JP2004354828A - Antireflection film, and polarizing plate and display device having the film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an antireflection film showing excellent characteristic in terms of all the items such as flatness, handleability, scratch resistance, pencil hardness, thermal cracks, antifouling property and solvent resistance, and to provide a polarizing plate and a display device using the film. <P>SOLUTION: The antireflection film having a hard coat layer, a high refractive index layer and a low refractive index layer in this order at least on one surface of a supporting body, is characterised in that the film thickness of the hard coat layer is 1 to 20μm, the high refractive index layer and the low refractive index layer are respectively formed by wet coating, and the nano indentation hardness (H) of the surface of the outermost layer is 2 to 4GPa and the nano indentation elastic modulus (Er) thereof is 10 to 30GPa. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

特に好ましくは、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。
【０１１３】
また、ＪＩＳ Ｂ ０６０１で規定される中心線平均表面粗さＲａが０．０５μｍ〜０．５μｍ程度の防眩層に対して中〜高屈折率層及び低屈折率層を塗設して反射防止加工する場合、防眩層の微細な凹凸上にできるだけ均一な層を形成するため、塗設後速やかに乾燥することが好ましく、沸点１３０℃以下、好ましくは１００℃以下の溶媒を全溶媒の３０質量％、より好ましくは５０質量％以上含有する溶媒を用いることが好ましい。これらの溶媒は特に限定されないが、アルコール類、ケトン類、炭化水素類、エーテル類、エステル類等から適宜選択される。好ましくは、前述の溶媒から選択することができる。
【０１１４】
また、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。具体的なシリコンオイルとしては表１に記載の化合物が挙げられる。
【０１１５】
【表１】

【０１１６】
これらの成分は支持体上への塗布や積層体作製時に予め塗設されている層に新たな塗布液を塗設するときの塗布性を高める効果がある。積層体最表面層に添加した場合には、塗膜の撥水、撥油性、防汚性を高めるばかりでなく、表面の耐擦り傷性にも効果を発揮する。これらの成分は添加量が多過ぎると塗布時にハジキの原因となるため、塗布液中の固形分成分に対し、０．０１質量％〜３質量％の範囲で添加することが好ましい。
【０１１７】
（塗布方法）：ウェットコーティング
本発明の反射防止フィルムの各層の中で、高屈折率層、低屈折率層の形成には、ウェットコーティング法が用いられることが必須要件である。また、中屈折率層、ハードコート層の作製方法についてもウェットコーティング法による層形成が好ましい。
【０１１８】
ここで、ウェットコーティング法の具体例としては、ディッピング、スピンコート、ナイフコート、バーコート、エアードクターコート、ブレードコート、スクイズコート、リバースロールコート、グラビアロールコート、スプレイコート、ダイコート（カーテンコート等）等の公知の塗布方法を用いてことができ、連続塗布または薄膜塗布が可能な塗布方法が好ましく用いられる。
【０１１９】
本発明の反射防止フィルムを構成する各層の組成物を支持体上に塗布する際、塗布液中の固形分濃度や塗布量を調整することにより、層の膜厚及び塗布均一性等をコントロールすることができる。また、組成物の塗布性を向上させるために、塗布液中に微量の界面活性剤等を添加してもよい。
【０１２０】
《支持体（基材フィルム、基板、基材等ともいう）》
本発明に係る支持体について説明する。
【０１２１】
本発明に係る支持体としては、製造が容易であること、ハードコート層やその他の層（防眩層、中間層等）が接着し易いこと、光学的に等方性であること、光学的に透明性であることが好ましい。これらの性質を有していれば何れでもよく、例えば、セルロースエステル系フィルム、ポリエステル系フィルム、ポリカーボネート系フィルム、ポリアリレート系フィルム、ポリスルホン（ポリエーテルスルホンも含む）系フィルム、ポリエチレンテレフタレート、ポリエチレンナフタレート等のポリエステルフィルム、ポリエチレンフィルム、ポリプロピレンフィルム、セロファン、セルロースジアセテートフィルム、セルロースアセテートブチレートフィルム、ポリ塩化ビニリデンフィルム、ポリビニルアルコールフィルム、エチレンビニルアルコールフィルム、シンジオタクティックポリスチレン系フィルム，ポリカーボネートフィルム、ノルボルネン樹脂系フィルム、ポリメチルペンテンフィルム、ポリエーテルケトンフィルム、ポリエーテルケトンイミドフィルム、ポリアミドフィルム、フッ素樹脂フィルム、ナイロンフィルム、ポリメチルメタクリレートフィルムまたはアクリルフィルム等を挙げることができるが、これらに限定されるわけではない。これらのうちセルローストリアセテートフィルム、ポリカーボネートフィルム、ポリスルホン（ポリエーテルスルホンを含む）が好ましく、本発明においては、特にセルローストリアセテートフィルムまたはセルロースアセテートプロピオネートフィルムが、製造上、コスト面、透明性、等方性、接着性等の面から好ましい。
【０１２２】
《セルロースエステルフィルム》
低反射率の積層体を得る観点から、基材としてはセルロースエステルフィルムを用いることが好ましい。セルロースエステルとしては、セルロースアセテート、セルロースアセテートブチレート（ＣＡＢ）、セルロースアセテートプロピオネート（ＣＡＰ）が好ましく、中でも、セルロースアセテートブチレート（ＣＡＢ）、セルロースアセテートプロピオネート（ＣＡＰ）が好ましく用いられる。
【０１２３】
特に、アセチル基の置換度をＸ、プロピオニル基またはブチリル基の置換度をＹとしたとき、ＸとＹが下記の範囲にあるセルロースの混合脂肪酸エステルを有する支持体上に高屈折率層及び低屈折率層を設けた反射防止フィルムが好ましく用いられる。
【０１２４】
２．３≦Ｘ＋Ｙ≦３．０
０．１≦Ｙ≦１．２
特に、
２．５≦Ｘ＋Ｙ≦２．８５
０．３≦Ｙ≦１．２であることが好ましい。
【０１２５】
本発明に係る支持体としてセルロースエステルを用いる場合、セルロースエステルの原料のセルロースとしては、特に限定はないが、綿花リンター、木材パルプ（針葉樹由来、広葉樹由来）、ケナフ等を挙げることができる。またそれらから得られたセルロースエステルはそれぞれ任意の割合で混合使用することができる。これらのセルロースエステルは、アシル化剤が酸無水物（無水酢酸、無水プロピオン酸、無水酪酸）である場合には、酢酸のような有機酸やメチレンクロライド等の有機溶媒を用い、硫酸のようなプロトン性触媒を用いてセルロース原料と反応させて得ることができる。
【０１２６】
アシル化剤が酸クロライド（ＣＨ_３ＣＯＣｌ、Ｃ_２Ｈ_５ＣＯＣｌ、Ｃ_３Ｈ_７ＣＯＣｌ）の場合には、触媒としてアミンのような塩基性化合物を用いて反応が行われる。具体的には、特開平１０−４５８０４号公報に記載の方法等を参考にして合成することができる。また、本発明に係るセルロースエステルは各置換度に合わせて上記アシル化剤量を混合して反応させたものであり、セルロースエステルはこれらアシル化剤がセルロース分子の水酸基に反応する。セルロース分子はグルコースユニットが多数連結したものからなっており、グルコースユニットに３個の水酸基がある。この３個の水酸基にアシル基が誘導された数を置換度（モル％）という。例えば、セルローストリアセテートはグルコースユニットの３個の水酸基全てにアセチル基が結合している（実際には２．６〜３．０）。
