JP2004361801A - Light control film, its manufacturing method, and ink jet device used for manufacturing the film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a light control film which can be easily manufactured, which is improved in terms of mechanical strength, improved in terms of a light shielding performance with reference to unnecessary incident light, which can obtain a bright clear image viewing from a prescribed direction, and also, where a dot, stripe, grid or honeycomb pattern can be freely formed, and to provide a manufacturing method of the light control film and an ink jet device used for manufacturing the film. <P>SOLUTION: As for the manufacturing method of the light control film, a light control pattern is formed on a transparent substrate by an ink jet system. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

【００９３】
式中、Ｒ_１、Ｒ_２、Ｒ_３、Ｒ_４及びＲ_５は同一でも異なってもよく、水素原子、ハロゲン原子、ニトロ基、ヒドロキシル基、アルキル基、アルケニル基、アリール基、アルコキシル基、アシルオキシ基、アリールオキシ基、アルキルチオ基、アリールチオ基、モノ若しくはジアルキルアミノ基、アシルアミノ基または５〜６員の複素環基を表し、Ｒ_４とＲ_５は閉環して５〜６員の炭素環を形成してもよい。
【００９４】
また、上記記載のこれらの基は、任意の置換基を有していてよい。
以下に本発明に係る紫外線吸収剤の具体例を挙げるが、本発明はこれらに限定されない。
【００９５】
ＵＶ−１：２−（２′−ヒドロキシ−５′−メチルフェニル）ベンゾトリアゾール
ＵＶ−２：２−（２′−ヒドロキシ−３′，５′−ジ−ｔｅｒｔ−ブチルフェニル）ベンゾトリアゾール
ＵＶ−３：２−（２′−ヒドロキシ−３′−ｔｅｒｔ−ブチル−５′−メチルフェニル）ベンゾトリアゾール
ＵＶ−４：２−（２′−ヒドロキシ−３′，５′−ジ−ｔｅｒｔ−ブチルフェニル）−５−クロロベンゾトリアゾール
ＵＶ−５：２−（２′−ヒドロキシ−３′−（３″，４″，５″，６″−テトラヒドロフタルイミドメチル）−５′−メチルフェニル）ベンゾトリアゾール
ＵＶ−６：２，２−メチレンビス（４−（１，１，３，３−テトラメチルブチル）−６−（２Ｈ−ベンゾトリアゾール−２−イル）フェノール）
ＵＶ−７：２−（２′−ヒドロキシ−３′−ｔｅｒｔ−ブチル−５′−メチルフェニル）−５−クロロベンゾトリアゾール
ＵＶ−８：２−（２Ｈ−ベンゾトリアゾール−２−イル）−６−（直鎖及び側鎖ドデシル）−４−メチルフェノール（ＴＩＮＵＶＩＮ１７１、Ｃｉｂａ社製）
ＵＶ−９：オクチル−３−〔３−ｔｅｒｔ−ブチル−４−ヒドロキシ−５−（クロロ−２Ｈ−ベンゾトリアゾール−２−イル）フェニル〕プロピオネートと２−エチルヘキシル−３−〔３−ｔｅｒｔ−ブチル−４−ヒドロキシ−５−（５−クロロ−２Ｈ−ベンゾトリアゾール−２−イル）フェニル〕プロピオネートの混合物（ＴＩＮＵＶＩＮ１０９、Ｃｉｂａ社製）
また、ベンゾフェノン系紫外線吸収剤としては下記一般式（２）で表される化合物が好ましく用いられる。
【００９６】
【化２】

