduction. For example, a liquid crystal display element using a transparent substrate formed by curing a composition containing a specific bis (meth) acrylate having an alicyclic structure, an aromatic or the like with an active energy ray or the like has been studied. (For example, refer to Patent Document 1.)
However, since plastic has a larger linear expansion coefficient than a glass plate, among plastics for a display element, particularly when used for a substrate for an active matrix display element, in the heating step at the time of its manufacture, metal and silicon and their metals are used. Problems such as cracks and peeling may occur in the inorganic thin film such as an oxide, which is a problem. Therefore, a sheet that is light and can be bent and is light and has a small linear expansion coefficient is desired.
[0003]
On the other hand, it has been studied to make the glass substrate as thin as possible so that it can be bent lightly. In such a case, it has been proposed to apply a resin in order to avoid fragility. (For example, see Non-Patent Document 1.) However, the lower limit of the thickness of a glass substrate is about 50 μm, and it is difficult to reduce the weight as much as plastic. The cost is high because it is obtained by etching.
Conventionally, a transparent inorganic thin film is formed on a resin film as a gas barrier layer. (See, for example, Patent Documents 2 and 3.) However, these are not invented for the purpose of lowering the coefficient of linear expansion, and have a thickness of 0.01 to 0.2 mm which does not crack even when there is no resin layer on one surface. Since it is used with a thin thickness of 1 μm, it is not effective in lowering the linear expansion coefficient. As resin films having a low linear expansion coefficient, polyimide and polyethylene naphthalate (PEN) are known, and the former generally has absorption in a short wavelength region even in visible light and has a yellow to brown color, and is preferable for optical use. On the other hand, the latter has a large phase difference and is not preferable for applications requiring optical isotropy.
[0004]
[Patent Document 1]
JP-A-10-90667 (pages 2-3)
[Non-patent document 1]
A. Weber, Thin Glass-Polymer System as Flexible Substrate for Displays, SID INTERNATIONAL SYMPOSIMUM DIGEST OFTECHNICAL PAPERS 2002 Vol. XXXIII, No. 1P. 53-55
[Patent Document 2]
JP-A-9-39151 (pages 1-3)
[Patent Document 3]
JP-A-10-329254 (pages 2-3)
[0005]
[Problems to be solved by the invention]
An object of the present invention is to provide a transparent sheet which has a low linear expansion coefficient and can be suitably used for a liquid crystal display element substrate, an organic EL display element substrate, a solar cell substrate, and the like.
[0006]
[Means for Solving the Problems]
The present inventors have conducted intensive studies to achieve the above object, and as a result, a sheet having a transparent inorganic layer having a thickness of at least 0.6 μm or more and 10 μm or less and a transparent resin layer sandwiching the transparent inorganic layer has a substrate for a liquid crystal display element or an organic EL display. The present inventors have found that they can be suitably used for element substrates, particularly substrates for active matrix display elements, and have reached the present invention.
That is, the present invention
(1) A transparent inorganic layer having a thickness of at least 0.6 μm or more and less than 50 μm, a transparent resin layer 1 and a transparent resin layer 2 sandwiching the transparent inorganic layer, and a linear expansion coefficient in the in-plane direction at 30 ° C. to 100 ° C. of 40 ppm / ° C. A transparent sheet having a phase difference of 10 nm or less and a light transmittance at a wavelength of 400 nm of 80% or more.
(2) The transparent sheet according to (1), wherein the transparent inorganic layer is formed by physical vapor deposition and / or chemical vapor deposition.
(3) The transparent sheet according to (2), wherein the physical vapor deposition is a vacuum deposition method or an ion plating method.
(4) The transparent sheet according to (2), wherein the chemical vapor deposition is performed under atmospheric pressure.
(5) The transparent sheets (1) to (4) in which a transparent inorganic layer and a transparent resin layer 2 are laminated on the transparent resin layer 1 by a roll-to-roll method.
It is.
[0007]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the present invention will be described in detail.
Examples of the transparent inorganic layer in the present invention include a silicon compound having a visible light transmittance such as silicon oxide and silicon oxynitride, and a visible light such as aluminum oxide, lead oxide, zinc oxide, titanium oxide and tantalum oxide. Examples thereof include a metal oxide having transparency. These may be used as a single layer or two or more layers.