【０１２７】
本発明に係るセルロースエステルとしては、セルロースアセテートプロピオネート、セルロースアセテートブチレート、またはセルロースアセテートプロピオネートブチレートのようなアセチル基の他にプロピオネート基またはブチレート基が結合したセルロースの混合脂肪酸エステルが特に好ましく用いられる。なお、ブチレートを形成するブチリル基としては、直鎖状でも分岐していてもよい。
【０１２８】
プロピオネート基を置換基として含むセルロースアセテートプロピオネートは耐水性に優れ、液晶画像表示装置用のフィルムとして有用である。
【０１２９】
アシル基の置換度の測定方法はＡＳＴＭ−Ｄ８１７−９６の規定に準じて測定することができる。
【０１３０】
セルロースエステルの数平均分子量は、７０，０００〜２５０，０００の範囲のものが、成型した場合の機械的強度が強く、塗布液調製時には、適度なドープ粘度となり好ましく、更に好ましくは、８０，０００〜１５０，０００である。
【０１３１】
ここで、上記のセルロースエステルの数平均分子量は、当該業者公知のＧＰＣ（ゲルパーミエーションクロマトグラフィ）法を用いて測定することが出来る。
【０１３２】
《製膜》
これらセルロースエステルは後述するように一般的に流延法と呼ばれるセルロースエステル溶解液（ドープ）を、例えば、無限に移送する無端の金属ベルトまたは回転する金属ドラムの流延用支持体上に加圧ダイからドープを流延（キャスティング）し製膜する方法で製造される。これらドープの調製に用いられる有機溶媒としては、セルロースエステルを溶解でき、かつ、適度な沸点であることが好ましく、例えばメチレンクロライド、酢酸メチル、酢酸エチル、酢酸アミル、アセトン、テトラヒドロフラン、１，３−ジオキソラン、１，４−ジオキサン、シクロヘキサノン、ギ酸エチル、２，２，２−トリフルオロエタノール、２，２，３，３−テトラフルオロ−１−プロパノール、１，３−ジフルオロ−２−プロパノール、１，１，１，３，３，３−ヘキサフルオロ−２−メチル−２−プロパノール、１，１，１，３，３，３−ヘキサフルオロ−２−プロパノール、２，２，３，３，３−ペンタフルオロ−１−プロパノール、ニトロエタン、１，３−ジメチル−２−イミダゾリジノン等を挙げることができるが、メチレンクロライド等の有機ハロゲン化合物、ジオキソラン誘導体、酢酸メチル、酢酸エチル、アセトン等が好ましい有機溶媒（即ち、良溶媒）として挙げられる。
【０１３３】
また、下記の製膜工程に示すように、溶媒蒸発工程において流延用支持体上に形成されたウェブ（ドープ膜）から溶媒を乾燥させるときに、ウェブ中の発泡を防止する観点から、用いられる有機溶媒の沸点としては、３０〜８０℃が好ましく、例えば、上記記載の良溶媒の沸点は、メチレンクロライド（沸点４０．４℃）、酢酸メチル（沸点５６．３２℃）、アセトン（沸点５６．３℃）、酢酸エチル（沸点７６．８２℃）等である。
【０１３４】
上記記載の良溶媒の中でも溶解性に優れるメチレンクロライド、酢酸メチルが好ましく用いられ、特にメチレンクロライドが全有機溶媒に対して５０質量％以上含まれていることが好ましい。
【０１３５】
上記有機溶媒の他に、０．１質量％〜３０質量％の炭素原子数１〜４のアルコールを含有させることが好ましい。特に好ましくは、５質量％〜３０質量％で前記アルコールが含まれることが好ましい。これらは上記記載のドープを流延用支持体に流延後、溶媒が蒸発を始めアルコールの比率が多くなるとウェブ（ドープ膜）がゲル化し、ウェブを丈夫にし流延用支持体から剥離することを容易にするゲル化溶媒として用いられたり、これらの割合が少ない時は非塩素系有機溶媒のセルロースエステルの溶解を促進する役割もある。
【０１３６】
炭素原子数１〜４のアルコールとしては、メタノール、エタノール、ｎ−プロパノール、ｉｓｏ−プロパノール、ｎ−ブタノール、ｓｅｃ−ブタノール、ｔｅｒｔ−ブタノール等を挙げることができる。
【０１３７】
これらの溶媒のうち、ドープの安定性がよく、沸点も比較的低く、乾燥性もよく、且つ毒性がないこと等からエタノールが好ましい。好ましくは、メチレンクロライド７０質量％〜９５質量％に対してエタノール５質量％〜３０質量％を含む溶媒を用いることが好ましい。環境上の制約でハロゲンを含む溶媒を避ける場合は、メチレンクロライドの代わりに酢酸メチルを用いることもできる。このとき、冷却溶解法によりドープを調製してもよい。
【０１３８】
《可塑剤》
本発明の反射防止フィルムの支持体にセルロースエステルを用いる場合、このセルロースエステルには可塑剤を含有するのが好ましい。可塑剤としては、特に限定はないが、リン酸エステル系可塑剤、フタル酸エステル系可塑剤、トリメリット酸エステル系可塑剤、ピロメリット酸系可塑剤、グリコレート系可塑剤、クエン酸エステル系可塑剤、ポリエステル系可塑剤等が好ましく用いられる。
【０１３９】
リン酸エステル系可塑剤では、トリフェニルホスフェート、トリクレジルホスフェート、クレジルジフェニルホスフェート、オクチルジフェニルホスフェート、ジフェニルビフェニルホスフェート、トリオクチルホスフェート、トリブチルホスフェート等、フタル酸エステル系可塑剤では、ジエチルフタレート、ジメトキシエチルフタレート、ジメチルフタレート、ジオクチルフタレート、ジブチルフタレート、ジ−２−エチルヘキシルフタレート、ブチルベンジルフタレート、ジフェニルフタレート、ジシクロヘキシルフタレート等、トリメリット酸系可塑剤では、トリブチルトリメリテート、トリフェニルトリメリテート、トリエチルトリメリテート等、ピロメリット酸エステル系可塑剤では、テトラブチルピロメリテート、テトラフェニルピロメリテート、テトラエチルピロメリテート等、グリコレート系可塑剤では、トリアセチン、トリブチリン、エチルフタリルエチルグリコレート、メチルフタリルエチルグリコレート、ブチルフタリルブチルグリコレート等、クエン酸エステル系可塑剤では、トリエチルシトレート、トリ−ｎ−ブチルシトレート、アセチルトリエチルシトレート、アセチルトリ−ｎ−ブチルシトレート、アセチルトリ−ｎ−（２−エチルヘキシル）シトレート等を好ましく用いることができる。その他のカルボン酸エステルの例には、オレイン酸ブチル、リシノール酸メチルアセチル、セバシン酸ジブチル、種々のトリメリット酸エステルが含まれる。
【０１４０】
ポリエステル系可塑剤として脂肪族二塩基酸、脂環式二塩基酸、芳香族二塩基酸等の二塩基酸とグリコールの共重合ポリマーを用いることができる。脂肪族二塩基酸としては特に限定されないが、アジピン酸、セバシン酸、フタル酸、テレフタル酸、１，４−シクロヘキシルジカルボン酸等を用いることができる。グリコールとしては、エチレングリコール、ジエチレングリコール、１，３−プロピレングリコール、１，２−プロピレングリコール、１，４−ブチレングリコール、１，３−ブチレングリコール、１，２−ブチレングリコール等を用いることができる。これらの二塩基酸及びグリコールはそれぞれ単独で用いてもよいし、二種以上混合して用いてもよい。
【０１４１】
特に、特開２００２−１４６０４４号公報記載のエポキシ系化合物、ロジン系化合物、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、ケトン樹脂、トルエンスルホンアミド樹脂等の添加物を有するセルロースエステルも好ましく用いられる。
【０１４２】
具体的には、ロジン及びロジン誘導体としては、以下の構造式のものが挙げられる。
【０１４３】
【化１】

【０１４４】
上記化合物のうち、ＫＥ−６０４とＫＥ−６１０は荒川化学工業（株）からそれぞれ酸価２３７と１７０で市販されている。同じく、荒川化学工業（株）からアビエチン酸、デヒドロアビエチン酸及びパラストリン酸３者の混合物のエステル化物として、ＫＥ−１００及びＫＥ−３５６が、それぞれの酸価は８と０で市販されている。また、アビエチン酸、デヒドロアビエチン酸及びパラストリン酸３者の混合物は、播磨化成（株）からそれぞれの酸価１６７、１６８のＧ−７及びハートールＲ−Ｘで市販されている。
【０１４５】
本発明に用いるエポキシ樹脂としては、例えば、以下の構造を有するものが挙げられる。
【０１４６】
【化２】

【０１４７】
アラルダイドＥＰＮ１１７９及びアラルダイドＡＥＲ２６０は旭チバ（株）から市販されている。
【０１４８】