【００９７】
式中、Ｙは水素原子、ハロゲン原子またはアルキル基、アルケニル基、アルコキシル基、及びフェニル基を表し、これらのアルキル基、アルケニル基及びフェニル基は置換基を有していてもよい。Ａは水素原子、アルキル基、アルケニル基、フェニル基、シクロアルキル基、アルキルカルボニル基、アルキルスルホニル基または−ＣＯ（ＮＨ）_ｎ−１−Ｄ基を表し、Ｄはアルキル基、アルケニル基または置換基を有していてもよいフェニル基を表す。ｍ及びｎは１または２を表す。
【００９８】
上記において、アルキル基としては、例えば、炭素数２４までの直鎖または分岐の脂肪族基を表し、アルコキシル基としては例えば、炭素数１８までのアルコキシル基を表し、アルケニル基としては例えば、炭素数１６までのアルケニル基でアリル基、２−ブテニル基等を表す。また、アルキル基、アルケニル基、フェニル基への置換基としてはハロゲン原子、例えば、塩素原子、臭素原子、フッ素原子等、ヒドロキシル基、フェニル基（このフェニル基にはアルキル基またはハロゲン原子等を置換していてもよい）等が挙げられる。
【００９９】
以下に一般式（２）で表されるベンゾフェノン系化合物の具体例を示すが、本発明はこれらに限定されない。
【０１００】
ＵＶ−１０：２，４−ジヒドロキシベンゾフェノン
ＵＶ−１１：２，２′−ジヒドロキシ−４−メトキシベンゾフェノン
ＵＶ−１２：２−ヒドロキシ−４−メトキシ−５−スルホベンゾフェノン
ＵＶ−１３：ビス（２−メトキシ−４−ヒドロキシ−５−ベンゾイルフェニルメタン）
本発明で好ましく用いられる紫外線吸収剤としては、透明性が高く、偏光板や液晶の劣化を防ぐ効果に優れたベンゾトリアゾール系紫外線吸収剤やベンゾフェノン系紫外線吸収剤が好ましく、不要な着色がより少ないベンゾトリアゾール系紫外線吸収剤が特に好ましく用いられる。
【０１０１】
また、特開２００１−１８７８２５号に記載されている分配係数が９．２以上の紫外線吸収剤は、支持体の面品質を向上させ、塗布性にも優れている。特に分配係数が１０．１以上の紫外線吸収剤を用いることが好ましい。
【０１０２】
また、特開平６−１４８４３０号に記載の一般式（１）または一般式（２）、特願２０００−１５６０３９号の一般式（３）、（６）、（７）記載の高分子紫外線吸収剤（または紫外線吸収性ポリマー）も好ましく用いられる。高分子紫外線吸収剤としては、ＰＵＶＡ−３０Ｍ（大塚化学（株）製）等が市販されている。
【０１０３】
また、インクジェット方式により形成したパターンの耐熱性を高めるために、光硬化反応を抑制しないような酸化防止剤を選んで用いることができる。例えば、ヒンダードフェノール誘導体、チオプロピオン酸誘導体、ホスファイト誘導体等を挙げることができる。具体的には、例えば、４，４′−チオビス（６−ｔｅｒｔ−３−メチルフェノール）、４，４′−ブチリデンビス（６−ｔｅｒｔ−ブチル−３−メチルフェノール）、１，３，５−トリス（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシベンジル）イソシアヌレート、２，４，６−トリス（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシベンジル）メシチレン、ジ−オクタデシル−４−ヒドロキシ−３，５−ジ−ｔｅｒｔ−ブチルベンジルホスフェート等を挙げることができる。
【０１０４】
本発明に係るインクには、ＳｎＯ_２、ＩＴＯ、ＺｎＯ等の導電性微粒子や架橋カチオンポリマー粒子等の帯電防止剤を含有させることが好ましい。また、これらの化合物は、透明基材上に設ける後述のハードコート層に添加してもよい。
【０１０５】
本発明において、インクジェット方式により形成した層が活性光線硬化型樹脂を含む場合、活性光線の照射方法としては、インク液滴を透明基体上に着弾させた直後に、活性光線を照射することが好ましい。
【０１０６】
〔インクの吐出及び硬化条件〕
本発明でいうインク液滴を透明基体上に着弾させた直後とは、具体的にはインク液滴が着弾後０．００１〜２．０秒の間が好ましく、より好ましくは０．００１〜１．０秒の間である。照射光源の照射間隔が０．００１秒より短いと、ノズル部と照射光源の距離が接近しすぎて、硬化反応により昇華物質によるヘッドの汚染や、照射光のインク出射部への回り込みにより、ノズル部での硬化によりノズル詰まりを起こすため好ましくない。また、照射光源の照射間隔が２．０秒を超えると、着弾したインク液滴の流動、変形等により、本発明で規定する所望の凹凸構造を得ることが困難となる。
【０１０７】
上記照射時のノズル部への光の回り込みを防止するため、本発明のインクジェット方式においては、活性光源照射部をインクジェットヘッド（特にそのノズル部）に直接作用させない位置に配置することが好ましく、更に、照射される活性光線が、インクジェットヘッドのノズル部に作用しないように遮光板をその間に設けることが好ましい。
【０１０８】
また、インク液滴が着弾した直後の活性光線の照射は、着弾したインク液滴の流動性を低下させ、所望の凹凸構造が形成できる程度に照射すればよく、ハーフキュア状態でもよい。この場合には、別途下流側に設置した活性光源を照射して、完全に硬化させることができる。このようにすることにより、インクジェットヘッドのノズル部に、活性光線が作用し目詰まりを起こすことを防止することができる。
【０１０９】
本発明に使用することができる活性光線としては、紫外線、電子線、γ線等で、パターン形成組成物である活性光線硬化型樹脂を活性化させる光源であれば制限なく使用できるが、紫外線、電子線が好ましく、特に取り扱いが簡便で高エネルギーが容易に得られるという点で紫外線が好ましい。紫外線反応性化合物を光重合させる紫外線の光源としては、紫外線を発生する光源であれば何れも使用できる。例えば、低圧水銀灯、中圧水銀灯、高圧水銀灯、超高圧水銀灯、カーボンアーク灯、メタルハライドランプ、キセノンランプ等を用いることができる。また、ＡｒＦエキシマレーザ、ＫｒＦエキシマレーザ、エキシマランプまたはシンクロトロン放射光等も用いることができる。照射条件はそれぞれのランプによって異なるが、照射光量は１ｍＪ／ｃｍ^２以上が好ましく、更に好ましくは、２０〜１００００ｍＪ／ｃｍ^２であり、特に好ましくは、５０〜２０００ｍＪ／ｃｍ^２である。
【０１１０】
また、電子線も同様に使用できる。電子線としては、コックロフトワルトン型、バンデグラフ型、共振変圧型、絶縁コア変圧器型、直線型、ダイナミトロン型、高周波型等の各種電子線加速器から放出される５０〜１０００ｋｅＶ、好ましくは１００〜３００ｋｅＶのエネルギーを有する電子線を挙げることができる。
【０１１１】
本発明においては、活性線照射の時の雰囲気中の酸素濃度が１％以下であることがより好ましい。
【０１１２】
また、本発明においては、活性光線の硬化反応を効率的に進めるため、透明基材等を加熱することもできる。加熱方法としては、特に制限はないが、ヒートプレート、ヒートロール、サーマルヘッド、あるいは着弾したインク表面に熱風を吹き付ける等の方法を使用するのが好ましい。また、インクジェット出射部の透明支持体を挟んで反対側に用いられるバックロールを、ヒートロールとして、連続的に加熱を施してもよい。
【０１１３】
加熱温度としては、使用する活性光線硬化型樹脂の種類により一概には規定できないが、透明基材への熱変形等の影響を与えない温度範囲であることが好ましく、３０〜２００℃が好ましく、更に５０〜１２０℃が好ましく、特に好ましくは７０〜１００℃である。
【０１１４】
〔熱硬化性樹脂〕
次いで、本発明に係る熱硬化性樹脂について説明する。
【０１１５】
本発明で用いることのできる熱硬化性樹脂としては、不飽和ポリエステル樹脂、エポキシ樹脂、ビニルエステル樹脂、フェノール樹脂、熱硬化性ポリイミド樹脂、熱硬化性ポリアミドイミドなどを挙げることができる。
【０１１６】
不飽和ポリエステル樹脂としては、例えば、オルソフタル酸系樹脂、イソフタル酸系樹脂、テレフタル酸系樹脂、ビスフェノール系樹脂、プロピレングリコール−マレイン酸系樹脂、ジシクロペンタジエンないしその誘導体を不飽和ポリエステル組成に導入して低分子量化した、或いは被膜形成性のワックスコンパウンドを添加した低スチレン揮発性樹脂、熱可塑性樹脂（ポリ酢酸ビニル樹脂、スチレン・ブタジエン共重合体、ポリスチレン、飽和ポリエステルなど）を添加した低収縮性樹脂、不飽和ポリエステルを直接Ｂｒ_２でブロム化する、或いはヘット酸、ジブロムネオペンチルグリコールを共重合するなどした反応性タイプ、塩素化パラフィン、テトラブロムビスフェノール等のハロゲン化物と三酸化アンチモン、燐化合物の組み合わせや水酸化アルミニウムなどを添加剤として用いる添加タイプの難燃性樹脂、ポリウレタンやシリコーンとハイブリッド化、またはＩＰＮ化した強靭性（高強度、高弾性率、高伸び率）の強靭性樹脂等がある。
【０１１７】
エポキシ樹脂としては、例えば、ビスフェノールＡ型、ノボラックフェノール型、ビスフェノールＦ型、臭素化ビスフェノールＡ型を含むグリシジルエーテル系エポキシ樹脂、グリシジルアミン系、グリシジルエステル系、環式脂肪系、複素環式エポキシ系を含む特殊エポキシ樹脂等を挙げることができる。
【０１１８】
ビニルエステル樹脂としては、例えば、普通エポキシ樹脂とメタクリル酸等の不飽和一塩基酸とを開環付加反応して得られるオリゴマーをスチレン等のモノマーに溶解した物である。また、分子末端や側鎖にビニル基を持ちビニルモノマーを含有する等の特殊タイプもある。グリシジルエーテル系エポキシ樹脂のビニルエステル樹脂としては、例えば、ビスフェノール系、ノボラック系、臭素化ビスフェノール系等があり、特殊ビニルエステル樹脂としてはビニルエステルウレタン系、イソシアヌル酸ビニル系、側鎖ビニルエステル系等がある。
【０１１９】
フェノール樹脂は、フェノール類とフォルムアルデヒド類を原料として重縮合して得られ、レゾール型とノボラック型がある。
【０１２０】
熱硬化性ポリイミド樹脂としては、例えば、マレイン酸系ポリイミド、例えばポリマレイミドアミン、ポリアミノビスマレイミド、ビスマレイミド−Ｏ，Ｏ′−ジアリルビスフェノール−Ａ樹脂、ビスマレイミド−トリアジン樹脂等、またナジック酸変性ポリイミド、及びアセチレン末端ポリイミド等がある。
【０１２１】
また、上述した活性光線硬化型樹脂の一部も、熱硬化性樹脂として用いることができる。
【０１２２】
なお、本発明に係る熱硬化性樹脂からなるインクには、活性光線硬化型樹脂を含むインクに記載した酸化防止剤や紫外線吸収剤を適宜用いてもよい。
【０１２３】
本発明において、インクジェット方式により形成した層が熱硬化性樹脂を含む場合、加熱方法としては、インク液滴を透明基体上に着弾させた直後に、加熱処理を行うことが好ましい。
【０１２４】
本発明でいうインク液滴を透明基体上に着弾させた直後とは、具体的にはインク液滴が着弾と同時または５秒以内に加熱が開始されることが好ましく、より好ましくは０．００１〜２．０秒の間である。加熱間隔が０．００１秒より短いと、ノズル部と加熱部の距離が接近しすぎて、熱がヘッド部に伝達すると、ノズル部での硬化によりノズル詰まりを起こすため注意が必要である。また、加熱間隔が５．０秒を超えると、着弾したインク液滴の流動、変形等により、本発明で規定する所望の特性を得ることが困難となる。
【０１２５】
これらをインクとして使用する場合につき、活性光線硬化型インクと異なる事項を中心に記載する。
【０１２６】
上記加熱時のノズル部への熱の伝達を防止するため、本発明のインクジェット方式においては、加熱部をインクジェットヘッド（特にノズル部）に直接作用させない位置に配置することが好ましい。
【０１２７】
加熱方法としては、特に制限はないが、ヒートプレート、ヒートロール、サーマルヘッド、あるいは着弾したインク表面に熱風を吹き付ける等の方法を使用するのが好ましい。また、インクジェット出射部の透明支持体を挟んで反対側に設けるバックロールを、ヒートロールとして、連続的に加熱を施してもよい。加熱温度としては、使用する熱硬化性樹脂の種類により一概には規定できないが、透明基材への熱変形等の影響を与えない温度範囲であることが好ましく、３０〜２００℃が好ましく、更に５０〜１２０℃が好ましく、特に好ましくは７０〜１００℃である。
【０１２８】
本発明に係るインクにおいては、上述した活性光線硬化型樹脂、熱硬化性樹脂のいずれも用いることができるが、好ましくは活性光線硬化型樹脂を用いることである。
【０１２９】
本発明に係る上記インクには、必要に応じて溶媒を含有させることができる。例えば、水系溶媒に前記活性光線硬化型樹脂モノマー成分、あるいは熱硬化性樹脂モノマー成分を溶解もしくは分散させてもよく、あるいは有機溶媒を用いてもよい。有機溶媒は低沸点のものでも高沸点のものでも適宜選択して用いることができ、これらの溶媒の添加量や種類、組成はインクの粘度を調整するため適宜調整することが好ましい。
【０１３０】
本発明に係るインクで用いることができる溶剤としては、例えば、メタノール、エタノール、１−プロパノール、２−プロパノール、ブタノール等のアルコール類；アセトン、メチルエチルケトン、シクロヘキサノン等のケトン類；ベンゼン、トルエン、キシレン等の芳香族炭化水素類；エチレングリコール、プロピレングリコール、ヘキシレングリコール等のグリコール類；エチルセルソルブ、ブチルセルソルブ、エチルカルビトール、ブチルカルビトール、ジエチルセルソルブ、ジエチルカルビトール、プロピレングリコールモノメチルエーテル等のグリコールエーテル類；Ｎ−メチルピロリドン、ジメチルフォルムアミド、乳酸メチル、乳酸エチル、酢酸メチル、酢酸エチル、酢酸アミル等のエステル類；ジエチルエーテル等のエーテル類、水等が挙げられ、それらを単独または２種以上混合して使用することができる。また、分子内にエーテル結合をもつものが特に好ましく、グリコールエーテル類も好ましく用いられる。
【０１３１】
グリコールエーテル類としては、具体的には下記の溶剤が挙げられるが、特にこれらに限定されない。プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノブチルエーテル、ジエチレングリコールジメチルエーテル、エチレングリコールモノメチルエーテル、エチレングリコールモノメチルエーテルＡｃ、エチレングリコールモノブチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノエチルエーテルＡｃ、エチレングリコールジエチルエーテル等を挙げることができる、なおＡｃはアセテートを表す。本発明に係るインクにおいては、上記溶剤の中でも、沸点が１００℃未満の溶剤が好ましい。
【０１３２】
〔パターン形成層以外の層〕
次いで、本発明におけるインクジェット方式によるパターン形成層以外の層を形成する好ましい態様について説明する。
【０１３３】
本発明のライトコントロールフィルムは、透明基材上に好ましくは防眩層を有し、その上に光学干渉によって反射率が減少するように屈折率、膜厚、層の数、層順等を考慮して積層されていることが好ましい。
【０１３４】
防眩層とは、表面に微細な凹凸構造を有し、不要な表面反射を防止して、画面を見やすくするために塗設される層である。その凹凸の度合いは中心線平均粗さ（Ｒａ）が０．０５〜５．０μｍ程度であり、樹脂と無機或いは有機の微粒子を含有させた透明インク状の防眩性付与組成物を、インクジェット方式により吐出させて形成するのが好ましい方法である。ライトコントロールフィルム面に形成される粗さをコントロールするには、無機或いは有機の微粒子の粒径を調整すればよい。
【０１３５】
本発明に係る反射防止層は、防眩層の上に、防眩層側から複数の屈折率層を設けることが好ましく、更には、高屈折率層、低屈折率層を順に積層したものであることが好ましい。屈折率の高低は、そこに含まれる金属または化合物によってほぼ決まり、例えばＴｉは高く、Ｓｉは低く、Ｆを含有する化合物は更に低く、このような組み合わせによって屈折率が設定される。屈折率と膜厚は、分光反射率の測定により計算して算出し得る。
【０１３６】
反射防止層は、支持体よりも屈折率の高い高屈折率層と、支持体よりも屈折率の低い低屈折率層を組み合わせて構成されている。得に好ましくは、３層以上の屈折率層から構成される反射防止層であり、支持体側から屈折率の異なる３層を、中屈折率層（支持体または防眩層よりも屈折率が高く、高屈折率層よりも屈折率の低い層）／高屈折率層／低屈折率層の順に積層されているものが好ましく用いられる。または、２層以上の高屈折率層と２層以上の低屈折率層とを交互に積層した４層以上の層構成の反射防止層も好ましく用いられる。
【０１３７】
また、必要に応じて、汚れや指紋のふき取りが容易となるように、最表面の低屈折率層の上に、さらに防汚層を設けることも好ましい。防汚層としては、含フッ素有機シラン化合物が好ましく用いられる。
【０１３８】
本発明に係る反射防止層は、前述の塗布方式により形成することもでき、また大気圧プラズマ処理、ＣＶＤ等のドライプロセスによって金属酸化物層（ＳｉＯ_２、ＴｉＯ_２、Ｔａ_２Ｏ_５、ＺｒＯ_２、ＺｎＯ、ＳｎＯ_２、ＩＴＯなど）を設けることができる。
【０１３９】
本発明に係る高屈折率層としては、好ましくはチタン酸化物を含有することが望ましい。これらは微粒子として添加することもできるが、より好ましくは、有機チタン化合物のモノマー、オリゴマーまたはそれらの加水分解物を含有する塗布液を塗布し乾燥させて形成させた屈折率１．５５〜２．５の層である。
【０１４０】
本発明に用いられる有機チタン化合物のモノマー、オリゴマーとしては、Ｔｉ（ＯＣＨ_３）_４、Ｔｉ（ＯＣ_２Ｈ_５）_４、Ｔｉ（Ｏ−ｎ−Ｃ_３Ｈ_７）_４、Ｔｉ（Ｏ−ｉ−Ｃ_３Ｈ_７）_４、Ｔｉ（Ｏ−ｎ−Ｃ_４Ｈ_９）_４、Ｔｉ（Ｏ−ｎ−Ｃ_３Ｈ_７）_４の２〜１０量体、Ｔｉ（Ｏ−ｉ−Ｃ_３Ｈ_７）_４の２〜１０量体、Ｔｉ（Ｏ−ｎ−Ｃ_４Ｈ_９）_４の２〜１０量体等が好ましい例として挙げられる。これらは単独で、または２種以上組み合わせて用いることができる。中でもＴｉ（Ｏ−ｎ−Ｃ_３Ｈ_７）_４、Ｔｉ（Ｏ−ｉ−Ｃ_３Ｈ_７）_４、Ｔｉ（Ｏ−ｎ−Ｃ_４Ｈ_９）_４、Ｔｉ（Ｏ−ｎ−Ｃ_３Ｈ_７）_４の２〜１０量体、Ｔｉ（Ｏ−ｎ−Ｃ_４Ｈ_９）_４の２〜１０量体が特に好ましい。
【０１４１】
本発明に用いられる有機チタン化合物のモノマー、オリゴマーまたはそれらの加水分解物は、塗布液に含まれる固形分中の５０．０〜９８．０質量％を占めていることが望ましい。固形分比率は５０〜９０質量％がより好ましく、５５〜９０質量％が更に好ましい。このほか、塗布組成物には有機チタン化合物のポリマー（あらかじめ有機チタン化合物の加水分解を行って架橋したもの）あるいは酸化チタン微粒子を添加することも好ましい。
【０１４２】
また、本発明においては、塗布液中に上記有機チタン化合物のモノマー、オリゴマーの部分または完全加水分解物を含むが、有機チタン化合物のモノマー、オリゴマーは、自己縮合して架橋し網状結合するものである。その反応を促進するために触媒や硬化剤を使用することができ、それらには、金属キレート化合物、有機カルボン酸塩等の有機金属化合物や、アミノ基を有する有機けい素化合物、光による酸発生剤（光酸発生剤）等がある。これらの触媒または硬化剤の中で特に好ましいのは、アルミキレート化合物と光酸発生剤である。アルミキレート化合物の例としては、エチルアセトアセテートアルミニウムジイソプロピレート、アルミニウムトリスエチルアセトアセテート、アルキルアセトアセテートアルミニウムジイソプロピレート、アルミニウムモノアセチルアセトネートビスエチルアセトアセテート、アルミニウムトリスアセチルアセトネート等であり、光酸発生剤の例としては、ベンジルトリフェニルホスホニウムヘキサフルオロホスフェート、その他のホスホニウム塩やトリフェニルホスホニウムヘキサフルオロホスフェートの塩等を挙げることができる。
【０１４３】
反射防止層の塗布液中の固形分比率として０．５〜２０質量％のバインダが含まれることが好ましい。
【０１４４】
バインダとしては、重合可能なビニル基、アリル基、アクリロイル基、メタクリロイル基、イソプロペニル基、エポキシ基、オキセタン環等の重合性基を２つ以上有し、活性光線照射により架橋構造または網目構造を形成するインクで用いたのと同様なアクリルまたはメタクリル系活性エネルギー線反応性化合物、エポキシ系活性エネルギー線反応性化合物またはオキセタン系活性エネルギー線反応性化合物を用いることができる。これらの化合物はモノマー、オリゴマー、ポリマーを含む。重合速度、反応性の点から、これらの活性基のうちアクリロイル基、メタクリロイル基またはエポキシ基が好ましく、多官能モノマーまたはオリゴマーがより好ましい。また、前述のインク及びハードコート層に用いられる活性光線硬化型樹脂も好ましく用いることができる。更に、アルコール溶解性アクリル樹脂も好ましく用いられる。
【０１４５】
チタン化合物を含む中〜高屈折率層には、バインダとしてアルコール溶解性アクリル樹脂も好ましく用いられ、これによって、膜厚むらが少ない中、高屈折率層を得ることができる。具体的には、アルキル（メタ）アクリレート重合体またはアルキル（メタ）アクリレート共重合体、例えばｎ−ブチルメタクリレート、イソブチルメタクリレート、メチルメタクリレート、エチルメタクリレート、プロピルメタクリレート等の共重合体が好ましく用いられるが、共重合成分としてはこれらに限定されるものではない。市販品としては、ダイヤナールＢＲ−５０、ＢＲ−５１、ＢＲ−５２、ＢＲ−６０、ＢＲ−６４、ＢＲ−６５、ＢＲ−７０、ＢＲ−７３、ＢＲ−７５、ＢＲ−７６、ＢＲ−７７、ＢＲ−７９、ＢＲ−８０、ＢＲ−８２、ＢＲ−８３、ＢＲ−８５、ＢＲ−８７、ＢＲ−８８、ＢＲ−８９、ＢＲ−９０、ＢＲ−９３、ＢＲ−９５、ＢＲ−９６、ＢＲ−１００、ＢＲ−１０１、ＢＲ−１０２、ＢＲ−１０５、ＢＲ−１０７、ＢＲ−１０８、ＢＲ−１１２、ＢＲ−１１３、ＢＲ−１１５、ＢＲ−１１６、ＢＲ−１１７、ＢＲ−１１８（以上、三菱レーヨン（株）製）等が使用できる。これらのモノマー成分も中〜高屈折率層用バインダとして添加することができる。バインダの添加比率を変更することによって屈折率を調整することができる。
【０１４６】
低屈折率層にはすべり剤を添加することが好ましく、滑り性を付与することによって耐傷性を改善することができる。すべり剤としては、シリコーンオイルまたはワックス状物質が好ましく用いられる。
【０１４７】
具体的には、ベヘン酸、ステアリン酸アミド、ペンタコ酸等の高級脂肪酸またはその誘導体、天然物としてこれらの成分を多く含んでいるカルナウバワックス、蜜蝋、モンタンワックスも好ましく使用できる。特公昭５３−２９２号に開示されているようなポリオルガノシロキサン、米国特許第４，２７５，１４６号に開示されているような高級脂肪酸アミド、特公昭５８−３３５４１号、英国特許第９２７，４４６号または特開昭５５−１２６２３８号及び同５８−９０６３３号に開示されているような高級脂肪酸エステル（炭素数が１０〜２４の脂肪酸と炭素数が１０〜２４のアルコールのエステル）、そして米国特許第３，９３３，５１６号に開示されているような高級脂肪酸金属塩、特開昭５１−３７２１７号に開示されているような炭素数１０までのジカルボン酸と脂肪族または環式脂肪族ジオールからなるポリエステル化合物、特開平７−１３２９２号に開示されているジカルボン酸とジオールからのオリゴポリエステル等を挙げることができる。
【０１４８】
低屈折率層に使用する滑り剤の添加量は０．０１〜１０ｍｇ／ｍ^２が好ましい。必要に応じて、中屈折率層や高屈折率層に添加することもできる。
【０１４９】
本発明の低屈折率層には、界面活性剤、柔軟剤、柔軟平滑剤等を添加することが好ましく、これによって耐擦り傷性が改善される。中でもアニオン系または非イオン系の界面活性剤が好ましく、例えば、ジアルキルスルホコハク酸ナトリウム塩、多価アルコール脂肪酸エステルの非イオン界面活性剤乳化物等が好ましい。例えば、リポオイルＮＴ−６、ＮＴ１２、ＮＴ−３３、ＴＣ−１、ＴＣ−６８、ＴＣ−７８、ＣＷ−６、ＴＣＦ−２０８、ＴＣＦ−６０８、ＮＫオイルＣＳ−１１、ＡＷ−９、ＡＷ−１０、ＡＷ−２０、ポリソフターＮ−６０６、塗料用添加剤ＰＣ−７００（日華化学（株）製）等が用いられる。
【０１５０】
本発明に係る低屈折率層は、酸化珪素等の珪素化合物微粒子あるいはフッ素含有化合物微粒子等を塗設して設けることが好ましい。好ましい有機けい素化合物としては、テトラメトキシシラン、テトラエトキシシラン、メチルトリメトキシシラン、メチルトリエトキシシラン、エチルトリメトキシシラン、エチルトリエトキシシラン等を挙げることができ、これらを加水分解することによりシリケートオリゴマーが得られる。加水分解反応は、公知の方法により行うことができ、例えば、上記テトラアルコキシシランに所定量の水を加えて、酸触媒の存在下に、副生するアルコールを留去しながら、通常、室温〜１００℃で反応させる。この反応によりアルコキシシランは加水分解し、続いて縮合反応が起こり、ヒドロキシル基を２個以上有する液状のシリケートオリゴマー（通常、平均重合度は２〜８、好ましくは３〜６）を加水分解物として得ることができる。
【０１５１】
硬化触媒としては、酸、アルカリ、有機金属、金属アルコキシド等を挙げることができるが、本発明においては酸、特にスルホニル基またはカルボキシル基を有する有機酸が好ましく用いられる。例えば、酢酸、ポリアクリル酸、ベンゼンスルホン酸、パラトルエンスルホン酸、メチルスルホン酸等が用いられる。有機酸は１分子内に水酸基とカルボキシル基を有する化合物であればいっそう好ましく、例えば、クエン酸または酒石酸等のヒドロキシジカルボン酸が用いられる。また、有機酸は水溶性の酸であることが更に好ましく、例えば上記クエン酸や酒石酸の他に、レブリン酸、ギ酸、プロピオン酸、リンゴ酸、コハク酸、メチルコハク酸、フマル酸、オキサロ酢酸、ピルビン酸、２−オキソグルタル酸、グリコール酸、Ｄ−グリセリン酸、Ｄ−グルコン酸、マロン酸、マレイン酸、シュウ酸、イソクエン酸、乳酸等が好ましく用いられる。また、安息香酸、ヒドロキシ安息香酸、アトロバ酸等も適宜用いることができる。
【０１５２】
上記有機酸を用いることで、硫酸、塩酸、硝酸、次亜塩素酸、ホウ酸等の無機酸の使用による生産時の配管腐蝕や安全性への懸念が解消できるばかりでなく、加水分解時のゲル化を起こすことなく、安定した加水分解物を得ることができる。添加量は、部分加水分解物１００質量部に対して０．１〜１０質量部、好ましくは０．２〜５質量部がよい。また、水の添加量については部分加水分解物が理論上１００％加水分解し得る量以上であればよく、１００〜３００％相当量、好ましくは１００〜２００％相当量を添加するのがよい。
【０１５３】
このようにして得られた低屈折率層用の塗布組成物は極めて安定である。
（熟成工程）
更に、本発明では熟成工程により、有機けい素化合物の加水分解、縮合による架橋が充分に進み、得られた被膜の特性が優れたものとなる。熟成は、オリゴマー液を放置すればよく、放置する時間は、上述の架橋が所望の膜特性を得るのに充分な程度進行する時間である。具体的には用いる触媒の種類にもよるが、塩酸では室温で１時間以上、マレイン酸では数時間以上、８時間〜１週間程度で充分であり、通常３日前後である。熟成温度は熟成時間に影響を与え、極寒地では２０℃付近まで加熱する手段をとった方がよいこともある。一般に高温では熟成が早く進むが、１００℃以上に加熱するとゲル化が起こるので、せいぜい５０〜６０℃までの加熱が適切である。また、本発明で用いるシリケートオリゴマーについては、上記の他に、例えばエポキシ基、アミノ基、イソシアネート基、カルボキシル基等の官能基を有する有機化合物（モノマー、オリゴマー、ポリマー）等により変性した変性物であってもよく、単独または上記シリケートオリゴマーと併用することも可能である。
【０１５４】
また、本発明においては上記低屈折率層に酸化けい素微粒子を含有させることができる。粒径０．１μｍ以下の酸化けい素微粒子を含むことが好ましい。例えば、アエロジル２００Ｖ（日本アエロジル（株）製）等を添加することができる。特に表面がアルキル基で修飾された酸化けい素微粒子が好ましく用いられ、例えばアエロジルＲ９７２、Ｒ９７２Ｖ（日本アエロジル（株）製）として市販されている表面がメチル基で修飾された酸化けい素微粒子を好ましく添加することができる。このほか特開２００１−２７９９号に記載されている表面がアルキル基で置換された酸化けい素微粒子を用いることもでき、前述のシリケートオリゴマーの加水分解後にアルキルシランカップリング剤により処理することでも容易に得ることができる。添加量としては低屈折率層中の固形分比率で０．１〜４０質量％の範囲となるように添加することが好ましい。
【０１５５】
本発明の各屈折率層には、屈折率の調整あるいは膜質の改善のために更にシラン化合物を添加することができる。
【０１５６】
本発明に係る高〜低屈折率層（光学干渉層ともいう）を塗設する際の塗布液に使用する溶媒は、メタノール、エタノール、１−プロパノール、２−プロパノール、ブタノール等のアルコール類；アセトン、メチルエチルケトン、シクロヘキサノン等のケトン類；ベンゼン、トルエン、キシレン等の芳香族炭化水素類；エチレングリコール、プロピレングリコール、ヘキシレングリコール等のグリコール類；エチルセルソルブ、ブチルセルソルブ、エチルカルビトール、ブチルカルビトール、ジエチルセルソルブ、ジエチルカルビトール、プロピレングリコールモノメチルエーテル等のグリコールエーテル類；Ｎ−メチルピロリドン、ジメチルフォルムアミド、乳酸メチル、乳酸エチル、水等が挙げられ、それらを単独または２種以上混合して使用することができる。
【０１５７】
また、分子内にエーテル結合をもつものが特に好ましく、グリコールエーテル類が更に好ましい。
【０１５８】
グリコールエーテル類としては、プロピレングリコールモノ（Ｃ１〜Ｃ４）アルキルエーテル、プロピレングリコールモノ（Ｃ１〜Ｃ４）アルキルエーテルエステルであり、具体的にはプロピレングリコールモノメチルエーテル（ＰＧＭＥ）、プロピレングリコールモノエチルエーテル、プロピレングリコールモノｎ−プロピルエーテル、プロピレングリコールモノイソプロピルエーテル、プロピレングリコールモノブチルエーテル等が挙げられる。また、プロピレングリコールモノ（Ｃ１〜Ｃ４）アルキルエーテルエステルとしては特にプロピレングリコールモノアルキルエーテルアセテートが挙げられ、具体的にはプロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート等が挙げられる。これらの溶媒は、塗布液中に全有機溶媒の１〜９０質量％添加されていることが好ましい。
【０１５９】
また、本発明に係る高〜低屈折率層の各層の塗布液には各種のレベリング剤、界面活性剤、シリコーンオイル等の低表面張力物質を添加することが好ましい。
【０１６０】
本発明に係る中〜高屈折率層及び低屈折率層の塗設後、金属アルコキシドを含む組成物の加水分解または硬化を促進するため、活性光線を照射することが好ましい。より好ましくは、各層を塗設するごとに活性エネルギー線を照射することである。
【０１６１】
本発明に使用する活性光線は、インクの硬化で用いるのと同様の光源を用いることができる。照射条件はそれぞれのランプによって異なるが、照射光量は２０ｍＪ／ｃｍ^２〜１０，０００ｍＪ／ｃｍ^２が好ましく、更に好ましくは、１００〜２，０００ｍＪ／ｃｍ^２であり、特に好ましくは、４００〜２，０００ｍＪ／ｃｍ^２である。
【０１６２】
紫外線を用いる場合、多層の反射防止層を１層ずつ照射してもよいし、積層後照射してもよいが、多層を積層した後、紫外線を照射することが特に好ましい。
【０１６３】
また、本発明においては、ドライプロセスにより反射防止層を設ける方法も好ましく用いることができ、例えば、特開平７−３３３４０４号、同１１−１３３２０５号、同１１−６１４０６、特開２００２−２２８８０３号に記載の方法に従って、反射防止層あるいは防汚層を形成することができるが、本発明においては、大気圧プラズマ処理方法により反射防止層を形成することが、特に好ましい。
【０１６４】
【実施例】
次に、本発明の具体的態様とその効果を記載して、本発明を更に説明するが、無論、本発明の実施態様はこれに限定されるものではない。
【０１６５】
〔実施例１〕
透明基材の作製
下記のようにドープを調製して、透明基材であるセルロースエステルフィルムを作製した。
【０１６６】