The transparent inorganic layer may be formed by physical vapor deposition such as vacuum deposition, ion plating, and sputtering; chemical vapor deposition such as plasma CVD in vacuum, catalytic CVD, and CVD under atmospheric pressure; It can be performed by a wet coating method such as a gel method. Of these, physical vapor deposition and chemical vapor deposition are preferred because a dense film can be obtained at a low temperature. Further, among the physical vapor deposition methods, vacuum deposition and ion plating have a high film formation rate and are preferable when a film having a thickness of 0.2 μm or more and less than 50 μm is continuously formed. Further, in the chemical vapor deposition method, a method in which this is performed under atmospheric pressure is preferable because a tact time can be shortened without requiring a vacuum step.
[0008]
The transparent resin used for the transparent resin layer 1 and the transparent resin layer 2 in the present invention refers to a resin having visible light transmittance. The transparency of the transparent resin of the present invention is preferably such that the light transmittance at 550 nm when formed into a sheet is 80% or more, more preferably 85% or more, and most preferably 90% or more. When used as a display element substrate, the content is preferably 85% or more.
The glass transition temperature of the transparent resin of the present invention is preferably 120 ° C. or higher, more preferably 180 ° C. or higher, and further preferably 200 ° C. or higher. When a resin having a glass transition temperature of less than 120 ° C. is used, for example, when the resin is applied to a liquid crystal display element substrate, deformation or undulation may occur in a heating step such as formation of an alignment film or bonding of substrates. Further, since the transparency and the phase difference are small, the transparent resin used for the transparent resin layer in the present invention is preferably amorphous. When the phase difference exceeds 10 nm, the contrast may decrease or color unevenness may occur in the case of a display element using polarized light. Therefore, the phase difference of the transparent sheet needs to be 10 nm or less.
[0009]
Examples of the transparent resin of the present invention include thermoplastic resins such as polycarbonate, polyarylate, polysulfone, polyethersulfone, and cycloolefin polymers, thermosetting resins such as epoxy resins, and reactive monomers such as acrylate with active energy rays. Crosslinked resins and the like are mentioned, and a resin obtained by crosslinking a reactive monomer such as an acrylate or an epoxy resin with active energy rays and / or heat is preferred because of its excellent solvent resistance. The reactive monomer is not particularly limited as long as it can be cross-linked by heat or active energy rays. From the viewpoint of transparency and heat resistance, (meth) acrylate having two or more functional groups and two or more Are preferred, and (meth) acrylates having two or more functional groups are particularly preferred. These resins may be used alone or in combination of two or more. Further, each transparent resin layer may have a multilayer structure of two or more layers. Further, the transparent resin layer 1 and the transparent resin layer 2 may have the same resin configuration or may be different.
[0010]
The transparent resin layer 1 of the present invention can be formed by a casting method or a casting method in the case of a crosslinkable resin, or by a melt extrusion method or a solution casting method in the case of a thermoplastic resin. In the case of producing by crosslinking with active energy rays such as ultraviolet rays, it is preferable to include a photopolymerization initiator that generates radicals in the resin composition. Examples of the photopolymerization initiator used at that time include benzophenone, benzoin methyl ether, benzoin propyl ether, diethoxyacetophenone, 1-hydroxy-cyclohexyl-phenyl ketone, 2,6-dimethylbenzoyldiphenylphosphine oxide, 2,4,6 -Trimethylbenzoyldiphenylphosphine oxide. Two or more of these photopolymerization initiators may be used in combination.
[0011]
In the present invention, when the transparent inorganic layer and the transparent resin layer 2 are sequentially laminated on the transparent resin layer 1, a roll serving as a base is prevented because the transparent inorganic layer is prevented from being damaged or cracked during the manufacturing process. A transparent inorganic layer is formed by a roll-to-roll method on a transparent resin layer 1 which is a raw sheet of a transparent sheet or the like, and then a transparent resin layer 2 is also formed thereon by a roll-to-roll method. Is preferred. In this case, as a method for forming the transparent resin layer 2, when a transparent inorganic layer is formed in a vacuum chamber by a physical vapor deposition method or the like, a vapor deposition polymerization method is used, and a sol-gel method or a method under atmospheric pressure is used. When a film is formed by a chemical vapor deposition method, a wet coating method such as a gravure coat or a die coat can be used.