ケトン樹脂としては、例えば、以下の構造のものが挙げられる。
【０１４９】
【化３】

【０１５０】
ハイラック１１０、ハイラック１１０Ｈは日立化成（株）の市販品である。
パラトルエンスルホンアミド樹脂としては、以下の構造のものが挙げられ、トップラーとして、フジアミドケミカル（株）から市販されている。
【０１５１】
【化４】

【０１５２】
これらの可塑剤は単独または併用するのが好ましい。
これらの可塑剤の使用量は、フィルム性能、加工性等の点で、セルロースエステルに対して１質量％〜２０質量％が好ましい。
【０１５３】
《支持体の光学特性》
支持体の光学特性は、光学異方性としては、支持体の面内方向のリターデーション値（Ｒ_０）は０ｎｍ〜１０００ｎｍのものが好ましく用いられ、厚み方向のリターデーション値（Ｒ_ｔ）は０ｎｍ〜３００ｎｍのものが、用途により好ましく用いられる。
【０１５４】
また、波長分散特性としては、Ｒ（６００）／Ｒ（４５０）が０．７〜１．３であることが好ましく、特に１．０〜１．３であることが好ましい。ここで、Ｒ（４５０）、Ｒ（６００）は、各々４５０ｎｍ、６００ｎｍの波長の光による面内リターデーション値（Ｒ_０）を示す。
【０１５５】
《ハードコート層》
本発明に係るハードコート層について説明する。
【０１５６】
本発明に係るハードコート層としては、光硬化樹脂層または熱硬化樹脂層が好ましく用いられる。本発明では、支持体（基材ともいう）上にハードコート層として光硬化樹脂層を設け、その上に光学干渉層（中屈折率層、高屈折率層、低屈折率層等）を設けることが好ましい。
【０１５７】
ここで、これらの光硬化性樹脂、特にハードコート加工のために光硬化性樹脂層が用いられる例について説明する。
【０１５８】
本発明に係るハードコート層は、支持体上に直接設層しても、帯電防止層または下引層等の他の層の上に設層してもよい。
【０１５９】
ハードコート層として光硬化樹脂層を設ける場合には、紫外線等光照射により硬化する光硬化樹脂を含有することが好ましい。光硬化樹脂は、前述の光硬化樹脂と同様なもの（例えば、エポキシ系光硬化性化合物を用いて形成された層等）を用いることができる。光の光源、照射量、光開始剤や光増感剤、それらの使用量、等についても前述と同様である。
【０１６０】
（ハードコート層の屈折率、膜厚）
本発明に係るハードコート層は、本発明の反射防止フィルムに低反射性を付与させるための光学設計上の観点から屈折率が１．４５〜１．６５の範囲にあることが好ましい。また、反射防止フィルムに充分な耐久性、耐衝撃性を付与し、且つ、適度な屈曲性、作製時の経済性等を鑑みた観点から、ハードコート層の膜厚としては、１μｍ〜２０μｍの範囲が好ましく、更に好ましくは、１μｍ〜１０μｍである。
【０１６１】
光硬化性樹脂層とは紫外線や電子線のような光照射（本発明では、『光』とは、電子線、中性子線、Ｘ線、アルファ線、紫外線、可視光線、赤外線等、種々の電磁波をすべて光と定義する）により架橋反応等を経て硬化した樹脂を主たる成分として含有する層をいう。光硬化性樹脂としては、紫外線硬化性樹脂や電子線硬化性樹脂等が代表的なものとして挙げられるが、紫外線や電子線以外の光照射によって硬化する樹脂でもよい。紫外線硬化性樹脂としては、例えば、紫外線硬化型アクリルウレタン系樹脂、紫外線硬化型ポリエステルアクリレート系樹脂、紫外線硬化型エポキシアクリレート系樹脂、紫外線硬化型ポリオールアクリレート系樹脂、または紫外線硬化型エポキシ樹脂等を挙げることができる。
【０１６２】
紫外線硬化型アクリルウレタン系樹脂、紫外線硬化型ポリエステルアクリレート系樹脂、紫外線硬化型エポキシアクリレート系樹脂、紫外線硬化型ポリオールアクリレート系樹脂、または紫外線硬化型エポキシ樹脂の具体例としては、前記バインダーの項に記載の化合物を挙げることができる。
【０１６３】
また、前記光反応開始剤も光増感剤としても使用できる。具体的には、アセトフェノン、ベンゾフェノン、ヒドロキシベンゾフェノン、ミヒラーケトン、α−アミロキシムエステル、チオキサントン等及びこれらの誘導体を挙げることができる。また、エポキシアクリレート系樹脂の合成に光反応剤を使用する際に、ｎ−ブチルアミン、トリエチルアミン、トリ−ｎ−ブチルホスフィン等の増感剤を用いることができる。塗布乾燥後に揮発する溶媒成分を除いた紫外線硬化性樹脂組成物に含まれる光反応開始剤また光増感剤は、組成物の２．５〜６質量％であることが好ましい。
【０１６４】
樹脂モノマーとしては、例えば、不飽和二重結合が１個のモノマーとして、メチルアクリレート、エチルアクリレート、ブチルアクリレート、酢酸ビニル、ベンジルアクリレート、シクロヘキシルアクリレート、スチレン等の一般的なモノマーを挙げることができる。また不飽和二重結合を２個以上持つモノマーとして、エチレングリコールジアクリレート、プロピレングリコールジアクリレート、ジビニルベンゼン、１，４−シクロヘキサンジアクリレート、１，４−シクロヘキシルジメチルアジアクリレート、前述のトリメチロールプロパントリアクリレート、ペンタエリスリトールテトラアクリルエステル等を挙げることができる。
【０１６５】
また、紫外線硬化性樹脂組成物の光硬化を妨げない程度に、紫外線吸収剤を紫外線硬化性樹脂組成物に含ませてもよい。紫外線吸収剤としては、前記基材に使用してもよい紫外線吸収剤と同様なものを用いることができる。
【０１６６】
また硬化された層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−ｔ−３−メチルフェノール）、４，４′−ブチリデンビス（６−ｔ−ブチル−３−メチルフェノール）、１，３，５−トリス（３，５−ジ−ｔ−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−ｔ−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−ｔ−ブチルベンジルホスフェート等を挙げることができる。
【０１６７】
紫外線硬化性樹脂としては、例えば、アデカオプトマーＫＲ、ＢＹシリーズのＫＲ−４００、ＫＲ−４１０、ＫＲ−５５０、ＫＲ−５６６、ＫＲ−５６７、ＢＹ−３２０Ｂ（以上、旭電化工業（株）製）、コーエイハードの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（以上、広栄化学工業（株）製）、セイカビームのＰＨＣ２２１０（Ｓ）、ＰＨＣＸ−９（Ｋ−３）、ＰＨＣ２２１３、ＤＰ−１０、ＤＰ−２０、ＤＰ−３０、Ｐ１０００、Ｐ１１００、Ｐ１２００、Ｐ１３００、Ｐ１４００、Ｐ１５００、Ｐ１６００、ＳＣＲ９００（以上、大日精化工業（株）製）、ＫＲＭ７０３３、ＫＲＭ７０３９、ＫＲＭ７１３０、ＫＲＭ７１３１、ＵＶＥＣＲＹＬ２９２０１、ＵＶＥＣＲＹＬ２９２０２（以上、ダイセル・ユーシービー（株））、ＲＣ−５０１５、ＲＣ−５０１６、ＲＣ−５０２０、ＲＣ−５０３１、ＲＣ−５１００、ＲＣ−５１０２、ＲＣ−５１２０、ＲＣ−５１２２、ＲＣ−５１５２、ＲＣ−５１７１、ＲＣ−５１８０、ＲＣ−５１８１（以上、大日本インキ化学工業（株）製）、オーレックスＮｏ．３４０クリヤ（中国塗料（株）製）、サンラッド Ｈ−６０１（三洋化成工業（株）製）、ＳＰ−１５０９、ＳＰ−１５０７（以上、昭和高分子（株）製）、ＲＣＣ−１５Ｃ（グレース・ジャパン（株）製）、アロニックスＭ−６１００、Ｍ−８０３０、Ｍ−８０６０（以上、東亞合成（株）製）、またはその他の市販のものから適宜選択して利用することができる。
【０１６８】
光硬化性樹脂層の塗布組成物は、固形分濃度は１０〜９５質量％であることが好ましく、塗布方法により適当な濃度が選ばれる。
【０１６９】
光硬化性樹脂を光硬化反応により硬化被膜層を形成するための光源としては、紫外線を発生する光源であればいずれでも使用できる。具体的には、前記光の項に記載の光源を使用できる。照射条件はそれぞれのランプによって異なるが、照射光量としては２０ｍＪ／ｃｍ^２〜１００００ｍＪ／ｃｍ^２の範囲が好ましく、更に好ましくは、５０ｍＪ／ｃｍ^２〜２０００ｍＪ／ｃｍ^２である。近紫外線領域から可視光線領域にかけてはその領域に吸収極大のある増感剤を用いることによって使用できる。
【０１７０】
光硬化性樹脂層を塗設する際の溶媒は、例えば、炭化水素類、アルコール類、ケトン類、エステル類、グリコールエーテル類、その他の溶媒の中から適宜選択し、または混合して使用できる。好ましくは、プロピレングリコールモノ（Ｃ１〜Ｃ４）アルキルエーテルまたは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を５質量％以上、さらに好ましくは５質量％〜８０質量％以上含有する溶媒が用いられる。