ドープ組成物を密封容器に投入し、７０℃まで加熱し、撹拌しながらセルローストリアセテート（ＴＡＣ）を完全に溶解しドープを得た。溶解に要した時間は４時間であった。ドープ組成物を濾過した後、ベルト流延装置を用い、ドープ（温度３５℃）を２２℃のステンレスバンド支持体上に均一に流延した。ステンレスバンド支持体の温度は２０℃であった。
【０１６７】
その後、剥離可能な範囲まで乾燥させた後、ステンレスバンド支持体上からドープを剥離した。このときのドープの残留溶媒量は２５％であった。ドープ流延から剥離までに要した時間は３分であった。ステンレスバンド支持体から剥離した後、幅方向に保持しながら１２０℃で乾燥させた後、幅保持を解放して、多数のロールで搬送させながら１２０℃、１３５℃の乾燥ゾーンで乾燥を終了させ、フィルム両端に幅１０ｍｍ、高さ５μｍのナーリング加工を施して、膜厚４０μｍのセルローストリアセテートフィルムを作製した。フィルム幅は１３００ｍｍ、巻き取り長は３０００ｍとした。巻き取り張力は、初期張力１５０Ｎ／１３００ｍｍ、最終巻張力１００Ｎ／１３００ｍｍとした。
【０１６８】
上記作製したセルロースエステルフィルムにおいて、縞（ストライプ）パターンを有するライトコントロールフィルムをインクジェット方式で形成した。
【０１６９】
ライトコントロールフィルムの作製
セルロースエステルフィルム上に、下記の黒色インク液１をインクジェット方式によりインク液滴として１ｐｌで出射し、０．２秒後に活性光線照射部より１００ｍＪ／ｃｍ^２の照射強度で紫外線照射して硬化させた後、線幅５μｍの縞パターンを形成する。また縞以外の場所を下記透明インク液２を同様にインクジェット方式によりインク液滴として１ｐｌで出射し、０．２秒後に活性光線照射部より１００ｍＪ／ｃｍ^２の照射強度で紫外線照射して硬化させる。これを繰り返して、膜厚を３０μｍとする。その後、熱風の温度、風速を徐々に強め最終的に８５℃で乾燥し、更に１００ｍＪ／ｃｍ^２の照射強度で紫外線照射してライトコントロールフィルムを形成した。
【０１７０】
〈インクジェット出射方法〉
インクジェット出射装置は、ラインヘッド方式（図１０（ａ）と同様構造）を使用し、ノズル径が３．５μｍのノズルを所定数有するインクジェットヘッド１０基を準備した。インクジェットヘッドは図９に記載の構成のものを使用した。
【０１７１】
インク供給系は、インク供給タンク、フィルター、ピエゾ型のインクジェットヘッド及び配管から構成されており、インク供給タンクからインクジェットヘッド部までは、断熱及び加温（４０℃）し、出射温度は４０℃、駆動周波数は２０ｋＨｚで行った。
【０１７２】
〈黒色インク液１の組成〉
カーボンブラック ２０質量部
ジペンタエリスリトールヘキサアクリレート １００質量部
（２量体及び３量体以上の成分を含む）
光反応開始剤（ジメトキシベンゾフェノン） ４質量部
プロピレングリコールモノメチルエーテル ３０質量部
メチルエチルケトン １００質量部
〈透明インク液２の組成〉
ジペンタエリスリトールヘキサアクリレート １００質量部
（２量体及び３量体以上の成分を含む）
光反応開始剤（ジメトキシベンゾフェノン） ４質量部
プロピレングリコールモノメチルエーテル ３０質量部
メチルエチルケトン １００質量部
形成されたのは図１（ａ）、（ｂ）に示すものと同様のライトコントロールフィルムである。
【０１７３】
上記ライトコントロールフィルムの縞（ストライプ）と直角方向（図ｂの上下方向）の光入射角度と光透過率の関係は、図２に示す通りであった。
【０１７４】
〔実施例２〕
実施例１と同様な方法により、図３に示す通りの格子パターンを有するライトコントロールフィルムをインクジェット方式で形成した。
【０１７５】
上記格子状パターンのライトコントロールフィルムの上下方向と左右方向の光入射角度と光透過率の関係は、図４（ａ）、（ｂ）の如くであった。
【０１７６】
〔実施例３〕
実施例１と同様な方法により、図５に示す点状パターンを有するライトコントロールフィルムをインクジェット方式で形成した。
【０１７７】
上記点状パターンのライトコントロールフィルムの上下方向と左右方向の光入射角度と光透過率の関係は、図６（ａ）、（ｂ）の如くであった。
【０１７８】
〔実施例４〕
実施例１と同様な方法により、図７に示すハニカムパターンを有するライトコントロールフィルムをインクジェット方式で形成した。
【０１７９】
上記ハニカムパターンのライトコントロールフィルムの上下方向と左右方向の光入射角度と光透過率は図８（ａ）、（ｂ）に示した通りである。
【０１８０】
〔実施例５〕
実施例１で作製したセルロースエステルフィルムにおいて、下記ハードコート層を塗設した後、実施例１記載のインクジェット方式で、ライトコントロールフィルムを形成した。
【０１８１】
ハードコート層の塗布
セルロースエステルフィルムの一方の面に、下記のハードコート層塗布組成物をスリットダイで塗布し、熱風の温度、風速を徐々に強め最終的に８５℃で乾燥し、続いて活性光線照射部より１１５ｍＪ／ｃｍ^２の照射強度で紫外線照射し、乾燥膜厚で５μｍの中心線平均表面粗さ（Ｒａ）１２ｎｍのハードコート層を設けた。
【０１８２】

〔実施例６〕
実施例１で作製したライトコントロールフィルム上に、下記の防眩層を塗布方式で用いて形成した。
【０１８３】
防眩層の塗布
ライトコントロールフィルム上に、下記の防眩層塗布組成物をウェット膜厚で１０μｍとなるようにスリットダイで塗布し、熱風の温度、風速を徐々に強め最終的に８５℃で乾燥し、続いて活性光線照射部より１１５ｍＪ／ｃｍ^２の照射強度で紫外線照射し、乾燥膜厚で５μｍの防眩層を設けた。
【０１８４】

得られたライトコントロールフィルムを 液晶表示パネル（ＮＥＣ（株）製 カラー液晶ディスプレイ ＭｕｌｔｉＳｙｎｃ ＬＣＤ１５２５Ｊ：型名 ＬＡ−１５２９ＨＭ）の前面に装着して、視認性の評価を実施した。
【０１８５】
その結果、オフィス内のもっとも近い蛍光灯の写り込みが全く気にならず、またフォントの大きさ８以下の文字もはっきりと読める状態であった。
【０１８６】
〔実施例７〕
実施例１で作製したライトコントロールフィルム上に、下記のようにして中屈折率層、高屈折率層、次いで低屈折率層の順に反射防止層を塗設した。
【０１８７】
中屈折率層の塗布
ライトコントロールフィルム上に、下記中屈折率層組成物を押し出しコーターで塗布し、８０℃で５分間乾燥させた後、高圧水銀ランプ（８０Ｗ）を用いて紫外線を１７５ｍＪ／ｃｍ^２照射して硬化させ、厚さが７８ｎｍとなるように中屈折率層を設けた。なお、この中屈折率層の屈折率は１．７０であった。
【０１８８】

高屈折率層の形成
上記中屈折率層上に、下記の高屈折率層組成物を押し出しコーターで塗布し、８０℃で５分間乾燥させた後、高圧水銀ランプ（８０Ｗ）を用いて紫外線を１７５ｍＪ／ｃｍ^２照射して硬化させ、厚さが６６ｎｍとなるように高屈折率層を設けた。尚、この高屈折率層の屈折率は１．８５であった。
【０１８９】