[0012]
If necessary, the transparent resin layer of the present invention may contain an antioxidant, an ultraviolet absorber, and a dye / pigment as long as properties such as transparency and heat resistance are not impaired.
[0013]
The linear expansion coefficient of the transparent sheet of the present invention needs to be 40 ppm / ° C. or less. In the case of a linear expansion coefficient exceeding 50 ppm / ° C. as obtained with a conventional transparent sheet, cracks occur in inorganic thin films such as metals, silicon, and oxides thereof in a heating step at the time of manufacturing a display element. In some cases, problems such as peeling and peeling may occur.
[0014]
【Example】
EXAMPLES Hereinafter, the content of the present invention will be described in detail with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist.
(Example 1)
A roll of a polycarbonate film having a width of 600 mm and a thickness of 10 μm was prepared by a melt extrusion method. On this film, using a roll-to-roll coating machine having a gravure coater and a UV irradiation device, photopolymerization was started to a mixture of 90 parts by weight of norbornane dimethylol diacrylate and 10 parts by weight of an epoxy acrylate having an average molecular weight of 500. A resin composition to which 0.5 part by weight of 1-hydroxy-cyclohexyl-phenyl-ketone was added as an agent was applied with a gravure coater to a film thickness of 1 μm, and then cured by irradiating with UV light of 500 mJ / cm 2 to obtain a transparent resin. Layer 1 was prepared. After cutting the sheet to a size of 300 mm x 400 mm and fixing it to a plate-shaped jig, Al2O3 is sputtered to a thickness of 0.6 µm by a reactive sputtering rig using an Al target by a pulse DC type multilayer sputtering apparatus to form a transparent inorganic material. A layer was deposited. The sheet fixed to the jig was taken out of the sputtering apparatus, and a mixture of 90 parts by weight of norbornane dimethylol diacrylate and 10 parts by weight of an epoxy acrylate having an average molecular weight of 500 was added to a mixture of 90 parts by weight using a single-wafer die coater as a photopolymerization initiator. -A resin composition containing 0.5 parts by weight of cyclohexyl-phenyl-ketone is applied to a thickness of 3 µm, and cured by irradiating it with UV light of 500 mJ / cm 2 by a UV irradiation device to obtain a sheet-like transparent sheet. Was.
[0015]
(Example 2)
A roll of a polyethersulfone film having a width of 600 mm and a thickness of 10 μm was prepared by a melt extrusion method. On this film, using a roll-to-roll coating machine having a gravure coater and a UV irradiation device, photopolymerization was started to a mixture of 90 parts by weight of norbornane dimethylol diacrylate and 10 parts by weight of an epoxy acrylate having an average molecular weight of 500. A resin composition to which 0.5 part by weight of 1-hydroxy-cyclohexyl-phenyl-ketone was added as an agent was applied with a gravure coater to a film thickness of 1 μm, and then cured by irradiating with UV light of 500 mJ / cm 2 to obtain a transparent resin. Layer 1 was prepared. Subsequently, SiO 2 was deposited to a thickness of 1 μm using a roll-to-roll vacuum deposition apparatus to form a transparent inorganic layer. After taking out from the vacuum film formation, the mixture of 90 parts by weight of norbornane dimethylol diacrylate and 10 parts by weight of epoxy acrylate having an average molecular weight of 500 was added again as a photopolymerization initiator using a roll-to-roll type coating machine. A resin composition to which 0.5 part by weight of hydroxy-cyclohexyl-phenyl-ketone was added was applied in a thickness of 3 μm, and was cured by irradiating it with UV light of 500 mJ / cm 2 to obtain a roll-shaped transparent sheet.