【０１７１】
光硬化性樹脂組成物塗布液の塗布方法としては、グラビアコータ、スピナーコータ、ワイヤーバーコータ、ロールコータ、リバースコータ、押出コータ、エアードクターコータ等公知の方法を用いることができる。塗布量はウェット膜厚で０．１μｍ〜３０μｍが適当で、好ましくは０．５μｍ〜１５μｍである。塗布速度は１０ｍ／分〜６０ｍ／分の範囲が好ましい。
【０１７２】
光硬化性樹脂組成物は塗布乾燥された後、紫外線を照射するが、照射時間は０．５秒〜５分がよく、紫外線硬化性樹脂の硬化効率、作業効率から３秒〜２分がより好ましい。
【０１７３】
こうして硬化被膜層を得ることができるが、液晶表示装置パネルの表面に防眩性を与えるために、また他の物質との対密着性を防ぎ、対擦り傷性等を高めるために、硬化被膜層用の塗布組成物中に無機または有機の微粒子を加えることもできる。
【０１７４】
例えば、無機微粒子としては酸化珪素、酸化チタン、酸化アルミニウム、酸化錫、酸化亜鉛、炭酸カルシウム、硫酸バリウム、タルク、カオリン、硫酸カルシウム等を挙げることができる。
【０１７５】
また、有機微粒子としては、ポリメタアクリル酸メチルアクリレート樹脂粉末、アクリルスチレン系樹脂粉末、ポリメチルメタクリレート樹脂粉末、シリコン系樹脂粉末、ポリスチレン系樹脂粉末、ポリカーボネート樹脂粉末、ベンゾグアナミン系樹脂粉末、メラミン系樹脂粉末、ポリオレフィン系樹脂粉末、ポリエステル系樹脂粉末、ポリアミド系樹脂粉末、ポリイミド系樹脂粉末、またはポリ弗化エチレン系樹脂粉末等を挙げることができる。これらは紫外線硬化性樹脂組成物に加えて用いることができる。これらの微粒子粉末の平均粒径としては、０．０１μｍ〜１０μｍであり、使用量は紫外線硬化樹脂組成物１００質量部に対して、０．１質量部〜２０質量部となるように配合することが望ましい。防眩効果を付与するには、平均粒径０．１μｍ〜１μｍの微粒子を紫外線硬化樹脂組成物１００質量部に対して１質量部〜１５質量部用いるのが好ましい。
【０１７６】
このような微粒子を紫外線硬化樹脂に添加することによって、中心線平均表面粗さＲａが０．１μｍ〜０．５μｍの好ましい凹凸を有する防眩層を形成することができる。また、このような微粒子を紫外線硬化性樹脂組成物に添加しない場合、中心線平均表面粗さＲａは０．０５μｍ未満、より好ましくは０．００２μｍ〜０．０４μｍ未満の良好な平滑面を有するハードコート層を形成することができる。これらハードコート層等の上にはさらに高屈折率層（好ましくは屈折率１．６〜２．３）、低屈折率層（好ましくは屈折率１．３５〜１．５）等から構成される反射防止層を形成することもできる。またはさらに中屈折率層を設けることが好ましい。
【０１７７】
この他、ブロッキング防止機能を果たすものとして、上述したのと同じ成分で、体積平均粒径０．００５μｍ〜０．１μｍの極微粒子を樹脂組成物１００質量部に対して０．１質量部〜５質量部を用いることもできる。
【０１７８】
《反射防止フィルムの裏面（支持体の裏面ともいう）》
本発明の反射防止フィルムの裏面には、高さ０．１μｍ〜１０μｍの突起を１個〜５００個／０．０１ｍｍ^２が設けられていることが好ましく、更に好ましくは、１０個〜４００個／０．０１ｍｍ^２であり、特に好ましくは、１５個〜３００個／０．０１ｍｍ^２である。
【０１７９】
これによって、各光学干渉層塗設中に一旦ロール状に巻き取りをしてもブロッキングの発生が防止できるだけでなく、次の光学干渉層を塗設する際の塗布むらを著しく低減することができる。塗布むらの原因は完全に明らかにはなっていないが、原因の１つとしてロール状に巻き取ったフィルムを塗布工程に送り出す際の剥離帯電が関係していると推測される。
【０１８０】
前記裏面に突起を設ける手段としては、支持体基材フィルム中に微粒子を添加することで、裏面に高さ０．１μｍ〜１０μｍの突起を１個〜５００個／０．０１ｍｍ^２有するようにすることができる。このとき、基材フィルムを多層構成として、表層のみに微粒子を含ませることもできる。
【０１８１】
添加する微粒子の種類としては、有機化合物でも無機化合物でもよく、例えば二酸化珪素、二酸化チタン、酸化アルミニウム、酸化ジルコニウム、炭酸カルシウム、カオリン、タルク、焼成ケイ酸カルシウム、水和ケイ酸カルシウム、ケイ酸アルミニウム、ケイ酸マグネシウム、リン酸カルシウム等の無機微粒子や架橋高分子微粒子を含有させることが好ましい。中でも二酸化珪素がフィルムのヘイズを小さくできるので好ましい。微粒子の２次粒子の平均粒径は０．１〜１０μｍで、その含有量は基材のセルロースエステルに対して０．０４〜０．３質量％が好ましい。二酸化珪素のような微粒子には有機物により表面処理されている場合が多いが、これはフィルムのヘイズを低下できるため好ましい。表面処理で好ましい有機物としては、ハロシラン類、アルコキシシラン類（特にメチル基を有するアルコキシシラン類）、シラザン、シロキサン等が挙げられる。微粒子の平均粒径は大きい方がマット効果が大きく、反対に平均粒径の小さい方は透明性に優れるため、好ましい微粒子の一次粒子の平均粒径は５ｎｍ〜５０ｎｍで、より好ましくは７ｎｍ〜１６ｎｍである。二酸化珪素の微粒子としてはアエロジル（株）製のＡＥＲＯＳＩＬ（アエロジル）２００、２００Ｖ、３００、Ｒ９７２、Ｒ９７２Ｖ、Ｒ９７４、Ｒ２０２、Ｒ８１２，ＯＸ５０、ＴＴ６００等を挙げることができ、好ましくはＡＥＲＯＳＩＬ（アエロジル）２００Ｖ、Ｒ９７２、Ｒ９７２Ｖ、Ｒ９７４、Ｒ２０２、Ｒ８１２である。これらの微粒子は２種以上併用してもよい。２種以上併用する場合、任意の割合で混合して使用することができる。この場合、平均粒径や材質の異なる微粒子、例えばＡＥＲＯＳＩＬ（アエロジル）２００ＶとＲ９７２Ｖを質量比で０．１：９９．９〜９９．９：０．１の範囲で使用できる。
【０１８２】
本発明において、微粒子はドープ調製時にセルロースエステル、他の添加剤及び有機溶媒とともに含有させて分散してもよいが、セルロースエステル溶液とは別に微粒子分散液のような十分に分散させた状態でドープを調製するのが好ましい。微粒子を分散させるために、前もって有機溶媒にひたしてから高剪断力を有する分散機（高圧分散装置）で細分散させておくのが好ましい。その後により多量の有機溶媒に分散して、セルロースエステル溶液と合流させ、インラインミキサーで混合してドープとすることが好ましい。この場合、微粒子分散液に紫外線吸収剤を加え紫外線吸収剤液としてもよい。
【０１８３】
また、光学干渉層を有する反射防止フィルムの裏面側に微粒子を含む層を塗設することによって、裏面に高さ０．１μｍ〜１０μｍの突起を１個〜５００個／０．０１ｍｍ^２有する反射防止フィルム（低反射積層体ともいう）を提供することができる。
【０１８４】
《カール特性》
本発明の反射防止フィルムのカール特性について説明する。
【０１８５】
フィルムの片面だけに表面加工を施した場合や、両面に異なる種類または異なる程度の表面加工を施した場合等には、フィルムが丸まってしまうというカール現象が起こり易い。カールするとこれを用いて偏光板を作製する際等に取扱い難く不都合である。
【０１８６】
カールを防止するため、ハードコート層を塗設した反対側にアンチカール層を設けることができる。すなわち、アンチカール層を設けた面を内側にして丸まろうとする性質を持たせることにより、カールの度合いをバランスさせるものである。なお、アンチカール層は好ましくはブロッキング層を兼ねて塗設され、その場合、塗布組成物にはブロッキング防止機能を持たせるための前述の無機微粒子及び／または有機微粒子を含有させることができる。（この層は、バックコート層とも言う。）
アンチカール機能の付与は、具体的には基材を溶解させる溶媒または膨潤させる溶媒を含む組成物を塗布することによって行われる。用いる溶媒としては、溶解させる溶媒または膨潤させる溶媒の混合物の他、さらに溶解させない溶媒を含む場合もある。これらを樹脂フィルムのカール度合や樹脂の種類によって適宜選択した割合で混合した組成物及び塗布量を用いて行う。
【０１８７】
カール防止機能を強めたい場合は、溶解させる溶媒または膨潤させる溶媒の混合比率を大きくし、溶解させない溶媒の比率を小さくするのが効果的である。この混合比率は好ましくは、（溶解させる溶媒または膨潤させる溶媒）：（溶解させない溶媒）＝１０：０〜１：９で用いられる。このような混合組成物に含まれる、溶解または膨潤させる溶媒としては、例えば、ベンゼン、トルエン、キシレン、ジオキサン、アセトン、メチルエチルケトン、Ｎ，Ｎ−ジメチルホルムアミド、酢酸メチル、酢酸エチル、トリクロロエチレン、メチレンクロライド、エチレンクロライド、テトラクロロエタン、トリクロロエタン、クロロホルム等がある。溶解させない溶媒としては、例えば、メタノール、エタノール、ｎ−プロピルアルコール、ｉ−プロピルアルコール、ｎ−ブタノール等がある。