低屈折率層の形成
上記高屈折率層上に、下記の低屈折率層組成物を押し出しコーターで塗布し、８０℃で５分間乾燥させた後、更に１２０℃で５分間熱硬化させ、さらに紫外線を１７５ｍＪ／ｃｍ^２照射して硬化させ、厚さ９５ｎｍとなるように低屈折率層を設けた。尚、この低屈折率層の屈折率は１．４５であった。
【０１９０】
〈テトラエトキシシラン加水分解物Ａの調製〉
まず、テトラエトキシシラン５８０ｇとエタノール１１４４ｇを混合し、これにクエン酸水溶液（クエン酸１水和物５．４ｇを水２７２ｇに溶解したもの）を添加した後に、室温（２５℃）にて１時間撹拌することでテトラエトキシシラン加水分解物Ａを調製した。
【０１９１】
〈低屈折率層組成物〉
プロピレングリコールモノメチルエーテル ３０３質量部
イソプロピルアルコール ３０５質量部
テトラエトキシシラン加水分解物Ａ １３９質量部
γ−メタクリロキシプロピルトリメトキシシラン
（信越化学（株）製 ＫＢＭ５０３） １．６質量部
１０％ＦＺ−２２０７、プロピレングリコールモノメチルエーテル溶液
（日本ユニカー（株）製） １．３質量部
得られたライトコントロールフィルムを 液晶表示パネル（ＮＥＣ（株）製 カラー液晶ディスプレイ ＭｕｌｔｉＳｙｎｃ ＬＣＤ１５２５Ｊ：型名 ＬＡ−１５２９ＨＭ）の前面に装着して、視認性の評価を実施した。
【０１９２】
その結果、オフィス内のもっとも近い蛍光灯の写り込みが全く気にならず、またフォントの大きさ８以下の文字もはっきりと読める状態であった。
【０１９３】
また、動画及び鮮鋭性評価用のテストチャート画像を出力し、画像のしまり及び鮮鋭性を下記の基準に則り評価した。その結果、動画の黒のしまりが非常に良好で、かつテストパターンが、極めて鮮鋭に映し出されていた。
【０１９４】
〔比較例１〕
特開昭５１−４４１８６号記載の方法により、膜厚１８０μｍの透明な薄い板（セルロースアセチルブチレート）と膜厚２０μｍ黒色の薄い板（カーボンブラックを含有したセルロースアセチルブチレート）と交互に積層し、所望の厚さになった処で積層方向に対して垂直方向にフィルム状にスライスしてルーバー付きライトコントロールフィルムを作製した。
【０１９５】
しかし、断面に形成されたパターンが不規則になり、透過率が３０％と低くなってしまった。
【０１９６】
【発明の効果】
本発明により、製造が容易であり、機械的強度に優れ、不要な入射光の遮光性に優れ、所定方向から見た画像は明るく鮮明であり、かつ、点、縞、格子またはハニカム模様等のパターン形成が自由に出来る、ライトコントロールフィルムとその製造方法、及び製造に用いるインクジェット装置を提供することが出来る。
【図面の簡単な説明】
【図１】本発明のライトコントロールフィルムの構造を説明する断面図と上面図。
【図２】ストライプ状パターンと直角方向（図１の上下方向）の光入射角度と光透過率の関係を説明する図。
【図３】格子状パターンを説明する図。
【図４】格子状タイプのライトコントロールフィルムの上下方向と左右方向の光入射角度と光透過率との関係を説明する図。
【図５】点状パターンを説明する図。
【図６】点状タイプのライトコントロールフィルムの上下方向と左右方向の光入射角度と光透過率との関係を説明する図。
【図７】ハニカム状パターンを説明する図。
【図８】ハニカムタイプのライトコントロールフィルムの上下方向と左右方向の光入射角度と光透過率との関係を説明する図。
【図９】インクジェットヘッドの断面図とその矢視拡大図。
【図１０】インクジェットヘッド部、ノズルプレートの一例を示す概略図。
【図１１】インクジェット方式の一例の概念図。
【符号の説明】
１ 透明基体（支持体）
２ パターン像
１０ インクジェットヘッド
１１ 基板
１２ 圧電素子
１３ 流路板
１３ａ インク流路
１３ｂ 壁部
１４ 共通液室構成部材
１４ａ 共通液室
１５ インク供給パイプ
１６ ノズルプレート
１６ａ ノズル
１７ 駆動用回路プリント板（ＰＣＢ）
１８ リード部
１９ 駆動電極
２０ 溝
２１ 保護板
２２ 流体抵抗
２３、２４ 電極
２５ 上部隔壁
２６ ヒータ
２７ ヒータ電源
２８ 伝熱部材[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a light control film, a method for producing the same, and an ink jet device used for the production.
[0002]
[Prior art]
2. Description of the Related Art Conventionally, a light control film has been used to block external light incident on an image surface of a CRT or the like so that an image can be easily viewed. The film is capable of selectively transmitting light at a specific incident angle and blocking other light.
[0003]
Typical production methods are described in JP-B-47-43845, JP-A-50-92751, and JP-A-50-92751, and Patent Literature 1 below, which describe an invention of a plastic film with a louver and a method for producing the same. . These are made by alternately laminating a transparent thin plate and a translucent or opaque thin plate to a desired thickness, thinly slicing from the direction perpendicular to the laminating direction into a film, and producing a plastic film with louvers. A method called the Bing method is disclosed. The characteristics of the finished film are that it transmits the light parallel to the laminating direction most, and the light that enters obliquely to the laminating direction cannot be transmitted because the opaque part blocks the light as the incident angle increases. Will have.
[0004]
Further, in the following Patent Document 2 and JP-A-58-215880, a photosensitive resin is coated on a transparent support, and dots, stripes, or a lattice-shaped relief are formed by light irradiation. A light control film prepared by dyeing a relief is described.
[0005]
However, the light control film produced by the above-described method has the following problems. That is, in the techniques disclosed in JP-B-47-43845, JP-A-50-92751, and JP-A-50-92751, an opaque area and a transparent area are formed by laminating a plate having a certain thickness, and the thickness is reduced. Since slicing is complicated in terms of the process, and since the cross-sectional portion of the laminate is used as the light control film surface, a large-sized one is extremely difficult to produce.
[0006]
On the other hand, the techniques disclosed in Patent Literature 2 and JP-A-58-215880 can form various and fine relief images, but have a problem that the mechanical strength is not sufficient.
[0007]
Further, in order to solve the above problem, there is disclosed an invention in which a silver salt photosensitive layer is provided on a transparent support, and a pattern is formed by exposing and developing the photosensitive layer to form a light control film (Patent Document 1). 3).
[0008]
This method is epoch-making in that it has relatively high productivity and can form a variety of pattern shapes. However, since the pattern is formed with an aqueous developer, the photosensitive layer must be water-absorbing and cannot have a very high film strength. In addition, since a pattern is formed by exposure, if a high-density pattern is to be formed, there is a problem that the accuracy in the direction perpendicular to the film surface (depth direction) becomes insufficient due to light scattering or the like.
[0009]
[Patent Document 1]
JP-A-51-44186
[0010]
[Patent Document 2]
Japanese Patent Publication No. 2-19449
[0011]
[Patent Document 3]
JP-A-11-72603
[0012]
[Problems to be solved by the invention]
An object of the present invention is easy to manufacture, excellent in mechanical strength, excellent in blocking light of unnecessary incident light, an image viewed from a predetermined direction is bright and clear, and points, stripes, lattices or honeycomb patterns It is an object of the present invention to provide a light control film, a method for producing the same, and an ink jet apparatus used for the production, which can freely form a pattern such as a film.
[0013]
[Means for Solving the Problems]
As a result of intensive studies, the present inventors have found that the object of the present invention can be achieved by adopting the following configuration.
[0014]
[1] A method for producing a light control film, comprising forming a pattern for light control on a transparent substrate by an inkjet method.
[0015]
[2] The method for producing a light control film according to [1], wherein the pattern for light control is any one of a dot, a stripe, a lattice pattern, and a honeycomb pattern.
[0016]
[3] A pattern for light control is formed by emitting ink droplets containing at least a resin and a dye or a pigment, and regions other than the pattern are formed by emitting ink droplets containing a transparent resin as a main component. The method for producing a light control film according to [1] or [2].
[0017]
[4] The resin according to [3], wherein the resin contained in the ink droplets for pattern formation and the transparent resin contained in the ink droplets for regions other than the pattern are actinic ray-curable resins. Manufacturing method of light control film.
[0018]
[5] The method for producing a light control film according to [4], wherein an actinic ray is irradiated immediately after the ink droplets have landed on a transparent substrate.
[0019]
[6] The light according to [3], wherein the resin contained in the ink droplets for pattern formation and the transparent resin contained in the ink droplets for regions other than the pattern are thermosetting resins. Control film manufacturing method.
[0020]
[7] The method for producing a light control film according to [6], wherein a heat treatment is performed immediately after the ink droplets land on a transparent substrate.
[0021]
[8] A light control film produced by the method for producing a light control film according to any one of [1] to [7].
[0022]
[9] The light according to [8], wherein the transmittance of vertically incident light to the light control film is 40% or more, and the transmittance of light rays coming from a 30-degree oblique direction is 20% or less. Control film.
[0023]
[10] A light control film, wherein a fine uneven structure is formed on the light control film surface according to [8] or [9] by an inkjet method to impart antiglare properties.
[0024]
[11] At least one hard coat layer is formed on the surface of the light control film according to [8] or [9], and a fine uneven structure is formed thereon by an inkjet method to impart antiglare property. Light control film characterized by the following.
[0025]
[12] A light control film, wherein an antireflection layer is provided on the light control film surface according to [8] or [9].
[0026]
[13] A light control film, wherein an antiglare layer is formed on the light control film surface according to [8] or [9], and an antireflection layer is provided on the antiglare layer.
[0027]
[14] An ink jet apparatus for producing the light control film according to any one of [8] to [13], wherein an actinic ray irradiating section or an actinic ray irradiating section is provided so that actinic rays or heat does not directly act on the ink jet head section. An ink-jet apparatus comprising a heating unit.
[0028]
BEST MODE FOR CARRYING OUT THE INVENTION
Next, materials, compounds, production apparatuses, and the like that can be used in the present invention will be described.
[0029]
(Transparent substrate)
Preferred requirements for the transparent substrate (support) according to the present invention include easy production, optical isotropicity, and transparency.
[0030]
The term “transparent” as used in the present invention means that the visible light transmittance is 60% or more, preferably 80% or more, and particularly preferably 90% or more.
[0031]
There is no particular limitation as long as it has the above properties. For example, cellulose ester films, polyester films, polycarbonate films, polyarylate films, polysulfone (including polyethersulfone) films, polyethylene terephthalate, polyethylene Polyester film such as naphthalate, polyethylene film, polypropylene film, cellophane, cellulose diacetate film, cellulose triacetate, cellulose acetate butyrate film, polyvinylidene chloride film, polyvinyl alcohol film, ethylene vinyl alcohol film, syndiotactic polystyrene film, Polycarbonate film, norbornene resin film (ARTON (manufactured by JSR Corporation), NEX, ZEONEA (Nippon Zeon Co., Ltd.)), polymethylpentene film, polyetherketone film, polyetherketoneimide film, polyamide film, fluororesin film, nylon film, polymethylmethacrylate (PMMA) film, acrylic Examples include a film or a glass plate. These are preferably used from the viewpoint of production, cost, transparency, isotropy, adhesiveness and the like.
[0032]
[Characteristics of light control film]
The transmittance of the normal incident light of 40% or more means that 40% or more of the light incident perpendicular to the light control film surface is transmitted through the film surface. A 30 degree (°) oblique light transmittance of 20% or less means that when the angle between the film surface and the incident light is 30 °, the transmittance of the light beam is 20% or less. When this value varies depending on the direction of incident light, it means that the minimum transmittance is 20% or less. In addition, the transmittance of light rays from these oblique directions can be consciously changed by changing the width of a striped pattern formed on the light control film surface in the vertical and horizontal directions as described later. It is.
[0033]
The pattern formed on the transparent substrate may be any of those having dots, stripes, lattice patterns, honeycomb patterns, or the like.
[0034]
The structure of the obtained light control film is, for example, as shown in FIG. 1 (FIG. 1A is a sectional view, and FIG. 1B is a top view). Stripes having a line width of 5 μm and a depth of 30 μm are regularly formed at intervals of 15 μm. Reference numeral 2 denotes a pattern image, and 1 denotes a PMMA plate (1 mm thick) transparent substrate.
[0035]
The characteristics of this light control film were as follows.
The light transmittance of vertically incident light having an angle of 90 ° with the support was 60%. The light transmittance of incident light having an angle of 30 ° with the support was 1%.
[0036]
The relationship between the stripe pattern of the light control film and the light incident angle and the light transmittance in a direction perpendicular to the vertical direction (the vertical direction in FIG. 1) was as shown in FIG.
[0037]
A grid pattern was formed in the same manner as in FIG. 1 except that a grid pattern having a line width (light transmitting portion) of 5 μm and a line space (light shielding portion) of 15 μm shown in FIG. 3 was used instead of the stripe pattern. A light control film having a pattern was obtained.
[0038]
In this case, the relationship between the light transmittance in the vertical and horizontal directions and the light incident angle of the light control film of the lattice type is shown in FIG.
[0039]
As described above, it is understood that the use of a lattice-shaped document makes it possible to produce a light control film having a lattice-like pattern whose transmittance can be changed depending on the angle of incident light in the vertical and horizontal directions.
[0040]
Next, a dot-like pattern is formed in the same manner as that shown in FIG. 1 except that a dot-like pattern shown in FIG. 5 is formed on the transparent substrate in place of the stripe-like pattern shown in FIG. Was obtained. FIG. 5 shows the dot sizes and intervals of the document.
[0041]
FIG. 6 shows the relationship between the light transmittance in the vertical and horizontal directions and the light incident angle of the point type light control film.
[0042]
From the results shown in FIG. 6, it can be seen that a light control film in which the light transmittance is changed in the vertical and horizontal directions can be easily formed by using the dot pattern.
[0043]
Further, a light control film having a honeycomb pattern was obtained in the same manner except that the honeycomb pattern shown in FIG. 7 was used instead of the stripe pattern described in FIG. The size and interval of the honeycomb pattern of the document are shown in FIG.
[0044]
FIG. 8 shows the relationship between the light transmittance in the vertical and horizontal directions and the light incident angle of the honeycomb type light control film. This shows that a light control film in which light transmittance is changed in the vertical and horizontal directions can be more easily produced.
[0045]
[Formation of pattern]
The pattern of the light control film is prepared by an inkjet method.
[0046]
Next, the ink jet system according to the present invention will be described.
FIG. 9 is a cross-sectional view illustrating an example of an inkjet head that can be used in the inkjet method according to the present invention.
[0047]
FIG. 9A is a cross-sectional view of the inkjet head, and FIG. 9B is an enlarged view taken along line AA of FIG. 9A. In the figure, 11 is a substrate, 12 is a piezoelectric element, 13 is a flow path plate, 13a is an ink flow path, 13b is a wall, 14 is a common liquid chamber constituent member, 14a is a common liquid chamber, 15 is an ink supply pipe, 16 Is a nozzle plate, 16a is a nozzle, 17 is a driving circuit printed circuit board (PCB), 18 is a lead portion, 19 is a driving electrode, 20 is a groove, 21 is a protection plate, 22 is a fluid resistance, 23 and 24 are electrodes, 25 Is an upper partition, 26 is a heater, 27 is a heater power supply, 28 is a heat transfer member, and 10 is an ink jet head.
[0048]
In the integrated inkjet head 10, the laminated piezoelectric element 12 having the electrodes 23 and 24 is subjected to groove processing in the direction of the flow path 13a corresponding to the flow path 13a, and the groove 20 and the driving piezoelectric element 12b are formed. And a non-driven piezoelectric element 12a. A filler is sealed in the groove 20. The channel plate 13 is joined to the grooved piezoelectric element 12 via an upper partition 25. That is, the upper partition 25 is supported by the non-driven piezoelectric element 12a and the wall 13b separating the adjacent flow path. The width of the driving piezoelectric element 12b is slightly smaller than the width of the flow path 13a, and the driving piezoelectric element 12b selected by the driving circuit on the driving circuit printed circuit board (PCB) receives the driving piezoelectric element when a pulse signal voltage is applied. The element 12b changes in the thickness direction, and the volume of the flow path 13a changes through the upper partition wall 25. As a result, ink droplets are ejected from the nozzles 16a of the nozzle plate 16.
[0049]
The heaters 26 are bonded to the flow path plate 13 via heat transfer members 28, respectively. The heat transfer member 28 is provided so as to extend around the nozzle surface. The heat transfer member 28 aims at efficiently transmitting the heat from the heater 26 to the flow path plate 13 and carrying the heat from the heater 26 to the vicinity of the nozzle surface to warm the air near the nozzle surface. A material having good conductivity is used. For example, preferable materials include metals such as aluminum, iron, nickel, copper, and stainless steel, and ceramics such as SiC, BeO, and AlN.
[0050]
When the piezoelectric element is driven, the piezoelectric element is displaced in a direction perpendicular to the longitudinal direction of the flow path, and the volume of the flow path changes. The change in the volume causes the nozzle to eject ink droplets. The piezoelectric element is given a signal to keep the flow path volume reduced at all times, and is displaced in a direction to increase the flow path volume with respect to the selected flow path. By applying a given pulse signal, ink is ejected from the nozzle corresponding to the flow path as an ink droplet.
[0051]
FIG. 10 is a schematic view showing an example of an ink jet head unit and a nozzle plate that can be used in the present invention.
[0052]
10, (a) of FIG. 10 is a sectional view of the head portion, and (b) of FIG. 10 is a plan view of the nozzle plate. In the figure, 1 is a transparent substrate, 31 is an ink droplet, 32 is a nozzle, and 29 is an actinic ray irradiation unit. The ink droplet 31 ejected from the nozzle 32 flies in the direction of the transparent substrate 1 and adheres. The ink droplets that have landed on the transparent substrate 1 are immediately irradiated with actinic rays from an actinic ray irradiating section 29 disposed upstream thereof, and are cured. In addition, 35 is a back roll that holds the transparent substrate 1.
[0053]
In the present invention, as shown in FIG. 10B, the nozzles of the ink jet head are preferably arranged in a staggered manner, and are provided in multiple stages in parallel in the transport direction of the transparent substrate 1. preferable.
[0054]
FIG. 11 shows a conceptual diagram of an example of an ink jet system that can be preferably used in the present invention.
[0055]
In FIG. 11, a) of FIG. 11 shows a method of arranging the inkjet head 10 in the width direction of the transparent substrate 1 and forming a pattern on the surface of the transparent substrate 1 while transporting the substrate 1 (line head method). FIG. 11B shows a method of forming a pattern on the surface of the inkjet head 10 while moving in the sub-scanning direction (flat head method). FIG. Is a method of forming a pattern on the surface while scanning in the width direction (capstan method), and any method can be used. In the present invention, the line head method is preferable from the viewpoint of productivity. Reference numeral 29 in FIGS. 11A to 11C denotes an actinic ray irradiation unit used when an actinic ray curable resin described later is used as the ink.
[0056]
Further, in the present invention, another actinic ray irradiation section may be provided on the downstream side in the transport direction of the transparent substrate in FIGS. 11A, 11B and 11C.
[0057]
In the present invention, the ink droplets are preferably 0.1 to 100 pl, more preferably 0.1 to 50 pl, and particularly preferably 0.1 to 10 pl.
[0058]
The viscosity of the ink droplet at 25 ° C. is preferably 0.1 to 100 mPa · s, and more preferably 0.1 to 50 mPa · s.
[0059]
(Patterning composition)
Next, the pattern imparting composition (also referred to as ink) used in the inkjet method according to the present invention will be described.
[0060]
In addition, in addition to the patterning composition, a transparent ink is applied to the area where the pattern is not formed, and the thickness of the light control film is made substantially the same in the area where the pattern is formed and in the area where it is not. Is preferred. In this case, the transparent “ink” to be applied to the area where the pattern is not formed may be obtained by removing the pigment or the dye from the “ink” of the patterning composition, or the resin composition may be different. A thing may be used. If any of the “inks” is ejected by an ink jet type device, the ink can be ejected accurately based on predetermined pattern information. However, it is preferable to unify whether the resin used is an actinic ray-curable resin or a thermosetting resin.
[0061]
The ink according to the present invention preferably uses an actinic ray-curable resin or a thermosetting resin.
[0062]
First, the actinic ray-curable resin according to the present invention will be described.
The actinic ray-curable resin is a resin which is cured through a cross-linking reaction or the like by irradiation with actinic rays such as ultraviolet rays or electron beams. Typical examples of the actinic ray curable resin include an ultraviolet ray curable resin and an electron beam curable resin, but a resin which is cured by irradiation with actinic rays other than ultraviolet rays and electron beams may be used.
[0063]
Examples of the ultraviolet-curable resin include an ultraviolet-curable acrylic urethane-based resin, an ultraviolet-curable polyester acrylate-based resin, an ultraviolet-curable epoxy acrylate-based resin, an ultraviolet-curable polyol acrylate-based resin, and an ultraviolet-curable epoxy resin. be able to.
[0064]
UV-curable acrylic urethane-based resins are generally obtained by reacting a polyester polyol with an isocyanate monomer or a prepolymer, and further adding 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate (hereinafter acrylate includes methacrylate). Can be easily obtained by reacting an acrylate monomer having a hydroxyl group such as 2-hydroxypropyl acrylate. For example, a mixture of 100 parts of Unidick 17-806 (produced by Dainippon Ink Co., Ltd.) and 1 part of Coronate L (produced by Nippon Polyurethane Co., Ltd.) described in JP-A-59-151110 is preferably used. .
[0065]
The UV-curable polyester acrylate resin can be easily obtained by reacting a monomer such as 2-hydroxyethyl acrylate, glycidyl acrylate, or acrylic acid with a hydroxyl group or a carboxyl group at the end of the polyester (see, for example, No. 59-151112).
[0066]
The ultraviolet-curable epoxy acrylate resin is obtained by reacting a monomer such as acrylic acid, acrylic acid chloride, or glycidyl acrylate with a hydroxyl group at the terminal of the epoxy resin.
[0067]
Examples of UV-curable polyol acrylate resins include ethylene glycol (meth) acrylate, polyethylene glycol di (meth) acrylate, glycerin tri (meth) acrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, and dipentane. Examples include erythritol pentaacrylate, dipentaerythritol hexaacrylate, and alkyl-modified dipentaerythritol pentaacrylate.
[0068]
As an example of the UV-curable epoxy acrylate resin and the UV-curable epoxy resin, useful epoxy active light-reactive compounds are shown.
[0069]
(A) Glycidyl ether of bisphenol A (this compound is obtained as a mixture having different degrees of polymerization by the reaction of epichlorohydrin and bisphenol A)
(B) A compound having a glycidyl ether group at the terminal by reacting a compound having two phenolic OH such as bisphenol A with epichlorohydrin, ethylene oxide and / or propylene oxide
(C) Glycidyl ether of 4,4'-methylenebisphenol
(D) Epoxy compound of phenol formaldehyde resin of novolak resin or resol resin
(E) Compound having an alicyclic epoxide, for example, bis (3,4-epoxycyclohexylmethyl) oxalate, bis (3,4-epoxycyclohexylmethyl) adipate, bis (3,4-epoxy-6-cyclohexylmethyl) Adipate, bis (3,4-epoxycyclohexylmethylpimelate), 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-1-methylcyclohexylmethyl-3 ', 4' -Epoxycyclohexanecarboxylate, 3,4-epoxy-1-methyl-cyclohexylmethyl-3 ', 4'-epoxy-1'-methylcyclohexanecarboxylate, 3,4-epoxy-6-methyl-cyclohexylmethyl-3' , 4'-epoxy-6'-me Le-1'-cyclohexane-carboxylate, 2- (3,4-epoxycyclohexyl-5 ', 5'-spiro-3 ", 4" - epoxy) cyclohexane - meta - dioxane
(F) Diglycidyl ethers of dibasic acids, for example, diglycidyl oxalate, diglycidyl adipate, diglycidyl tetrahydrophthalate, diglycidyl hexahydrophthalate, diglycidyl phthalate
(G) Diglycidyl ethers of glycols, for example, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, copoly (ethylene glycol-propylene glycol) diglycidyl Ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether
(H) glycidyl esters of polymer acids, for example, polyglycidyl esters of polyacrylic acid, polyester diglycidyl esters
(I) glycidyl ethers of polyhydric alcohols, for example, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol diglycidyl ether, pentaerythritol triglycidyl ether, pentaerythritol tetraglycidyl ether, glucose triglycidyl ether
(J) The diglycidyl ether of 2-fluoroalkyl-1,2-diol is the same as the compound example of the fluorine-containing epoxy compound of the fluorine-containing resin of the low refractive index substance.
(K) Examples of the fluorinated alkane-terminated diol glycidyl ether include fluorine-containing epoxy compounds of the above-mentioned fluorine-containing resin having a low refractive index.
Can be mentioned.
[0070]
The molecular weight of the epoxy compound is 2,000 or less, preferably 1,000 or less, as an average molecular weight.
[0071]
When the above-mentioned epoxy compound is cured by actinic rays, it is effective to use a mixture of (h) or (i) a compound having a polyfunctional epoxy group in order to further increase the hardness.
[0072]
The photopolymerization initiator or photosensitizer for cationically polymerizing the epoxy-based active light-reactive compound is a compound capable of releasing a cationic polymerization initiator by irradiation with actinic light, and is particularly preferably a compound that initiates cationic polymerization by irradiation. It is a group of double salts that release a functional Lewis acid.
[0073]
The actinic ray-reactive compound epoxy resin forms a polymerized, crosslinked structure or a network structure not by radical polymerization but by cationic polymerization. Unlike the radical polymerization, it is not affected by oxygen in the reaction system, and is therefore a preferred actinic ray-reactive resin.
[0074]
The actinic ray-reactive epoxy resin useful in the present invention is polymerized by a photopolymerization initiator or a photosensitizer that releases a substance that initiates cationic polymerization upon irradiation with actinic light. As the photopolymerization initiator, a group of double salts of an onium salt that releases a Lewis acid that initiates cationic polymerization by light irradiation is particularly preferable.
[0075]
A typical example thereof is a compound represented by the following general formula (a).
General formula (a)
[(R¹)_a(R²)_b(R³)_c(R⁴)_dZ]^{w +}[MeX_v]^w-
Wherein the cation is onium, Z is S, Se, Te, P, As, Sb, Bi, O, halogen (eg, I, Br, Cl), or N = N (diazo);¹, R², R³, R⁴Is an organic group which may be the same or different. a, b, c, and d are each an integer of 0 to 3, and a + b + c + d is equal to the valence of Z. Me is a metal or metalloid which is a central atom of the halide complex, and B, P, As, Sb, Fe, Sn, Bi, Al, Ca, In, Ti, Zn, Sc, V, Cr, Mn, Co and the like. X is a halogen, w is the net charge of the halide ion, and v is the number of halogen atoms in the halide ion.
[0076]
Anion [MeX] of the above general formula (a)_v]^w-As a specific example of tetrafluoroborate (BF₄ ⁻), Tetrafluorophosphate (PF₄ ⁻), Tetrafluoroantimonate (SbF₄ ⁻), Tetrafluoroarsenate (AsF₄ ⁻), Tetrachloroantimonate (SbCl₄ ⁻) And the like.
[0077]
Other anions are perchlorate ions (ClO₄ ⁻), Trifluoromethyl sulfite ion (CF₃SO₃ ⁻), Fluorosulfonate ion (FSO₃ ⁻), Toluenesulfonic acid ion, trinitrobenzene anion and the like.
[0078]
Among such onium salts, it is particularly effective to use an aromatic onium salt as a cationic polymerization initiator. Among them, the aromatic haonium salts described in JP-A Nos. 50-151996 and 50-158680 are particularly useful. Nos. 50-151997, 52-30899, 59-55420, 55-125105, and the like. VIA group aromatic onium salts described in JP-A-56-8428, 56-149402, Preferred are oxosulfoxonium salts described in JP-A-57-192429, aromatic diazonium salts described in JP-B-49-17040 and the like, and thiopyrilium salts described in U.S. Pat. No. 4,139,655 and the like. In addition, an aluminum complex and a photodecomposable silicon compound-based polymerization initiator can be used. The cationic polymerization initiator and a photosensitizer such as benzophenone, benzoin isopropyl ether, and thioxanthone can be used in combination.
[0079]
In the case of an actinic ray-reactive compound having an epoxy acrylate group, a photosensitizer such as n-butylamine, triethylamine, and tri-n-butylphosphine can be used. The photosensitizer or photoinitiator used in the actinic ray-reactive compound is sufficient to initiate a photoreaction at 0.1 to 15 parts by mass with respect to 100 parts by mass of the ultraviolet-reactive compound, and is preferably used. 1 to 10 parts by mass. The sensitizer preferably has an absorption maximum in the near ultraviolet region to the visible region.
[0080]
In the actinic ray-curable resin composition useful in the present invention, the polymerization initiator is generally used in an amount of 0.1 to 15 parts by mass based on 100 parts by mass of the actinic ray-curable epoxy resin (prepolymer). Preferably, the addition is more preferably in the range of 1 to 10 parts by mass.
[0081]
Further, an epoxy resin can be used in combination with the urethane acrylate type resin, polyether acrylate type resin, or the like. In this case, it is preferable to use an active ray radical polymerization initiator and an active ray cationic polymerization initiator in combination.
[0082]
In the present invention, an oxetane compound can also be used. The oxetane compound used is a compound having a three-membered oxetane ring containing oxygen or sulfur. Among them, compounds having an oxetane ring containing oxygen are preferred. The oxetane ring may be substituted with a halogen atom, a haloalkyl group, an arylalkyl group, an alkoxyl group, an allyloxy group, or an acetoxy group. Specifically, 3,3-bis (chloromethyl) oxetane, 3,3-bis (iodomethyl) oxetane, 3,3-bis (methoxymethyl) oxetane, 3,3-bis (phenoxymethyl) oxetane, 3-methyl Examples thereof include -3 chloromethyloxetane, 3,3-bis (acetoxymethyl) oxetane, 3,3-bis (fluoromethyl) oxetane, 3,3-bis (bromomethyl) oxetane, and 3,3-dimethyloxetane. In the present invention, any of a monomer, an oligomer and a polymer may be used.
[0083]
Specific examples of the ultraviolet curable resin that can be used in the present invention include, for example, Adeka Optomer KR, BY series KR-400, KR-410, KR-550, KR-566, KR-567, BY-320B (The above are manufactured by Asahi Denka Kogyo Co., Ltd.), Koeihard's A-101-KK, A-101-WS, C-302, C-401-N, C-501, M-101, M-102, T -102, D-102, NS-101, FT-102Q8, MAG-1-P20, AG-106, M-101-C (all manufactured by Koei Chemical Industry Co., Ltd.), Seika Beam PHC2210 (S), PHCX -9 (K-3), PHC2213, DP-10, DP-20, DP-30, P1000, P1100, P1200, P1300, P1400, P1500, P1600, CR900 (above, manufactured by Dainichi Seika Kogyo Co., Ltd.), KRM7033, KRM7039, KRM7130, KRM7131, UVECRYL29201, UVECRYL29202 (above, Daicel UCB Co., Ltd.), RC-5015, RC-5016, RC-5020, RC -5031, RC-5100, RC-5102, RC-5120, RC-5122, RC-5152, RC-5171, RC-5180, RC-5181 (all manufactured by Dainippon Ink and Chemicals, Inc.), Aurex No. 340 Clear (China Paint Co., Ltd.), Sunrad H-601, RC-750, RC-700, RC-600, RC-500, RC-611, RC-612 (all manufactured by Sanyo Chemical Industries, Ltd.) , SP-1509, SP-1507 (manufactured by Showa Polymer Co., Ltd.), RCC-15C (manufactured by Grace Japan Co., Ltd.), Aronix M-6100, M-8030, M-8060 (above, Toagosei Co., Ltd.) Or other commercially available products.
[0084]
In the ink according to the present invention, a binder such as a known thermoplastic resin or a hydrophilic resin such as gelatin can be used by mixing with the above-described actinic ray-curable resin. These resins preferably have a polar group in the molecule. As the polar group, -COOM, -OH, -NR₂, -NR₃X, -SO₃M, -OSO₃M, -PO₃M₂, -OPO₃M (where M represents a hydrogen atom, an alkali metal or ammonium group, X represents an acid that forms an amine salt, and R represents a hydrogen atom or an alkyl group) and the like.
[0085]
In order to start the photopolymerization or photocrosslinking reaction of the actinic ray-reactive compound used in the present invention, the actinic ray-reactive compound is started only with the actinic ray-reactive compound alone, but the induction period of the polymerization is long or the initiation of the polymerization is delayed. Therefore, it is preferable to use a photosensitizer or a photoinitiator, whereby the polymerization can be accelerated.
[0086]
When the ink according to the present invention contains an actinic ray-curable resin, a photoreaction initiator and a photosensitizer can be used during actinic ray irradiation.
[0087]
Specific examples include acetophenone, benzophenone, hydroxybenzophenone, Michler's ketone, α-amyloxime ester, thioxanthone and the like, and derivatives thereof. When a photoreactive agent is used in the synthesis of an epoxy acrylate resin, a sensitizer such as n-butylamine, triethylamine, and tri-n-butylphosphine can be used.
[0088]
When an ultraviolet ray-curable resin is used as the actinic ray-curable resin, an ultraviolet ray absorbent may be contained in the ultraviolet ray-curable resin composition to such an extent that the photo-curing of the ultraviolet ray-curable resin is not hindered.
[0089]
As the ultraviolet absorber, those having excellent absorption of ultraviolet light having a wavelength of 370 nm or less and little absorption of visible light having a wavelength of 400 nm or more are preferably used from the viewpoint of good liquid crystal display properties.
[0090]
Specific examples of the ultraviolet absorber preferably used in the present invention include, for example, oxybenzophenone-based compounds, benzotriazole-based compounds, salicylate-based compounds, benzophenone-based compounds, cyanoacrylate-based compounds, nickel complex-based compounds, and the like. However, the present invention is not limited to these.
[0091]
As the benzotriazole-based ultraviolet absorber, a compound represented by the following general formula (1) is preferably used.
[0092]
Embedded image