[0016]
(Example 3)
A roll of a polyethersulfone film having a width of 600 mm and a thickness of 10 μm was prepared by a melt extrusion method. A mixture of 90 parts by weight of dicyclopentadienyl diacrylate and 10 parts by weight of an epoxy acrylate having an average molecular weight of 500 was applied to this film using a roll-to-roll type coating machine having a gravure coater and a UV irradiation device. A resin composition to which 0.5 part by weight of 1-hydroxy-cyclohexyl-phenyl-ketone was added as a polymerization initiator was applied with a gravure coater to a film thickness of 1 μm, and then cured by irradiation with 500 mJ / cm 2 UV light, A transparent resin layer 1 was produced. Using a roll-to-roll type coating machine having an atmospheric pressure CVD apparatus, a gravure coater, and a UV irradiation apparatus, a transparent inorganic layer of SiO2 is formed to a thickness of 3 μm by CVD using tetramethoxysilane as a raw material gas. Resin composition obtained by adding 0.5 parts by weight of 1-hydroxy-cyclohexyl-phenyl-ketone as a photopolymerization initiator to a mixture of 90 parts by weight of dicyclopentadienyl diacrylate and 10 parts by weight of an epoxy acrylate having an average molecular weight of 500 Was applied with a gravure coater to a film thickness of 5 μm, and cured by irradiating UV light of 500 mJ / cm 2 to obtain a roll-shaped transparent sheet.
[0017]
(Example 4)
Using a roll-to-roll type coating machine having a gravure coater and a UV irradiation device, 70 parts by weight of dicyclopentadienyl diacrylate and an epoxy having an average molecular weight of 500 were formed on a release-treated polyester film having a thickness of 25 μm. A resin composition obtained by adding 0.5 parts by weight of 1-hydroxy-cyclohexyl-phenyl-ketone as a photopolymerization initiator to a mixture of 30 parts by weight of acrylate is applied to a film thickness of 10 μm, and irradiated with UV light of 750 mJ / cm 2. And cured to obtain a transparent resin layer 1. A transparent inorganic layer of SiO2 was formed to a thickness of 2 μm by a roll-to-roll type ion plating apparatus. After being taken out of the ion plating apparatus, a photopolymerization initiator was again added to a mixture of 90 parts by weight of dicyclopentadienyl diacrylate and 10 parts by weight of an epoxy acrylate having an average molecular weight of 500 by using a roll-to-roll coating machine again. A resin composition to which 0.5 part by weight of 1-hydroxy-cyclohexyl-phenyl-ketone was added was applied to a thickness of 8 μm, cured by irradiating 750 mJ / cm 2 of UV light, and peeled from the polyester film to be transparent. I got a sheet.
[0018]
(Comparative Example 1)
Resin composition obtained by adding 0.5 part by weight of 1-hydroxy-cyclohexyl-phenyl-ketone as a photopolymerization initiator to a mixture of 70 parts by weight of dicyclopentadienyl diacrylate and 30 parts by weight of epoxy acrylate having an average molecular weight of 500 Was applied to a release-treated glass plate by a single-wafer die coater, and cured by irradiating UV light of 300 mJ / cm 2 from both sides. Furthermore, after heating at about 100 ° C. for 3 hours in a vacuum oven, further heating at about 250 ° C. for 3 hours, a transparent sheet having a thickness of 20 μm was obtained.
[0019]
(Comparative Example 2)
A roll of a polyethersulfone film having a width of 600 mm and a thickness of 10 μm was prepared by a melt extrusion method. On this film, using a roll-to-roll coating machine having a gravure coater and a UV irradiation device, photopolymerization was started to a mixture of 90 parts by weight of norbornane dimethylol diacrylate and 10 parts by weight of an epoxy acrylate having an average molecular weight of 500. A resin composition to which 0.5 part by weight of 1-hydroxy-cyclohexyl-phenyl-ketone was added as an agent was applied with a gravure coater to a film thickness of 1 μm, and then cured by irradiating with UV light of 500 mJ / cm 2 to obtain a transparent resin. A layer was deposited. Subsequently, SiOx (1.5 <x <2.0), which is a gas barrier layer, was deposited to a film thickness of 0.1 μm by a reactive sputter rig using a Si target by a pulse DC type sputtering apparatus of a roll-to-roll method, and was transparent. An inorganic layer was formed. After taking out from the vacuum film formation, the mixture of 90 parts by weight of norbornane dimethylol diacrylate and 10 parts by weight of epoxy acrylate having an average molecular weight of 500 was added again as a photopolymerization initiator using a roll-to-roll type coating machine. A resin composition to which 0.5 part by weight of hydroxy-cyclohexyl-phenyl-ketone was added was applied in a thickness of 3 μm, and was cured by irradiating it with UV light of 500 mJ / cm 2 to obtain a roll-shaped transparent sheet.