【０１８８】
これらの塗布組成物をグラビアコータ、ディップコータ、リバースロールコータ、押し出しコータ等を用いて基材の表面にウェット膜厚１〜１００μｍ塗布するのが好ましいが、特に５〜３０μｍであるとよい。
【０１８９】
この塗布組成物には樹脂を含ませることができ、ここで用いられる樹脂としては、例えば塩化ビニル／酢酸ビニル共重合体、塩化ビニル樹脂、酢酸ビニル樹脂、酢酸ビニルとビニルアルコールの共重合体、部分加水分解した塩化ビニル／酢酸ビニル共重合体、塩化ビニル／塩化ビニリデン共重合体、塩化ビニル／アクリロニトリル共重合体、エチレン／ビニルアルコール共重合体、塩素化ポリ塩化ビニル、エチレン／塩化ビニル共重合体、エチレン／酢酸ビニル共重合体等のビニル系重合体または共重合体、ニトロセルロース、セルロースアセテートプロピオネート、ジアセチルセルロース、セルロースアセテートブチレート、セルロースアセテートプロピオネート樹脂等のセルロースエステル系樹脂、マレイン酸及び／またはアクリル酸の共重合体、アクリル酸エステル共重合体、アクリロニトリル／スチレン共重合体、塩素化ポリエチレン、アクリロニトリル／塩素化ポリエチレン／スチレン共重合体、メチルメタクリレート／ブタジエン／スチレン共重合体、アクリル樹脂、ポリビニルアセタール樹脂、ポリビニルブチラール樹脂、ポリエステルポリウレタン樹脂、ポリエーテルポリウレタン樹脂、ポリカーボネートポリウレタン樹脂、ポリエステル樹脂、ポリエーテル樹脂、ポリアミド樹脂、アミノ樹脂、スチレン／ブタジエン樹脂、ブタジエン／アクリロニトリル樹脂等のゴム系樹脂、シリコーン系樹脂、フッ素系樹脂等を挙げることができるが、これらに限定されるものではない。アクリル樹脂としては、アクリペットＭＤ、ＶＨ、ＭＦ、Ｖ（以上、三菱レーヨン（株）製）、ハイパールＭ−４００３、Ｍ−４００５、Ｍ−４００６、Ｍ−４２０２、Ｍ−５０００、Ｍ−５００１、Ｍ−４５０１（以上、根上工業（株）製）、ダイヤナールＢＲ−５０、ＢＲ−５２、ＢＲ−５３、ＢＲ−６０、ＢＲ−６４、ＢＲ−７３、ＢＲ−７５、ＢＲ−７７、ＢＲ−７９、ＢＲ−８０、ＢＲ−８２、ＢＲ−８３、ＢＲ−８５、ＢＲ−８７、ＢＲ−８８、ＢＲ−９０、ＢＲ−９３、ＢＲ−９５、ＢＲ−１００、ＢＲ−１０１、ＢＲ−１０２、ＢＲ−１０５、ＢＲ−１０６、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）等が用いられる。特に好ましくはジアセチルセルロース、セルロースアセテートプロピオネートのようなセルロースエステル樹脂が用いられる。
【０１９０】
アンチカール層を塗設する順番は、基材の反対側に光学的機能性層（例えば帯電防止層またはハードコート層、光学干渉層等）を塗設する前でも後でも構わないが、アンチカール層がブロッキング防止層を兼ねる場合は先に塗設することが望ましい。
【０１９１】
《偏光板》
本発明の偏光板について説明する。
【０１９２】
本発明の偏光板は、一般的な方法で作製することができる。例えば、本発明の光学補償フィルムをアルカリ鹸化処理した後に、沃素溶液中に浸漬延伸して作製した偏光膜の両面に、完全ケン化型ポリビニルアルコール水溶液を用いて貼り合わせる方法がある。アルカリ鹸化処理とは、水系接着剤の濡れを良くし、接着性を向上させるために、セルロースエステルフィルムを高温の強アルカリ液中に浸ける処理のことをいう。
【０１９３】
また、本発明の偏光板においては、二色性物質を含有する偏光子の光透過軸と前記偏光子に貼合する光学補償フィルムの流延製膜時の幅手方向の延伸方向とが略平行になるように貼合されることが好ましい。尚、本発明において、直交しているとは上記記載のように軸同士が略直交していることを表し、また、方向が一致しているとは、軸同士の向きが略平行であることを示す。ここで、略平行とは、当該各々の軸のなす角が±１０°以内であり、好ましくは±３°以内、さらに好ましくは±１°以内であり、特に好ましくは、±０°である場合を表す。
【０１９４】
本発明の偏光板に用いる偏光子としては、従来公知のものを用いることができる。例えば、ポリビニルアルコールの如き親水性ポリマーからなるフィルムを、ヨウ素の如き二色性染料で処理して延伸したものや、塩化ビニルの如きプラスチックフィルムを処理して配向させたものを用いる。こうして得られた偏光子を、セルロースエステルフィルムと貼合する。
【０１９５】
このとき、セルロールエステルフィルムのうちの少なくとも一枚は、本発明の光学補償フィルムが用いられる。もう一方の面には、別のセルロースエステルフィルムを用いることができる。もう一方の面にも本発明の光学補償フィルム用に製造したセルロースエステルフィルムを用いてもよいし、市販のセルロースエステルフィルム（コニカタック ＫＣ８ＵＸ２ＭＷ、ＫＣ４ＵＸ２ＭＷ、ＫＣ５ＵＮ（コニカ（株）製））を表面側のもう一方の面の偏光板保護フィルムとして用いることができる。表示装置の表面側に用いられる偏光板保護フィルムには防眩層あるいはクリアハードコート層のほか、反射防止層、帯電防止層、防汚層を有することが好ましい。反射防止層（酸化珪素層、酸化チタン層）、帯電防止層、防汚層は塗布、スパッタ、ＣＶＤ、大気圧プラズマＣＶＤ、真空蒸着等の方法で好ましく設けられる。
【０１９６】
《液晶表示装置》
上記ようにして得られる、本発明の偏光板を、液晶セルの両面に配置して貼合し、本発明の液晶表示装置を作製することが出来る。
【０１９７】
また、偏光板の作製時には、本発明の光学補償フィルムの遅相軸と偏光子の透過軸が平行となるように貼合することが好ましい。これによって、黒表示のときの光漏れが著しく改善され、１５型以上、好ましくは１９型以上の大画面の液晶表示装置であっても、画面周辺部での白抜けなどもなく、その効果が長期間維持され、特にＶＡ型液晶表示装置では顕著な効果が認められる。
【０１９８】
本発明の光学補償フィルムには必要に応じてさらに液晶性化合物を用いた光学異方性層を形成することができ、ＴＮ，ＶＡ，ＯＣＢ，ＨＡＮ等の各種駆動方式を採用した液晶表示装置の視野角特性を最適化することができる。
【０１９９】
【実施例】
以下、実施例により本発明を説明するが本発明はこれらに限定されない。
【０２００】
実施例１
《反射防止フィルム１の作製》
以下のようにして、反射防止フィルム１を作製した。作製した反射防止フィルムのハードコート層、高屈折率層、低屈折率層、中屈折率層等の光学干渉層の屈折率、膜厚は下記方法で測定した。
【０２０１】
（屈折率、膜厚）
各屈折率層やハードコート層等の屈折率と膜厚は、各層を単独で塗設したサンプルについて、分光光度計の分光反射率の測定結果から求めた。
【０２０２】
分光光度計はＵ−４０００型（日立製作所製）を用いて、サンプルの測定側の裏面を粗面化処理した後、黒色のスプレーで光吸収処理を行って裏面での光の反射を防止して、５度正反射の条件にて可視光領域（４００ｎｍ〜７００ｎｍ）の反射率の測定を行う。
【０２０３】
《ハードコート層の作製》
膜厚８０μｍのセルローストリアセテートフィルム（コニカ（株）製コニカタックＫＣ８ＵＸ２ＭＷ、屈折率１．４９、アセチル基の置換度２．８８）の片面に下記ハードコート層組成物（Ｃ−１）を乾燥膜厚３．５μｍとなるように塗布し、８０℃にて１分間乾燥した。次に高圧水銀ランプ（８０Ｗ）にて１５０ｍＪ／ｃｍ^２の条件で硬化させ、ハードコート層を作製した。
【０２０４】
ハードコート層の膜厚 ：３．５μｍ
ハードコート層の屈折率：１．５０
（ハードコート層組成物（Ｃ−１））
ジペンタエリスリトールヘキサアクリレート
単量体 １２０質量部
２量体 ４０質量部
３量体以上の成分 ４０質量部
ジエトキシベンゾフェノン（ＵＶ光開始剤） ２０質量部
プロピレングリコールモノメチルエーテル ３３０質量部
酢酸エチル ３３０質量部
《高屈折率層の作製》
次いで、前記ハードコート層の上に、下記高屈折率層組成物Ｈ−１をダイコータで塗布し、８０℃、０．１ｍ／秒の条件で１分間乾燥させた。乾燥後、高圧水銀ランプ（８０Ｗ）を用いて紫外線を１３０ｍＪ／ｃｍ^２照射して硬化させ、高屈折率層を形成した。
【０２０５】
高屈折率層の膜厚 ：７２ｎｍ
高屈折率層の屈折率：１．７０
（高屈折率層組成物（Ｈ−１））
固形分１５％酸化チタン微粒子分散物（シーアイ化成工業社製、
ＲＴＳＰＮＢ１５ＷＴ％−Ｇ０） ３３０質量部
ジ−ｉ−プロポキシ・ビス（アセチルアセトナト）チタン