[0093]
Where R₁, R₂, R₃, R₄And R₅May be the same or different; a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, an alkyl group, an alkenyl group, an aryl group, an alkoxyl group, an acyloxy group, an aryloxy group, an alkylthio group, an arylthio group, a mono- or dialkylamino group Represents an acylamino group or a 5- to 6-membered heterocyclic group,₄And R₅May be closed to form a 5- to 6-membered carbon ring.
[0094]
Further, these groups described above may have an arbitrary substituent.
Hereinafter, specific examples of the ultraviolet absorbent according to the present invention will be described, but the present invention is not limited thereto.
[0095]
UV-1: 2- (2'-hydroxy-5'-methylphenyl) benzotriazole
UV-2: 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) benzotriazole
UV-3: 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) benzotriazole
UV-4: 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole
UV-5: 2- (2'-hydroxy-3 '-(3 ", 4", 5 ", 6" -tetrahydrophthalimidomethyl) -5'-methylphenyl) benzotriazole
UV-6: 2,2-methylenebis (4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol)
UV-7: 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole
UV-8: 2- (2H-benzotriazol-2-yl) -6- (linear and side chain dodecyl) -4-methylphenol (TINUVIN171, manufactured by Ciba)
UV-9: octyl-3- [3-tert-butyl-4-hydroxy-5- (chloro-2H-benzotriazol-2-yl) phenyl] propionate and 2-ethylhexyl-3- [3-tert-butyl- Mixture of 4-hydroxy-5- (5-chloro-2H-benzotriazol-2-yl) phenyl] propionate (TINUVIN109, manufactured by Ciba)
As the benzophenone-based ultraviolet absorber, a compound represented by the following general formula (2) is preferably used.
[0096]
Embedded image