[0020]
Various characteristics of the optical sheet prepared as described above were measured by the following evaluation methods.
a) Linear expansion coefficient Using a TMA / SS120C type thermal stress strain measuring device manufactured by Seiko Denshi Co., Ltd., the temperature was increased from 30 ° C. to 150 ° C. in a nitrogen atmosphere at a rate of 5 ° C. per minute, and then once. After cooling to 0 ° C., the temperature was raised again at a rate of 5 ° C. per minute, and the value at 30 ° C. to 100 ° C. was measured and determined. The measurement was performed in a tensile mode with a load of 5 g. For the measurement, a quartz tension chuck (material: quartz, linear expansion coefficient: 0.5 ppm / ° C.) uniquely designed was used. Inconel chucks, which are generally used, have a problem in that the linear expansion of the chuck itself is high, the sample support form is inconvenient, and the measurement dispersion is large. Therefore, we decided to design the quartz tension chuck independently and use it to measure the linear expansion coefficient. It has been confirmed that by using this tension chuck, it is possible to measure with substantially the same value as when measuring in the compression mode.
b) Heat resistance (glass transition temperature)
The maximum value of tan δ at 1 Hz was measured with a DMS-210 type viscoelasticity measuring device manufactured by Seiko Electronics Co., Ltd., and was taken as the glass transition temperature (Tg).
c) Light transmittance The light transmittance at 550 nm was measured with a spectrophotometer U3200 (manufactured by Hitachi, Ltd.).
d) The value of the joining angle of 0 ° was measured using an automatic birefringence meter KOBRA-21 manufactured by Oji Scientific Instruments.
Table 1 shows the evaluation results.
[0021]
[Table 1]
Examples 1 to 4 exhibited low linear expansion coefficient, high heat resistance, high transparency (high light transmittance), and low retardation, and exhibited good characteristics.
In Comparative Example 1, the linear expansion coefficient was large because the transparent inorganic layer was not provided.
In Comparative Example 2, although having a transparent inorganic layer, since the layer was formed as a gas barrier layer and had a thickness of less than 0.6 μm, the coefficient of linear expansion was a large value exceeding 40 ppm / ° C.
【The invention's effect】
INDUSTRIAL APPLICABILITY The optical sheet of the present invention has excellent low linear expansion coefficient, transparency, and heat resistance, and thus can be suitably used as a substrate for an active matrix type liquid crystal display device or a substrate for an organic EL device.
Claims (5)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002298658A JP4098056B2 (en) | 2002-10-11 | 2002-10-11 | Transparent sheet |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002298658A JP4098056B2 (en) | 2002-10-11 | 2002-10-11 | Transparent sheet |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2004130709A true JP2004130709A (en) | 2004-04-30 |
| JP4098056B2 JP4098056B2 (en) | 2008-06-11 |
Family
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2002298658A Expired - Lifetime JP4098056B2 (en) | 2002-10-11 | 2002-10-11 | Transparent sheet |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4098056B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008062481A (en) * | 2006-09-06 | 2008-03-21 | Jsr Corp | Laminated film |
| US7579054B2 (en) | 2004-06-25 | 2009-08-25 | Sumitomo Chemical Company, Limited | Substrate for flexible displays |
| JP2011116054A (en) * | 2009-12-04 | 2011-06-16 | Tosoh Corp | Transparent laminated film |
-
2002
- 2002-10-11 JP JP2002298658A patent/JP4098056B2/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7579054B2 (en) | 2004-06-25 | 2009-08-25 | Sumitomo Chemical Company, Limited | Substrate for flexible displays |
| JP2008062481A (en) * | 2006-09-06 | 2008-03-21 | Jsr Corp | Laminated film |
| JP2011116054A (en) * | 2009-12-04 | 2011-06-16 | Tosoh Corp | Transparent laminated film |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4098056B2 (en) | 2008-06-11 |
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