（オルガチックスＴＣ１００ 松本製薬工業社製） ５質量部
ジペンタエリスリトールヘキサアクリレート単量体 ４０質量部
イルガキュア １８４ １０質量部
直鎖ジメチルシリコーン−ＥＯブロックコポリマー
（ＦＺ−２２０７ 日本ユニカー社製） １質量部
プロピレングリコールモノメチルエーテル １４７０質量部
イソプロピルアルコール ２６６０質量部
メチルエチルケトン ４９０質量部
《低屈折率層の作製》
得られた高屈折率層上に、下記低屈折率層組成物（Ｌ−１）をダイコータで塗布し、８０℃、０．１ｍ／秒の条件で１分間乾燥させた。乾燥後、高圧水銀ランプ（８０Ｗ）を用いて紫外線を１３０ｍＪ／ｃｍ^２照射して硬化させ、低屈折率層を形成し、更に１２０℃で５分間熱硬化させ低屈折率層を有する反射防止フィルム１を作製した。
【０２０６】
低屈折率層の膜厚：１００ｎｍ
低屈折率層屈折率：１．４４
（テトラエトキシシラン加水分解物Ａの調製）
テトラエトキシシラン２９ｇとエタノール５５ｇを混合し、これに酢酸の１．６質量％水溶液１６ｇを添加した後に、２５℃にて２０時間攪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。
【０２０７】
（低屈折率層組成物（Ｌ−１）の調製）
テトラエトキシシラン加水分解物Ａ ２３０質量部
γ−メタクリロキシプロピルトリメトキシシシラン
（ＫＢＭ５０３：：信越化学社製） ６質量部
直鎖ジメチルシリコーン−ＥＯブロックコポリマー
（ＦＺ−２２０７：日本ユニカー社製）の
１０％プロピレングリコールモノメチルエーテル溶液 ３質量部
プロピレングリコールモノメチルエーテル ３８０質量部
イソプロピルアルコール ３８０質量部
《反射防止フィルム２の作製》
反射防止フィルム１の作製において、ハードコート層の膜厚を７．０μｍに変更し、且つ、ナノインデンテーション硬度（Ｈ）、弾性率（Ｅｒ）を表１に記載のように調整した以外は同様にして反射防止フィルム２を作製した。
【０２０８】
《反射防止フィルム３の作製》
反射防止フィルム２の作製において、ハードコート層組成物を下記ハードコート層組成物（Ｃ−２）に変更し、且つ、ナノインデンテーション硬度（Ｈ）、弾性率（Ｅｒ）を表１に記載のように調整した以外は様にして反射防止フィルム３を作製した。
【０２０９】
〈ハードコート層組成物（Ｃ−２）〉
ジペンタエリスリトールヘキサアクリレート
単量体 １２０質量部
２量体 ４０質量部
３量体以上の成分 ４０質量部
ジエトキシベンゾフェノン（ＵＶ光開始剤） ２０質量部
プロピレングリコールモノメチルエーテル １１０質量部
酢酸エチル １１０質量部
《反射防止フィルム４の作製》
反射防止フィルム３の作製において、ハードコート層の膜厚を１５μｍに変更した以外、同様にして反射防止フィルム４を作製した。
【０２１０】
《反射防止フィルム５の作製》
反射防止フィルム３の作製において、ハードコート層組成物を下記ハードコート層組成物（Ｃ−３）に変更した以外は同様にして反射防止フィルム５を作製した。
【０２１１】
（ハードコート層組成物（Ｃ−３））
ジペンタエリスリトールヘキサアクリレート
単量体 ９０質量部
２量体 ３５質量部
３量体以上の成分 ３５質量部
アクリル樹脂（ダイヤナールＢＲ１０８、
三菱レーヨン社製） ２０質量部
ジエトキシベンゾフェノン（ＵＶ光開始剤） ２０質量部
プロピレングリコールモノメチルエーテル １１０質量部
酢酸エチル １１０質量部
《反射防止フィルム６の作製》
反射防止フィルム３の作製において、ハードコート層組成物を下記ハードコート層組成物（Ｃ−４）に変更した以外は同様にして反射防止フィルム６を作製した。
【０２１２】
〈ハードコート層組成物（Ｃ−４）〉
ＫＲＸ−５７４−７（旭電化工業社製ハードコート剤） １００質量部
プロピレングリコールモノメチルエーテル ５０質量部
酢酸エチル ５０質量部
《反射防止フィルム７の作製》
反射防止フィルム３の作製において、低屈折率層組成物（Ｌ−１）を下記低屈折率層組成物（Ｌ−２）に変更し、紫外線を５００ｍＪ／ｃｍ^２照射して硬化させた以外は同様にして反射防止フィルム７を作製した。
【０２１３】
（低屈折率層組成物（Ｌ−２））
オブスターＪＮ７２００（Ｆ系ポリマー：ＪＳＲ（株）） １０質量部
ＭＩＢＫ ４９０質量部
《反射防止フィルム８の作製》
反射防止フィルム１の作製において、ハードコート層の膜厚を０．５μｍに変更し、且つ、前記ハードコート層、低屈折率層の各々のナノインデンテーション硬度（Ｈ）、弾性率（Ｅｒ）を表１に記載のように変更した以外は同様にして反射防止フィルム８を作製した。
【０２１４】
《反射防止フィルム９の作製》
反射防止フィルム３の作製において、ハードコート層の膜厚を２２μｍに変更し、且つ、前記ハードコート層、低屈折率層の各々のナノインデンテーション硬度（Ｈ）、弾性率（Ｅｒ）を表１に記載のように変更した以外は同様にして反射防止フィルム９を作製した。
【０２１５】
《反射防止フィルム１０の作製》
反射防止フィルム３の作製において、ハードコート層上に下記のように高屈折率層組成物（Ｈ−２）、低屈折率層組成物（Ｌ−１）を各々押し出しコータを用いて層形成した以外は同様にして、反射防止フィルム１０を作製した。
【０２１６】
（高屈折率層の作製）
ハードコート層上に下記高屈折率層組成物（Ｈ−２）をダイコータで塗布し、８０℃、０．１ｍ／秒の条件で１分間乾燥させた。乾燥後、高圧水銀ランプ（８０Ｗ）を用いて紫外線を１３０ｍＪ／ｃｍ^２照射し、更に１２０℃で５分間熱処理を実施し、再び高圧水銀ランプ（８０Ｗ）を用いて紫外線を１３０ｍＪ／ｃｍ^２照射し、１２０℃で５分間熱処理を実施して、高屈折率層を形成した。
【０２１７】
高屈折率層の膜厚 ：７２ｎｍ
高屈折率層の屈折率：１．７０
〈高屈折率層組成物（Ｈ−２）〉
テトラ（ｎ）ブトキシチタン ５０質量部
γ−メタクリロキシプロピルトリメトキシシシラン
（ＫＢＭ５０３ 信越化学社製） ３４質量部
アクリル樹脂（ダイヤナールＢＲ１０２、
三菱レーヨン社製） １５質量部
直鎖ジメチルシリコーン−ＥＯブロックコポリマー
（ＦＺ−２２０７：日本ユニカー社製） １質量部
プロピレングリコールモノメチルエーテル １４７０質量部
イソプロピルアルコール ２９４０質量部
メチルエチルケトン ４９０質量部
次いで、上記の低屈折率層組成物（Ｌ−１）をダイコータで塗布し、８０℃、０．１ｍ／秒の条件で１分間乾燥させた。乾燥後、高圧水銀ランプ（８０Ｗ）を用いて紫外線を１３０ｍＪ／ｃｍ^２照射して硬化させ、低屈折率層を形成し、更に１２０℃で５分間熱処理を実施し、再び高圧水銀ランプ（８０Ｗ）を用いて紫外線を１３０ｍＪ／ｃｍ^２照射し、１２０℃で５分間熱処理を実施して低屈折率層を有する反射防止フィルム１０を作製した。
【０２１８】
低屈折率層の膜厚 ：１００ｎｍ
低屈折率層の屈折率：１．４４
また、最表面層である低屈折率層の表面、表面近傍、並びに層内部にわたるフッ素元素の含有率は下記のように行った。
【０２１９】
《低屈折率層のフッ素元素含有率の測定》
本発明に係る低屈折率層のフッ素元素含有率測定については、上記のＸ線光電子分光（ＸＰＳ）表面分析装置を用いた。分析は表面、表面近傍更に層内部にわたり分析を組成分析（フッ素元素分析）を行った。
【０２２０】
また、層内部の分析、即ち、深さ方向の組成分析はイオンエッチングを用いて表面層を削りながら行った。以下、イオンエッチングの具体的条件を記載する。
【０２２１】
イオンエッチング：ＶＧサイエンティフィック社製ＥＸ０５イオン銃使用
エッチングイオン：アルゴン、バリアブルリークバルブを通し導入量を調整
イオン量：３μＡ
加速電圧：３ｋＶ
イオンエッチングの面積はＰｈｙｓｉｃａｌＩｍａｇｉｎｇＵｎｉｔのＭＡＧＮＩＦＩＣＡＴＩＯＮを５に設定して行った。
【０２２２】
レンズモード：ＳＸＡ−１（分析径１ｍｍφ）に設定
エッチング時間は６０秒とし、エッチング後１０秒経過後、組成分析を行い、更に繰り返し２回エッジングと測定を繰り返し、合計３回の測定値の平均をとった。
【０２２３】
上記で作製した反射防止フィルム１〜１０の構成層の物性値（膜厚、屈折率、ナノインデンテーション硬度（Ｈ）、弾性率（Ｅｒ））、層形成方法、Ｆ含有率（フッ素原子含有率）等を表２に示す。
【０２２４】
【表２】

【０２２５】
得られた反射防止フィルム１〜１０の各々を下記のように評価した。
《平面性》
反射防止フィルム１〜１０の各々を黒色のビロード布を貼った台上に置き、目視で平面性を観測し、下記のようにランク評価した。
【０２２６】
◎：平面性が非常に良好である
○：平面性が良好である