[0097]
In the formula, Y represents a hydrogen atom, a halogen atom or an alkyl group, an alkenyl group, an alkoxyl group and a phenyl group, and these alkyl group, alkenyl group and phenyl group may have a substituent. A is a hydrogen atom, an alkyl group, an alkenyl group, a phenyl group, a cycloalkyl group, an alkylcarbonyl group, an alkylsulfonyl group or -CO (NH)_n-1Represents a -D group, and D represents an alkyl group, an alkenyl group or a phenyl group which may have a substituent. m and n represent 1 or 2.
[0098]
In the above, the alkyl group represents, for example, a linear or branched aliphatic group having up to 24 carbon atoms, the alkoxyl group represents, for example, an alkoxyl group having up to 18 carbon atoms, and the alkenyl group represents, for example, carbon atoms having up to 18 carbon atoms. An alkenyl group of up to 16 represents an allyl group, a 2-butenyl group or the like. Examples of the substituent for the alkyl group, alkenyl group and phenyl group include a halogen atom, for example, a chlorine atom, a bromine atom and a fluorine atom, a hydroxyl group and a phenyl group. May be used).
[0099]
Specific examples of the benzophenone-based compound represented by the general formula (2) are shown below, but the present invention is not limited thereto.
[0100]
UV-10: 2,4-dihydroxybenzophenone
UV-11: 2,2'-dihydroxy-4-methoxybenzophenone
UV-12: 2-hydroxy-4-methoxy-5-sulfobenzophenone
UV-13: bis (2-methoxy-4-hydroxy-5-benzoylphenylmethane)
As the ultraviolet absorber preferably used in the present invention, a benzotriazole-based ultraviolet absorber or a benzophenone-based ultraviolet absorber having high transparency and excellent in preventing deterioration of the polarizing plate and liquid crystal is preferable, and unnecessary coloring is less. Benzotriazole UV absorbers are particularly preferably used.
[0101]
Further, the ultraviolet absorber having a distribution coefficient of 9.2 or more described in JP-A-2001-187825 improves the surface quality of the support and is excellent in coatability. In particular, it is preferable to use an ultraviolet absorber having a distribution coefficient of 10.1 or more.
[0102]
Also, the high molecular ultraviolet absorber described in the general formula (1) or the general formula (2) described in JP-A-6-148430 or the general formulas (3), (6) and (7) described in Japanese Patent Application No. 2000-156039. (Or an ultraviolet absorbing polymer) is also preferably used. As the high-molecular ultraviolet absorber, PUVA-30M (manufactured by Otsuka Chemical Co., Ltd.) is commercially available.
[0103]
In order to increase the heat resistance of the pattern formed by the inkjet method, an antioxidant that does not suppress the photocuring reaction can be selected and used. For example, hindered phenol derivatives, thiopropionic acid derivatives, phosphite derivatives and the like can be mentioned. Specifically, for example, 4,4'-thiobis (6-tert-3-methylphenol), 4,4'-butylidenebis (6-tert-butyl-3-methylphenol), 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) mesitylene, di-octadecyl-4- Hydroxy-3,5-di-tert-butylbenzyl phosphate and the like can be mentioned.
[0104]
The ink according to the present invention includes SnO₂It is preferable to include an antistatic agent such as conductive fine particles such as ITO, ZnO and ZnO, and crosslinked cationic polymer particles. Further, these compounds may be added to a hard coat layer described later provided on the transparent substrate.
[0105]
In the present invention, when the layer formed by the inkjet method contains an actinic ray-curable resin, the actinic ray irradiation method is preferably to irradiate the actinic ray immediately after the ink droplets land on the transparent substrate. .
[0106]
[Ink ejection and curing conditions]
The term “immediately after the ink droplets have landed on the transparent substrate” in the present invention preferably means a period of 0.001 to 2.0 seconds after the ink droplets land, more preferably 0.001 to 2.0 seconds. 0.0 seconds. If the irradiation interval of the irradiation light source is shorter than 0.001 second, the distance between the nozzle portion and the irradiation light source is too short, and the head is contaminated by a sublimation substance due to a curing reaction, and the irradiation light is spilled to the ink ejection portion, so that the nozzle is not illuminated. This is not preferable because nozzle clogging occurs due to curing in the part. If the irradiation interval of the irradiation light source exceeds 2.0 seconds, it becomes difficult to obtain a desired concave-convex structure defined in the present invention due to the flow, deformation, and the like of the landed ink droplet.
[0107]
In order to prevent light from sneaking into the nozzle portion during the irradiation, in the ink jet system of the present invention, it is preferable to arrange the active light source irradiating portion at a position where it does not directly act on the ink jet head (particularly the nozzle portion). Preferably, a light-shielding plate is provided between the nozzles of the inkjet head so that the irradiated actinic light does not act on the nozzles.
[0108]
Irradiation with actinic rays immediately after the ink droplets have landed may be performed to such an extent that the fluidity of the landed ink droplets is reduced and a desired uneven structure can be formed, and may be in a half-cured state. In this case, it can be completely cured by irradiating an active light source separately installed on the downstream side. By doing so, it is possible to prevent actinic rays from acting on the nozzles of the ink jet head to cause clogging.
[0109]
The actinic rays that can be used in the present invention include, without limitation, ultraviolet rays, electron beams, γ rays, etc., as long as the light source activates the actinic ray-curable resin that is the pattern forming composition. Electron beams are preferred, and ultraviolet rays are particularly preferred in that they can be easily handled and high energy can be easily obtained. As a light source of ultraviolet rays for photopolymerizing the ultraviolet reactive compound, any light source that generates ultraviolet rays can be used. For example, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, and the like can be used. Further, an ArF excimer laser, a KrF excimer laser, an excimer lamp, synchrotron radiation, or the like can be used. Irradiation conditions differ for each lamp, but the amount of irradiation is 1 mJ / cm²More preferably, more preferably, 20 to 10,000 mJ / cm²And particularly preferably 50 to 2000 mJ / cm.²It is.
[0110]
In addition, an electron beam can be used as well. As the electron beam, 50 to 1000 keV, preferably 100 to 100 keV emitted from various electron beam accelerators such as Cockloft-Walton type, Bande graph type, Resonant transformer type, Insulating core transformer type, Linear type, Dynamitron type, High frequency type, etc. An electron beam having an energy of 300 keV can be used.
[0111]
In the present invention, the oxygen concentration in the atmosphere at the time of irradiation with active rays is more preferably 1% or less.
[0112]
Further, in the present invention, the transparent substrate or the like can be heated in order to efficiently promote the curing reaction of the actinic ray. The heating method is not particularly limited, but it is preferable to use a heat plate, a heat roll, a thermal head, or a method of blowing hot air onto the landed ink surface. In addition, the back roll used on the opposite side of the transparent support of the ink jet emission unit may be continuously heated by using a heat roll.
[0113]
The heating temperature cannot be specified unconditionally depending on the type of the actinic ray-curable resin to be used, but is preferably a temperature range that does not affect the transparent substrate such as thermal deformation, and is preferably 30 to 200 ° C. Further, the temperature is preferably from 50 to 120 ° C, particularly preferably from 70 to 100 ° C.
[0114]
(Thermosetting resin)
Next, the thermosetting resin according to the present invention will be described.
[0115]
Examples of the thermosetting resin that can be used in the present invention include an unsaturated polyester resin, an epoxy resin, a vinyl ester resin, a phenol resin, a thermosetting polyimide resin, and a thermosetting polyamideimide.
[0116]
As the unsaturated polyester resin, for example, orthophthalic acid resin, isophthalic acid resin, terephthalic acid resin, bisphenol resin, propylene glycol-maleic acid resin, dicyclopentadiene or a derivative thereof is introduced into the unsaturated polyester composition. Styrene volatile resin with low molecular weight or added with film-forming wax compound, low shrinkage with added thermoplastic resin (polyvinyl acetate resin, styrene-butadiene copolymer, polystyrene, saturated polyester, etc.) Resin, unsaturated polyester directly Br₂Reactive type such as brominated with acetic acid or copolymerized with dibromoneopentyl glycol, a combination of halide such as chlorinated paraffin, tetrabromobisphenol and antimony trioxide, phosphorus compound, aluminum hydroxide, etc. Additive-type flame-retardant resins used as additives, and toughness resins with high toughness (high strength, high elastic modulus, and high elongation rate) hybridized with IPN or polyurethane and silicone, and the like.
[0117]
Examples of the epoxy resin include glycidyl ether epoxy resins including bisphenol A type, novolak phenol type, bisphenol F type, and brominated bisphenol A type, glycidylamine type, glycidyl ester type, cyclic aliphatic type, and heterocyclic epoxy type. And special epoxy resins containing the same.
[0118]
The vinyl ester resin is, for example, a product obtained by dissolving an oligomer obtained by a ring-opening addition reaction between an ordinary epoxy resin and an unsaturated monobasic acid such as methacrylic acid in a monomer such as styrene. There are also special types such as those having a vinyl group at a molecular terminal or a side chain and containing a vinyl monomer. As the vinyl ester resin of the glycidyl ether epoxy resin, for example, there are bisphenol type, novolak type, brominated bisphenol type, etc., and as the special vinyl ester resin, vinyl ester urethane type, vinyl isocyanurate type, side chain vinyl ester type etc. There is.
[0119]
Phenol resins are obtained by polycondensation using phenols and formaldehydes as raw materials, and are classified into resol type and novolak type.
[0120]
Examples of the thermosetting polyimide resin include maleic acid-based polyimides such as polymaleimide amine, polyaminobismaleimide, bismaleimide-O, O'-diallylbisphenol-A resin, bismaleimide-triazine resin, and nadic acid-modified polyimide. And acetylene-terminated polyimide.
[0121]
Further, a part of the above-mentioned actinic ray curable resin can be used as the thermosetting resin.
[0122]
The ink composed of the thermosetting resin according to the present invention may appropriately use an antioxidant or an ultraviolet absorber described in the ink containing the actinic ray-curable resin.
[0123]
In the present invention, when the layer formed by the ink jet method contains a thermosetting resin, the heating method is preferably to perform a heat treatment immediately after the ink droplets land on the transparent substrate.
[0124]
Immediately after the ink droplet lands on the transparent substrate in the present invention, specifically, it is preferable that heating be started at the same time as or within 5 seconds when the ink droplet lands, more preferably 0.001. ２．０2.0 seconds. If the heating interval is shorter than 0.001 second, the distance between the nozzle portion and the heating portion is too short, and if heat is transmitted to the head portion, caution is required because the nozzle portion is clogged due to curing in the nozzle portion. Further, if the heating interval exceeds 5.0 seconds, it becomes difficult to obtain the desired characteristics specified in the present invention due to the flow, deformation, and the like of the landed ink droplets.
[0125]
When these are used as inks, matters different from those of the actinic ray-curable ink will be mainly described.
[0126]
In order to prevent the transfer of heat to the nozzle portion during the heating, in the ink jet system of the present invention, it is preferable that the heating portion is arranged at a position where it does not directly act on the ink jet head (particularly the nozzle portion).
[0127]
The heating method is not particularly limited, but it is preferable to use a heat plate, a heat roll, a thermal head, or a method of blowing hot air onto the landed ink surface. Further, a back roll provided on the opposite side of the transparent support of the ink jet emission unit may be used as a heat roll and may be continuously heated. The heating temperature cannot be specified unconditionally depending on the type of the thermosetting resin to be used, but is preferably a temperature range that does not affect the transparent substrate such as thermal deformation, and is preferably 30 to 200 ° C. The temperature is preferably from 50 to 120 ° C, particularly preferably from 70 to 100 ° C.
[0128]
In the ink according to the present invention, any of the above-mentioned actinic ray curable resins and thermosetting resins can be used, but it is preferable to use actinic ray curable resins.
[0129]
The ink according to the present invention can contain a solvent as needed. For example, the actinic ray-curable resin monomer component or the thermosetting resin monomer component may be dissolved or dispersed in an aqueous solvent, or an organic solvent may be used. An organic solvent having a low boiling point or a high boiling point can be appropriately selected and used, and the amount, type and composition of these solvents are preferably adjusted as appropriate in order to adjust the viscosity of the ink.
[0130]
Examples of the solvent that can be used in the ink according to the present invention include alcohols such as methanol, ethanol, 1-propanol, 2-propanol and butanol; ketones such as acetone, methyl ethyl ketone and cyclohexanone; benzene, toluene, xylene and the like. Aromatic hydrocarbons; glycols such as ethylene glycol, propylene glycol and hexylene glycol; ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, diethyl cellosolve, diethyl carbitol, propylene glycol monomethyl ether and the like Glycol ethers; esters such as N-methylpyrrolidone, dimethylformamide, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, amyl acetate; ethers such as diethyl ether S, water and the like, can be used as a mixture thereof alone or in combination. Those having an ether bond in the molecule are particularly preferable, and glycol ethers are also preferably used.
[0131]
The glycol ethers specifically include the following solvents, but are not particularly limited thereto. Propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, diethylene glycol dimethyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether Ac, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether Ac, ethylene glycol Diethyl ether and the like can be mentioned, and Ac represents acetate. In the ink according to the present invention, among the above solvents, a solvent having a boiling point of less than 100 ° C. is preferable.
[0132]
(Layers other than pattern formation layer)
Next, a preferred embodiment of forming a layer other than the pattern forming layer by the inkjet method in the present invention will be described.
[0133]
The light control film of the present invention preferably has an antiglare layer on a transparent substrate, and takes into consideration the refractive index, film thickness, number of layers, layer order, and the like so that the reflectance is reduced by optical interference thereon. It is preferable that they are laminated.
[0134]
The anti-glare layer is a layer that has a fine uneven structure on the surface, prevents unnecessary surface reflection, and is provided to make the screen easier to see. The degree of the irregularities is such that the center line average roughness (Ra) is about 0.05 to 5.0 μm, and a transparent ink-like antiglare imparting composition containing a resin and inorganic or organic fine particles is prepared by an inkjet method. It is a preferable method to form by discharging. In order to control the roughness formed on the surface of the light control film, the particle size of inorganic or organic fine particles may be adjusted.
[0135]
The antireflection layer according to the present invention, on the antiglare layer, it is preferable to provide a plurality of refractive index layers from the antiglare layer side, further, a high refractive index layer, a low refractive index layer is laminated in order. Preferably, there is. The level of the refractive index is substantially determined by the metal or compound contained therein, for example, Ti is high, Si is low, and the compound containing F is even lower. The refractive index is set by such a combination. The refractive index and the film thickness can be calculated by measuring the spectral reflectance.
[0136]
The antireflection layer is configured by combining a high refractive index layer having a higher refractive index than the support and a low refractive index layer having a lower refractive index than the support. It is particularly preferable to use an antireflection layer composed of three or more refractive index layers, and to form three layers having different refractive indices from the support side into a medium refractive index layer (having a higher refractive index than the support or the antiglare layer). , A layer having a lower refractive index than the high refractive index layer) / a high refractive index layer / a low refractive index layer are preferably used. Alternatively, an antireflection layer having four or more layers in which two or more high refractive index layers and two or more low refractive index layers are alternately laminated is also preferably used.
[0137]
Further, if necessary, it is preferable to further provide an antifouling layer on the low refractive index layer on the outermost surface so that dirt and fingerprints can be easily wiped off. As the antifouling layer, a fluorine-containing organic silane compound is preferably used.
[0138]
The anti-reflection layer according to the present invention can be formed by the above-mentioned coating method, and a metal oxide layer (SiO 2) can be formed by a dry process such as atmospheric pressure plasma treatment or CVD.₂, TiO₂, Ta₂O₅, ZrO₂, ZnO, SnO₂, ITO, etc.).
[0139]
The high refractive index layer according to the present invention preferably contains titanium oxide. These can be added as fine particles, but more preferably, a refractive index of 1.55 to 2 which is formed by applying and drying a coating solution containing a monomer, oligomer or a hydrolyzate of an organic titanium compound. 5 layers.
[0140]
Examples of the monomer and oligomer of the organic titanium compound used in the present invention include Ti (OCH₃)₄, Ti (OC₂H₅)₄, Ti (On-C₃H₇)₄, Ti (OiC₃H₇)₄, Ti (On-C₄H₉)₄, Ti (On-C₃H₇)₄2-10 mer, Ti (O-i-C₃H₇)₄2 to 10-mer, Ti (On-C₄H₉)₄Preferred examples include dimers to 10-mers. These can be used alone or in combination of two or more. Among them, Ti (On-C₃H₇)₄, Ti (OiC₃H₇)₄, Ti (On-C₄H₉)₄, Ti (On-C₃H₇)₄2 to 10-mer, Ti (On-C₄H₉)₄2 to 10-mers are particularly preferred.
[0141]
The monomer, oligomer or hydrolyzate of the organic titanium compound used in the present invention desirably accounts for 50.0 to 98.0% by mass of the solid content contained in the coating solution. The solid content ratio is more preferably from 50 to 90% by mass, and still more preferably from 55 to 90% by mass. In addition, it is also preferable to add a polymer of an organic titanium compound (crosslinked by hydrolysis of the organic titanium compound in advance) or titanium oxide fine particles to the coating composition.
[0142]
In the present invention, the coating liquid contains a monomer or oligomer of the above-mentioned organotitanium compound or a partial or complete hydrolyzate, but the monomer or oligomer of the organotitanium compound is self-condensed and crosslinked to form a network bond. is there. Catalysts and curing agents can be used to accelerate the reaction, including metal chelate compounds, organometallic compounds such as organic carboxylate salts, organosilicon compounds having an amino group, and acid generation by light. Agents (photoacid generators). Particularly preferred among these catalysts or curing agents are aluminum chelate compounds and photoacid generators. Examples of the aluminum chelate compound include ethyl acetoacetate aluminum diisopropylate, aluminum trisethyl acetoacetate, alkyl acetoacetate aluminum diisopropylate, aluminum monoacetylacetonate bisethylacetoacetate, and aluminum trisacetylacetonate. Examples of the acid generator include benzyltriphenylphosphonium hexafluorophosphate, other phosphonium salts and salts of triphenylphosphonium hexafluorophosphate.
[0143]
It is preferable that a binder of 0.5 to 20% by mass is contained as a solid content ratio in the coating solution of the antireflection layer.
[0144]
The binder has two or more polymerizable groups such as a polymerizable vinyl group, an allyl group, an acryloyl group, a methacryloyl group, an isopropenyl group, an epoxy group, and an oxetane ring, and has a crosslinked structure or a network structure by irradiation with actinic rays. The same acrylic or methacrylic active energy ray reactive compound, epoxy active energy ray reactive compound, or oxetane active energy ray reactive compound as used in the ink to be formed can be used. These compounds include monomers, oligomers, and polymers. From the viewpoint of polymerization rate and reactivity, among these active groups, an acryloyl group, a methacryloyl group or an epoxy group is preferable, and a polyfunctional monomer or oligomer is more preferable. Also, the actinic ray-curable resin used for the above-mentioned ink and hard coat layer can be preferably used. Further, an alcohol-soluble acrylic resin is also preferably used.
[0145]
In the middle to high refractive index layer containing a titanium compound, an alcohol-soluble acrylic resin is also preferably used as a binder, whereby a high refractive index layer can be obtained while the film thickness unevenness is small. Specifically, an alkyl (meth) acrylate polymer or an alkyl (meth) acrylate copolymer, for example, a copolymer such as n-butyl methacrylate, isobutyl methacrylate, methyl methacrylate, ethyl methacrylate, or propyl methacrylate is preferably used, The copolymerization component is not limited to these. Commercially available products include DIANAL BR-50, BR-51, BR-52, BR-60, BR-64, BR-65, BR-70, BR-73, BR-75, BR-76, BR-77. , BR-79, BR-80, BR-82, BR-83, BR-85, BR-87, BR-88, BR-89, BR-90, BR-93, BR-95, BR-96, BR -100, BR-101, BR-102, BR-105, BR-107, BR-108, BR-112, BR-113, BR-115, BR-116, BR-117, BR-118 (Mitsubishi Rayon Co., Ltd.) can be used. These monomer components can also be added as a binder for the medium to high refractive index layer. The refractive index can be adjusted by changing the addition ratio of the binder.
[0146]
It is preferable to add a slipping agent to the low refractive index layer, and the scratch resistance can be improved by imparting a slip property. As the sliding agent, silicone oil or a wax-like substance is preferably used.
[0147]
Specifically, higher fatty acids such as behenic acid, stearic acid amide, and pentacoic acid or derivatives thereof, and carnauba wax, beeswax, and montan wax containing a large amount of these components as natural products can also be preferably used. Polyorganosiloxanes as disclosed in JP-B-53-292, higher fatty acid amides as disclosed in U.S. Pat. No. 4,275,146, JP-B-58-33541, UK Patent 927,446. Or higher fatty acid esters (esters of fatty acids having 10 to 24 carbon atoms and alcohols having 10 to 24 carbon atoms) as disclosed in JP-A-55-126238 and JP-A-58-90633, and U.S. Pat. No. 3,933,516, higher fatty acid metal salts, dicarboxylic acids having up to 10 carbon atoms and aliphatic or cycloaliphatic diols as disclosed in JP-A-51-37217. Polyester compounds, oligopolyesters from dicarboxylic acids and diols disclosed in JP-A-7-13292, etc. It can be.
[0148]
The amount of the slip agent used in the low refractive index layer is 0.01 to 10 mg / m.²Is preferred. If necessary, it can be added to the middle refractive index layer and the high refractive index layer.
[0149]
It is preferable to add a surfactant, a softening agent, a softening smoothing agent, and the like to the low refractive index layer of the present invention, thereby improving abrasion resistance. Among them, anionic or nonionic surfactants are preferable, and for example, dialkyl sulfosuccinate sodium salt, nonionic surfactant emulsion of polyhydric alcohol fatty acid ester and the like are preferable. For example, Lipooil NT-6, NT12, NT-33, TC-1, TC-68, TC-78, CW-6, TCF-208, TCF-608, NK Oil CS-11, AW-9, AW-10 , AW-20, Polysofter N-606, a paint additive PC-700 (manufactured by Nichika Chemical Co., Ltd.) and the like.
[0150]
The low refractive index layer according to the present invention is preferably provided by coating silicon compound fine particles such as silicon oxide or fluorine-containing compound fine particles. Preferred organic silicon compounds include tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, and the like. An oligomer is obtained. The hydrolysis reaction can be performed by a known method.For example, a predetermined amount of water is added to the above tetraalkoxysilane, and in the presence of an acid catalyst, while distilling off by-produced alcohol, usually at room temperature to room temperature. React at 100 ° C. By this reaction, the alkoxysilane is hydrolyzed, followed by a condensation reaction, and a liquid silicate oligomer having two or more hydroxyl groups (usually having an average degree of polymerization of 2 to 8, preferably 3 to 6) as a hydrolyzate Obtainable.
[0151]
Examples of the curing catalyst include acids, alkalis, organic metals, metal alkoxides and the like. In the present invention, acids, especially organic acids having a sulfonyl group or a carboxyl group are preferably used. For example, acetic acid, polyacrylic acid, benzenesulfonic acid, p-toluenesulfonic acid, methylsulfonic acid and the like are used. The organic acid is more preferably a compound having a hydroxyl group and a carboxyl group in one molecule. For example, hydroxydicarboxylic acid such as citric acid or tartaric acid is used. Further, the organic acid is more preferably a water-soluble acid. For example, in addition to the citric acid and tartaric acid, levulinic acid, formic acid, propionic acid, malic acid, succinic acid, methylsuccinic acid, fumaric acid, oxaloacetic acid, pyruvine Acid, 2-oxoglutaric acid, glycolic acid, D-glyceric acid, D-gluconic acid, malonic acid, maleic acid, oxalic acid, isocitric acid, lactic acid and the like are preferably used. In addition, benzoic acid, hydroxybenzoic acid, atrobic acid and the like can also be used as appropriate.
[0152]
By using the above-mentioned organic acid, sulfuric acid, hydrochloric acid, nitric acid, hypochlorous acid, the use of inorganic acids such as boric acid not only can eliminate concerns about pipe corrosion and safety at the time of production, but also during hydrolysis. A stable hydrolyzate can be obtained without causing gelation. The addition amount is 0.1 to 10 parts by mass, preferably 0.2 to 5 parts by mass, per 100 parts by mass of the partial hydrolyzate. Further, the amount of water to be added may be at least the amount at which the partial hydrolyzate can theoretically hydrolyze 100%, and it is preferable to add 100 to 300%, preferably 100 to 200%.
[0153]
The coating composition for a low refractive index layer thus obtained is extremely stable.
(Aging process)
Further, in the present invention, by the aging step, the crosslinking by hydrolysis and condensation of the organosilicon compound sufficiently proceeds, and the properties of the obtained coating film become excellent. The aging may be performed by allowing the oligomer liquid to stand, and the leaving time is a time during which the above-mentioned crosslinking proceeds to an extent sufficient to obtain desired film properties. Specifically, depending on the type of catalyst used, 1 hour or more at room temperature for hydrochloric acid and several hours or more for maleic acid, about 8 hours to 1 week, are sufficient, usually about 3 days. The ripening temperature affects the ripening time, and it may be better to take a means of heating to around 20 ° C. in extremely cold regions. In general, aging proceeds rapidly at high temperatures, but gelation occurs when heated to 100 ° C. or higher. Therefore, heating to 50 to 60 ° C. at most is appropriate. The silicate oligomer used in the present invention is, in addition to the above, a modified product modified with an organic compound (monomer, oligomer, polymer) having a functional group such as an epoxy group, an amino group, an isocyanate group, and a carboxyl group. And it may be used alone or in combination with the above silicate oligomer.
[0154]
In the present invention, the low refractive index layer may contain silicon oxide fine particles. It is preferable to contain silicon oxide fine particles having a particle size of 0.1 μm or less. For example, Aerosil 200V (manufactured by Nippon Aerosil Co., Ltd.) or the like can be added. Particularly, silicon oxide fine particles whose surface is modified with an alkyl group are preferably used. For example, silicon oxide fine particles whose surface is modified with a methyl group, which are commercially available as Aerosil R972 and R972V (manufactured by Nippon Aerosil Co., Ltd.), are preferably used. Can be added. In addition, fine particles of silicon oxide having a surface substituted with an alkyl group described in JP-A-2001-2799 can also be used, and can be easily treated with an alkylsilane coupling agent after the hydrolysis of the silicate oligomer described above. Can be obtained. It is preferable to add the compound so that the solid content in the low refractive index layer is in the range of 0.1 to 40% by mass.
[0155]
A silane compound may be further added to each refractive index layer of the present invention for adjusting the refractive index or improving the film quality.
[0156]
Solvents used in the coating solution for coating the high to low refractive index layer (also referred to as an optical interference layer) according to the present invention include alcohols such as methanol, ethanol, 1-propanol, 2-propanol, and butanol; , Methyl ethyl ketone, cyclohexanone, etc .; ketones such as benzene, toluene and xylene; glycols such as ethylene glycol, propylene glycol and hexylene glycol; ethyl cellosolve, butyl cellosolve, ethyl carbitol and butyl carbine Glycol ethers such as tall, diethyl cellosolve, diethyl carbitol, and propylene glycol monomethyl ether; N-methylpyrrolidone, dimethylformamide, methyl lactate, ethyl lactate, water, and the like. These may be used alone or in combination of two or more. hand It is possible to use.
[0157]
Those having an ether bond in the molecule are particularly preferred, and glycol ethers are more preferred.
[0158]
Glycol ethers include propylene glycol mono (C1 to C4) alkyl ether and propylene glycol mono (C1 to C4) alkyl ether ester, and specifically, propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether, propylene Glycol mono n-propyl ether, propylene glycol monoisopropyl ether, propylene glycol monobutyl ether, and the like. Examples of the propylene glycol mono (C1-C4) alkyl ether ester include propylene glycol monoalkyl ether acetate, and specifically, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and the like. These solvents are preferably added to the coating liquid in an amount of 1 to 90% by mass of the total organic solvent.
[0159]
Further, it is preferable to add various leveling agents, surfactants, and low surface tension substances such as silicone oil to the coating liquid for each of the high to low refractive index layers according to the present invention.
[0160]
After the application of the middle to high refractive index layer and the low refractive index layer according to the present invention, it is preferable to irradiate active light in order to promote hydrolysis or curing of the composition containing the metal alkoxide. More preferably, the active energy ray is irradiated each time each layer is coated.
[0161]
The same light source as that used for curing the ink can be used as the actinic ray used in the present invention. Irradiation conditions are different for each lamp, but the amount of irradiation is 20 mJ / cm²-10,000mJ / cm²Is preferably, and more preferably, 100 to 2,000 mJ / cm.²And particularly preferably, 400 to 2,000 mJ / cm.²It is.
[0162]
When ultraviolet rays are used, the multilayer antireflection layer may be irradiated one layer at a time, or may be irradiated after lamination, but it is particularly preferable to irradiate ultraviolet rays after laminating the multilayers.
[0163]
Further, in the present invention, a method of providing an antireflection layer by a dry process can also be preferably used. The antireflection layer or the antifouling layer can be formed according to the method described, but in the present invention, it is particularly preferable to form the antireflection layer by the atmospheric pressure plasma treatment method.
[0164]
【Example】
Next, the present invention will be further described by describing specific embodiments of the present invention and the effects thereof, but of course, embodiments of the present invention are not limited thereto.
[0165]
[Example 1]
Preparation of transparent substrate
A dope was prepared as described below to prepare a cellulose ester film as a transparent substrate.
[0166]

The dope composition was charged into a sealed container, heated to 70 ° C., and completely stirred to dissolve cellulose triacetate (TAC) to obtain a dope. The time required for dissolution was 4 hours. After filtering the dope composition, the dope (temperature: 35 ° C.) was uniformly cast on a stainless steel band support at 22 ° C. using a belt casting apparatus. The temperature of the stainless steel band support was 20 ° C.
[0167]
Then, after drying to a range where the peeling was possible, the dope was peeled off from the stainless steel band support. At this time, the residual solvent amount of the dope was 25%. The time required from dope casting to peeling was 3 minutes. After peeling from the stainless steel band support, drying at 120 ° C. while holding in the width direction, releasing the width holding, and drying in a drying zone at 120 ° C. and 135 ° C. while being conveyed by a number of rolls. A knurling process with a width of 10 mm and a height of 5 μm was performed on both ends of the film to prepare a cellulose triacetate film having a thickness of 40 μm. The film width was 1300 mm and the winding length was 3000 m. The winding tension was 150 N / 1300 mm in initial tension and 100 N / 1300 mm in final winding tension.
[0168]
In the produced cellulose ester film, a light control film having a stripe pattern was formed by an inkjet method.
[0169]
Production of light control film
On a cellulose ester film, the following black ink liquid 1 was ejected as ink droplets at 1 pl by an ink jet method, and 100 mJ / cm from the actinic ray irradiation part 0.2 seconds later.²After curing by irradiating with ultraviolet light at an irradiation intensity of 5 mm, a stripe pattern having a line width of 5 μm is formed. Similarly, the following transparent ink liquid 2 was ejected as ink droplets at 1 pl from an area other than the stripes by the ink jet method, and 100 mJ / cm from the actinic ray irradiation section 0.2 seconds later.²Irradiation with ultraviolet light at an irradiation intensity of, and curing. This is repeated to make the film thickness 30 μm. Thereafter, the temperature and speed of the hot air were gradually increased, and finally dried at 85 ° C., and further 100 mJ / cm.²A light control film was formed by irradiating with ultraviolet light at an irradiation intensity of.
[0170]
<Inkjet emission method>
As the inkjet emitting device, a line head system (same structure as in FIG. 10A) was used, and ten inkjet heads having a predetermined number of nozzles having a nozzle diameter of 3.5 μm were prepared. The ink jet head having the configuration shown in FIG. 9 was used.
[0171]
The ink supply system is composed of an ink supply tank, a filter, a piezo-type inkjet head, and a pipe. From the ink supply tank to the inkjet head, heat insulation and heating (40 ° C) are performed. The driving frequency was 20 kHz.
[0172]
<Composition of black ink liquid 1>
20 parts by mass of carbon black
Dipentaerythritol hexaacrylate 100 parts by mass
(Including dimer and trimer components)
Photoreaction initiator (dimethoxybenzophenone) 4 parts by mass
Propylene glycol monomethyl ether 30 parts by mass
100 parts by mass of methyl ethyl ketone
<Composition of the transparent ink liquid 2>
Dipentaerythritol hexaacrylate 100 parts by mass
(Including dimer and trimer components)
Photoreaction initiator (dimethoxybenzophenone) 4 parts by mass
Propylene glycol monomethyl ether 30 parts by mass
100 parts by mass of methyl ethyl ketone
What was formed was a light control film similar to that shown in FIGS. 1 (a) and 1 (b).
[0173]
The relationship between the light incident angle and the light transmittance in the direction perpendicular to the stripes (stripe) of the light control film (the vertical direction in FIG. B) was as shown in FIG.
[0174]
[Example 2]
In the same manner as in Example 1, a light control film having a grid pattern as shown in FIG. 3 was formed by an inkjet method.
[0175]
The relationship between the light incident angle and the light transmittance in the vertical and horizontal directions of the light control film having the lattice pattern was as shown in FIGS. 4 (a) and 4 (b).
[0176]
[Example 3]
In the same manner as in Example 1, a light control film having a dot pattern shown in FIG. 5 was formed by an inkjet method.
[0177]
The relationship between the light incident angle and the light transmittance in the vertical and horizontal directions of the light control film having the dot pattern was as shown in FIGS. 6 (a) and 6 (b).
[0178]
[Example 4]
In the same manner as in Example 1, a light control film having a honeycomb pattern shown in FIG. 7 was formed by an inkjet method.
[0179]
The light incident angles and light transmittances of the honeycomb pattern light control film in the vertical and horizontal directions are as shown in FIGS. 8 (a) and 8 (b).
[0180]
[Example 5]
After the following hard coat layer was applied to the cellulose ester film produced in Example 1, a light control film was formed by the ink jet method described in Example 1.
[0181]
Application of hard coat layer
On one surface of the cellulose ester film, the following hard coat layer coating composition was applied by a slit die, the temperature and speed of hot air were gradually increased, and finally dried at 85 ° C., and subsequently 115 mJ from the actinic ray irradiation unit. / Cm²Irradiation with ultraviolet light at an irradiation intensity of 5 μm was performed to provide a hard coat layer having a center line average surface roughness (Ra) of 12 μm and a dry film thickness of 5 μm.
[0182]