△：多少凹凸が観察される
×：多くの凹凸が観察される
《取り扱い性》
フィルムの取り扱いで、爪折れ跡や割れの発生しやすさを評価した。
【０２２７】
○：爪折れ跡がつきにくい
△：爪折れ跡は多少残るが、割れは発生しにくい
×：爪折れ跡が残りやすく、割れも発生しやすい
《耐擦傷性》
フィルムを平滑な台の上に置き、＃００００のスチールウール上に１ｃｍ^２あたり２００ｇの荷重をかけて、フィルム表面を２０往復擦り、擦る方向と垂直方向に１ｃｍの範囲で発生した傷の本数を目視で数え、以下の基準で評価した。
【０２２８】
◎：０本
○：１〜５本
△：５〜２０本
×：２０本以上
《鉛筆硬度》
ＪＩＳ Ｋ ５４００に準拠した鉛筆硬度試験を行った。ただし、荷重は５００ｇとして実施した。
【０２２９】
《防汚性》
反射防止処理面に指で指紋をつけ、指紋がベンコットで拭取れるかどうか調べた。
【０２３０】
◎：非常に間単位ふき取れる
○：ふき取れる
×：ふき残る
《耐溶剤性》
反射防止処理面を、メチルエチルケトンを含浸したベンコットで強く擦り、反射防止処理面の状態の変化を観察した。
【０２３１】
○：変化なし
△：わずかに膜剥がれなどが発生する
×：膜剥がれなど外観に変化を生ずる
《熱クラック》
反射防止フィルムを１００℃の恒温槽に投入し、４００時間保持した後、反射防止処理面の裏面に黒色テープを貼り、反射防止処理面を顕微鏡観察（対物レンズ２０倍、接眼レンズ１０倍）し、クラックの発生を目視により下記のようにランク評価した。
【０２３２】
○：クラックなし
△：弱く、短いクラックが発生する
×：長いクラックが発生する
得られた結果を表３に示す。
【０２３３】
【表３】

【０２３４】
表３から、比較に比べて、本発明の反射防止フィルムは、平面性、取り扱い性、耐擦傷性、鉛筆硬度、熱クラック、防汚性、耐溶剤性の全ての項目において、優れた特性を示すことが明らかである。
【０２３５】
実施例２
《反射防止フィルム１１の作製》
実施例１の反射防止フィルム３の作製において、ハードコート層上に下記のように中屈折率層、高屈折率層、次いで、前記低屈折率層を各々設けた以外は同様にして反射防止フィルム１１を作製した。
【０２３６】
（中屈折率層の作製）
反射防止フィルム３のハードコート層上に、下記中屈折率層組成物Ｍ−１をダイコータで塗布し、８０℃、０．１ｍ／秒の条件で１分間乾燥させた。乾燥後、高圧水銀ランプ（８０Ｗ）を用いて紫外線を１３０ｍＪ／ｃｍ^２照射して硬化させ、中屈折率層を形成した。
【０２３７】
中屈折率層の膜厚 ：８６ｎｍ
中屈折率層の屈折率：１．６４
（中屈折率層組成物（Ｍ−１））
テトラ（ｎ）ブトキシチタン ４５質量部
γ−メタクリロキシプロピルトリメトキシシシラン
（信越化学社製、ＫＢＭ５０３） ３９質量部
アクリル樹脂（ダイヤナールＢＲ１０２、
三菱レーヨン社製） １５質量部
直鎖ジメチルシリコーン−ＥＯブロックコポリマー
（日本ユニカー社製 ＦＺ−２２０７） １質量部
プロピレングリコールモノメチルエーテル １４７０質量部
イソプロピルアルコール ２９４０質量部
メチルエチルケトン ４９０質量部
（高屈折率層の作製）
次いで、中屈折率層の上に、下記高屈折率層組成物Ｈ−３をダイコータで塗布し、８０℃、０．１ｍ／秒の条件で１分間乾燥させた。乾燥後、高圧水銀ランプ（８０Ｗ）を用いて紫外線を１３０ｍＪ／ｃｍ^２照射し、１２０℃で５分間熱処理を実施して、高屈折率層を形成した。
【０２３８】
高屈折率層の膜厚 ：８０ｎｍ
高屈折率層の屈折率：１．８７
（高屈折率層組成物Ｈ−３）
テトラ（ｎ）ブトキシチタン ８９質量部
γ−メタクリロキシプロピルトリメトキシシシラン
（ＫＢＭ５０３ 信越化学社製） ５質量部
アクリル樹脂（ダイヤナールＢＲ１０２、
三菱レーヨン社製） ５質量部
直鎖ジメチルシリコーン−ＥＯブロックコポリマー
（ＦＺ２２０７、日本ユニカー社製） １質量部
プロピレングリコールモノメチルエーテル １４７０質量部
イソプロピルアルコール ２９４０質量部
メチルエチルケトン ４９０質量部
《低屈折率層の作製》
ついで、高屈折率層の上に、前記低屈折率層組成物Ｌ−１をダイコータで塗布し、８０℃、０．１ｍ／秒の条件で１分間乾燥させた。乾燥後、高圧水銀ランプ（８０Ｗ）を用いて紫外線を１３０ｍＪ／ｃｍ^２照射して硬化させ、低屈折率層を形成し、更に１２０℃で５分間熱硬化させ低屈折率層を有する反射防止フィルム１１を作製した。
【０２３９】
低屈折率層の膜厚 ：１００ｎｍ
低屈折率層の屈折率：１．４４
《反射防止フィルム１２の作製》
反射防止フィルム１１の作製において、低屈折率層の作製に下記低屈折率層組成物（Ｌ−３）を用いた以外は同様にしてを反射防止フィルム１２を作製した。
【０２４０】
〈加水分解物Ｂの調製〉
トリフルオロプロピルトリメトキシシラン（ＫＢＭ７１０３、信越化学社製）１４ｇ、エタノール７８ｇを混合し、これに酢酸の４．０質量％水溶液７．５ｇを添加した後に、２５℃にて２０時間攪拌することでトリフルオロプロピルトリメトキシシラン加水分解物Ｂを調製した。
【０２４１】
《低屈折率層組成物（Ｌ−３）》
テトラエトキシシラン加水分解物Ａ ５２０質量部
トリフルオロプロピルトリメトキシシラン加水分解物Ｂ ５０質量部
γ−メタクリロキシプロピルトリメトキシシシラン
（ＫＢＭ５０３、信越化学社製） ６質量部
直鎖ジメチルシリコーン−ＥＯブロックコポリマー
（日本ユニカー社製：ＦＺ−２２０７）の１０％プロピレン
グリコールモノメチルエータル溶液 ５０質量部
プロピレングリコールモノメチルエーテル １２００質量部
イソプロピルアルコール １２００質量部
低屈折率層の膜厚 ：１００ｎｍ
低屈折率層の屈折率：１．４３
低屈折率層のフッ素元素の含有率は５％。
【０２４２】
《反射防止フィルム１３の作製》
反射防止フィルム１１の作製において、ハードコート層上に下記のように中屈折率層、高屈折率層、次いで、低屈折率層を各々設けた以外は同様にして反射防止フィルム１３を作製した。
【０２４３】
（中屈折率層）
ハードコート層上に、下記中屈折率層組成物Ｍ−２をダイコータで塗布し、８０℃、０．１ｍ／秒の条件で１分間乾燥させた。乾燥後、高圧水銀ランプ（８０Ｗ）を用いて紫外線を１３０ｍＪ／ｃｍ^２照射して硬化させ、中屈折率層を形成した。
【０２４４】
（中屈折率層組成物Ｍ−２）
固形分１５％酸化チタン微粒子分散物（シーアイ化成工業社製
ＲＴＳＰＮＢ１５ＷＴ％−Ｇ０） ２７０質量部
ジ−ｉ−プロポキシ・ビス（アセチルアセトナト）チタン
（オルガチックスＴＣ１００：松本製薬工業社製） ５質量部
ジペンタエリスリトールヘキサアクリレート
（ＫＡＹＡＲＡＤ ＤＰＨＡ：日本化薬社製） ４０質量部
イルガキュア１８４ １０質量部
直鎖ジメチルシリコーン−ＥＯブロックコポリマー
（ＦＺ−２２０７、日本ユニカー社製） １質量部
プロピレングリコールモノメチルエーテル １４７０質量部
イソプロピルアルコール ２７２０質量部
メチルエチルケトン ４９０質量部
中屈折率層の膜厚 ：８６ｎｍ
中屈折率層の屈折率：１．６４
（高屈折率層の作製）
次いで、中屈折率層の上に、下記高屈折率層組成物Ｈ−４をダイコータで塗布し、８０℃、０．１ｍ／秒の条件で１分間乾燥させた。乾燥後、高圧水銀ランプ（８０Ｗ）を用いて紫外線を１３０ｍＪ／ｃｍ^２照射し、１００℃で１分間熱処理を実施して、高屈折率層を形成した。
【０２４５】
（高屈折率層組成物Ｈ−４）
固形分１５％酸化チタン微粒子分散物（シーアイ化成工業社製、
ＲＴＳＰＮＢ１５ＷＴ％−Ｇ０） ５３０質量部
テトラ（ｎ）ブトキシチタン １０質量部
γ−メタクリロキシプロピルトリメトキシシシラン
（ＫＢＭ５０３ 信越化学社製） １０質量部
直鎖ジメチルシリコーン−ＥＯブロックコポリマー
（ＦＺ−２２０７ 日本ユニカー社製） １質量部
プロピレングリコールモノメチルエーテル １４７０質量部
イソプロピルアルコール ２４９０質量部
メチルエチルケトン ４９０質量部
高屈折率層の膜厚 ：８０ｎｍ
高屈折率層の屈折率：１．８５
次いで、反射防止フィルム１２の作製に用いた、前記低屈折率層組成物（Ｌ−２）を用いて低屈折率層を形成した後、６５℃、１２０時間エージング処理を行ない、反射防止フィルム１３を得た。
【０２４６】
《反射防止フィルム１４の作製》
反射防止フィルム１３の作製において、低屈折率層の作製に下記低屈折率組成物（Ｌ−３）を用いた以外は同様にして反射防止フィルム１４を作製した。
【０２４７】
低屈折率層の膜厚 ：１００ｎｍ
低屈折率層の屈折率：１．４３
低屈折率層のフッ素元素の含有率は５％。
【０２４８】
《反射防止フィルム１５の作製》