[Example 6]
On the light control film produced in Example 1, the following antiglare layer was formed by a coating method.
[0183]
Application of anti-glare layer
On a light control film, the following antiglare layer coating composition was applied with a slit die so as to have a wet film thickness of 10 μm, the temperature of hot air was gradually increased, and finally the temperature was increased to 85 ° C., followed by drying at 85 ° C. 115 mJ / cm from actinic ray irradiator²Irradiation was performed at an irradiation intensity of 5 μm to provide an antiglare layer having a dry film thickness of 5 μm.
[0184]

The obtained light control film was mounted on the front surface of a liquid crystal display panel (color liquid crystal display MultiSync LCD1525J: model name LA-1529HM manufactured by NEC Corporation), and visibility was evaluated.
[0185]
As a result, the reflection of the nearest fluorescent light in the office was completely unnoticeable, and characters with a font size of 8 or less could be clearly read.
[0186]
[Example 7]
On the light control film produced in Example 1, an antireflection layer was applied in the order of a middle refractive index layer, a high refractive index layer, and then a low refractive index layer as follows.
[0187]
Application of medium refractive index layer
The following medium refractive index layer composition was applied on a light control film by an extrusion coater, dried at 80 ° C. for 5 minutes, and then irradiated with ultraviolet rays at 175 mJ / cm using a high-pressure mercury lamp (80 W).²Irradiation and curing were performed, and a middle refractive index layer was provided so as to have a thickness of 78 nm. The refractive index of the middle refractive index layer was 1.70.
[0188]

Formation of high refractive index layer
The following high-refractive-index layer composition was applied on the medium-refractive-index layer by an extrusion coater, dried at 80 ° C. for 5 minutes, and then irradiated with ultraviolet rays at 175 mJ / cm using a high-pressure mercury lamp (80 W).²Irradiation and curing were performed, and a high refractive index layer was provided so as to have a thickness of 66 nm. The high refractive index layer had a refractive index of 1.85.
[0189]

Formation of low refractive index layer
On the high refractive index layer, the following low refractive index layer composition was applied by an extrusion coater, dried at 80 ° C. for 5 minutes, thermally cured at 120 ° C. for 5 minutes, and further irradiated with ultraviolet rays at 175 mJ / cm.²Irradiation and curing were performed, and a low refractive index layer was provided so as to have a thickness of 95 nm. The low refractive index layer had a refractive index of 1.45.
[0190]
<Preparation of tetraethoxysilane hydrolyzate A>
First, 580 g of tetraethoxysilane and 1144 g of ethanol were mixed, and an aqueous citric acid solution (a solution of 5.4 g of citric acid monohydrate dissolved in 272 g of water) was added thereto, followed by 1 hour at room temperature (25 ° C.). By stirring, a tetraethoxysilane hydrolyzate A was prepared.
[0191]
<Low refractive index layer composition>
Propylene glycol monomethyl ether 303 parts by mass
Isopropyl alcohol 305 parts by mass
139 parts by mass of tetraethoxysilane hydrolyzate A
γ-methacryloxypropyltrimethoxysilane
(KBM503 manufactured by Shin-Etsu Chemical Co., Ltd.) 1.6 parts by mass
10% FZ-2207, propylene glycol monomethyl ether solution
(Manufactured by Nippon Unicar Co., Ltd.) 1.3 parts by mass
The obtained light control film was mounted on the front surface of a liquid crystal display panel (color liquid crystal display MultiSync LCD1525J: model name LA-1529HM manufactured by NEC Corporation), and visibility was evaluated.
[0192]
As a result, the reflection of the nearest fluorescent light in the office was completely unnoticeable, and characters with a font size of 8 or less could be clearly read.
[0193]
In addition, a moving image and a test chart image for sharpness evaluation were output, and the tightness and sharpness of the image were evaluated according to the following criteria. As a result, the blackness of the moving image was very good, and the test pattern was projected very sharply.
[0194]
[Comparative Example 1]
According to the method described in JP-A-51-44186, a transparent thin plate having a thickness of 180 μm (cellulose acetyl butyrate) and a thin plate having a black thickness of 20 μm (cellulose acetyl butyrate containing carbon black) are alternately laminated. A louver-equipped light control film was prepared by slicing the film at a desired thickness in a direction perpendicular to the laminating direction.
[0195]
However, the pattern formed on the cross section became irregular, and the transmittance was reduced to 30%.
[0196]
【The invention's effect】
According to the present invention, it is easy to manufacture, has excellent mechanical strength, has excellent light-shielding properties for unnecessary incident light, an image viewed from a predetermined direction is bright and clear, and has dots, stripes, lattices, honeycomb patterns, or the like. It is possible to provide a light control film, a method for producing the same, and an ink jet apparatus used for the production, which can freely form a pattern.
[Brief description of the drawings]
FIG. 1 is a cross-sectional view and a top view illustrating the structure of a light control film of the present invention.
FIG. 2 is a view for explaining a relationship between a light incidence angle and a light transmittance in a direction perpendicular to the stripe pattern (the vertical direction in FIG. 1).
FIG. 3 is a diagram illustrating a lattice pattern.
FIG. 4 is a view for explaining the relationship between the light incident angle and the light transmittance in the vertical and horizontal directions of a light control film of a lattice type.
FIG. 5 is a diagram illustrating a dot pattern.
FIG. 6 is a view for explaining the relationship between the light incident angle and the light transmittance in the vertical and horizontal directions of a point-type light control film.
FIG. 7 is a diagram illustrating a honeycomb pattern.
FIG. 8 is a view for explaining the relationship between the light incident angle and the light transmittance in the vertical and horizontal directions of a honeycomb type light control film.
FIG. 9 is a cross-sectional view of the ink-jet head and an enlarged view of the cross-section.
FIG. 10 is a schematic diagram illustrating an example of an inkjet head unit and a nozzle plate.
FIG. 11 is a conceptual diagram of an example of an ink jet system.
[Explanation of symbols]
1 transparent substrate (support)
2 pattern image
10 Inkjet head
11 Substrate
12 Piezoelectric element
13 Channel plate
13a Ink flow path
13b wall
14 Common liquid chamber components
14a Common liquid chamber
15 Ink supply pipe
16 Nozzle plate
16a nozzle
17 Driving circuit printed circuit board (PCB)
18 Lead part
19 Drive electrode
20 grooves
21 Protection plate
22 Fluid resistance
23, 24 electrodes
25 Upper partition
26 heater
27 Heater power supply
28 Heat transfer member

Claims (14)

A method for producing a light control film, comprising forming a light control pattern on a transparent substrate by an inkjet method. The method for producing a light control film according to claim 1, wherein the light control pattern is any one of a dot, a stripe, a lattice pattern, and a honeycomb pattern. A light control pattern is formed by emitting ink droplets containing at least a resin and a dye or a pigment, and regions other than the pattern are formed by emitting ink droplets containing a transparent resin as a main component. The method for producing a light control film according to claim 1. 4. The light control film according to claim 3, wherein the resin contained in the ink droplets for forming the pattern and the transparent resin contained in the ink droplets for the area other than the pattern are actinic ray-curable resins. Manufacturing method. 5. The method for producing a light control film according to claim 4, wherein actinic rays are irradiated immediately after the ink droplets have landed on a transparent substrate. 4. The light control film according to claim 3, wherein the resin contained in the ink droplets for pattern formation and the transparent resin contained in the ink droplets for the area other than the pattern are thermosetting resins. Production method. 7. The method for manufacturing a light control film according to claim 6, wherein a heat treatment is performed immediately after the ink droplets have landed on a transparent substrate. A light control film produced by the method for producing a light control film according to claim 1. 9. The light control film according to claim 8, wherein the transmittance of vertically incident light to the light control film is 40% or more, and the transmittance of light rays obliquely directed at 30 degrees is 20% or less. 10. A light control film, wherein a fine uneven structure is formed on the surface of the light control film according to claim 8 by an ink-jet method to impart antiglare properties. 10. A light, wherein at least one hard coat layer is formed on the surface of the light control film according to claim 8 or 9, and a fine uneven structure is formed thereon by an ink jet method to impart an antiglare property. Control film. A light control film, comprising an antireflection layer provided on the light control film surface according to claim 8. 10. A light control film comprising: an antiglare layer formed on the light control film surface according to claim 8; and an antireflection layer provided on the antiglare layer. An inkjet device for producing the light control film according to any one of claims 8 to 13, wherein an actinic ray irradiation unit or a heating unit is arranged so that actinic rays or heat does not directly act on the inkjet head unit. An ink jet apparatus, comprising:

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