反射防止フィルム１３の作製において、下記低屈折率組成物（Ｌ−４）を用いて低屈折率層を作製した以外は同様にして反射防止フィルム１５を作製した。
【０２４９】
（加水分解物Ｃの調製）
ヘプタデカトリフルオロデシルトリメトキシシラン（ＫＢＭ７８０３、信越化学社製）５ｇ、エタノール８０ｇを混合し、これに酢酸の２．５質量％水溶液１２ｇを添加した後に、２５℃にて２０時間攪拌することでヘプタデカトリフルオロデシルトリメトキシシラン加水分解物Ｃ（単に加水分解物Ｃともいう）を調製した。
【０２５０】
（低屈折率層組成物（Ｌ−４）の調製）
テトラエトキシシラン加水分解物Ａ ７２０質量部
ヘプタデカトリフルオロデシル−
トリメトキシシラン加水分解物Ｃ １４０質量部
γ−メタクリロキシプロピルトリメトキシシシラン
（ＫＢＭ５０３、信越化学社製） ９質量部
直鎖ジメチルシリコーン−ＥＯブロックコポリマー
（日本ユニカー社製、ＦＺ−２２０７）の
１０％プロピレングリコールモノメチルエータル溶液 ７質量部
プロピレングリコールモノメチルエーテル １７６０質量部
イソプロピルアルコール １７６０質量部
低屈折率層の膜厚 ：１００ｎｍ
低屈折率層の屈折率：１．４２
低屈折率層のフッ素元素の含有率は２５％。
【０２５１】
《反射防止フィルム１６の作製》
反射防止フィルム１３の作製において、下記低屈折率組成物（Ｌ−５）を用いて低屈折率層を作製した以外は同様にして反射防止フィルム１６を作製した。
【０２５２】
（低屈折率層組成物（Ｌ−５）の調製）
テトラエトキシシラン加水分解物Ａ ５６０質量部
ヘプタデカトリフルオロデシル−
トリメトキシシラン加水分解物Ｃ ４２０質量部
γ−メタクリロキシプロピルトリメトキシシシラン
（ＫＢＭ５０３、信越化学社製） ９質量部
直鎖ジメチルシリコーン−ＥＯブロックコポリマー
（日本ユニカー社製 ＦＺ−２２０７）の
１０％プロピレングリコールモノメチルエータル溶液 ７質量部
プロピレングリコールモノメチルエーテル １７００質量部
イソプロピルアルコール １７００質量部
低屈折率層の膜厚 ：１００ｎｍ
低屈折率層の屈折率：１．４１
低屈折率層のフッ素元素の含有率は４５％。
【０２５３】
反射防止フィルム１１〜１６の構成層の物性値（膜厚、屈折率、ナノインデンテーション硬度（Ｈ）、弾性率（Ｅｒ））、層形成方法、Ｆ含有率（フッ素原子含有率）等を測定し、更に、各反射防止フィルムを９０℃、７２時間の熱処理を実施し、ナノインデンテーション弾性率Ｅｒ（Ｇｐａ）を測定し、熱処理前と熱処理後での変化量（ΔＥｒ）を求めた。得られた結果を表４に示す。
【０２５４】
【表４】

【０２５５】
次いで、得られた反射防止フィルム１１〜１６の評価については、実施例１と同様に評価した。但し、熱クラックについては、別途下記の評価を行った。
【０２５６】
《熱クラック》
反射防止フィルムを１００℃熱処理（１００℃の恒温槽に投入し、４００時間保持）した後、反射防止処理面の裏面に黒色テープを貼り、反射防止処理面を顕微鏡（対物レンズ２０倍、接眼レンズ１０倍）にて観察し、クラックの発生を確認した。
【０２５７】
更に、反射防止フィルムを１２０℃熱処理（１２０℃の恒温槽に投入し、２４時間保持）した後、反射防止処理面の裏面に黒色テープを貼り、反射防止処理面を顕微鏡（対物レンズ２０倍、接眼レンズ１０倍）にて観察し、クラック発生をランク評価した。
【０２５８】
◎：１２０℃熱処理でもクラック発生なし
○：１００℃熱処理でクラックなし
△：弱く、短いクラックが発生する
×：長いクラックが発生する
本発明では○、◎が実用可である。
【０２５９】
得られた評価結果を表５に示す。
【０２６０】
【表５】

【０２６１】
表５から、比較に比べて、本発明の反射防止フィルムは、平面性、取り扱い性、耐擦傷性、鉛筆硬度、熱クラック、防汚性、耐溶剤性の全ての項目において、優れた特性を示すことが明らかである。
【０２６２】
実施例３
《偏光板１〜１０の作製》
延伸処理したポリビニルアルコールフィルムにヨウ素を吸着させて偏光膜を作製し、ポリビニルアルコール系接着剤を用いて、実施例１の本発明の反射防止フィルム１〜６、比較の反射防止フィルム７〜１０の各々を偏光膜の片側に貼り付けた。もう一方の面には市販のセルローストリアセテートフィルム（コニカタックＫＣ８ＵＸ２ＭＷ、コニカ（株）製）に鹸化処理を行い、ポリビニルアルコール系接着剤を用いて、偏光膜の反対側に貼合し、偏光板１〜１０を作製した。
【０２６３】
得られた偏光板１〜１０の視認性評価（目視評価）を行ったところ、比較の反射防止フィルム７〜１０を各々用いて作製した偏光板７〜１０に比べて、本発明の反射防止フィルム１〜６を各々用いて作製した、本発明の偏光板１〜６は、視認性が高く、また、故障発生（泡や異物の巻き込み等の故障）がなく、大画面用として断裁する場合でも、高収率であった。
【０２６４】
【表６】

【０２６５】
実施例４
《液晶パネル１〜１０の作製》
視野角測定を行う液晶パネルを以下のようにして作製し、液晶表示装置としての特性を評価した。
【０２６６】
富士通製１５型ディスプレイＶＬ−１５０ＳＤのあらかじめ貼合されていた両面の偏光板を剥がして、上記作製した本発明の偏光板１〜６及び比較の偏光板７〜１０を各々液晶セルのガラス面に貼合したものを作製した。
【０２６７】
その際、その偏光板の貼合の向きは、市販のセルローストリアセテートフィルム（コニカタックＫＣ８ＵＸ２ＭＷ、コニカ（株）製）の面が、液晶セル側となるように、且つ、あらかじめ貼合されていた偏光板と同一の方向に吸収軸が向くように行い、液晶パネル１〜１０を各々作製した。
【０２６８】
得られた液晶パネル１〜１０について下記に記載のようにして視認性評価を行ったところ、比較に比べて、本発明の液晶パネルは、いずれも○〜◎であり視認性が優れていることがわかった。
【０２６９】
《視認性評価》
液晶パネル（液晶表示装置）を目視観察し、斜め方向の視認性を下記のようにランク評価した。
【０２７０】
◎：黒がしまって見え、鮮明であり、像の白抜けも認められない
○：黒がしまって見え、鮮明であるが、わずかに像の白抜けが認められる
△：黒のしまりがなく、鮮明さがやや低く、像の白抜けが認められる
×：黒のしまりがなく、鮮明さが低く、像の白抜けが気になる
本発明においては、○、◎が実用可である。
【０２７１】
【発明の効果】
本発明により、平面性、取り扱い性、耐擦傷性、鉛筆硬度、熱クラック、防汚性、耐溶剤性の全ての項目において、優れた特性を示す反射防止フィルム、該反射防止フィルムを用いた偏光板及び表示装置を提供することが出来た。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to an antireflection film, a polarizing plate having the antireflection film, and a display device.
[0002]
[Prior art]
2. Description of the Related Art Conventionally, anti-reflection techniques for reducing surface reflection to improve transmittance and contrast and reduce glare have been proposed mainly in fields such as optical lenses, CRTs, and liquid crystal image display devices of computers and word processors. I have. As an anti-reflection technique, it is effective to reduce the light reflection at the interface between the laminate and the air by laminating several layers having appropriate values of the refractive index and the optical thickness as the optical interference layer.
[0003]
Such an antireflection layer is made of TiO as a high refractive index material.₂, ZrO₂, Ta₂O₅Etc., and SiO as a low refractive index material₂, MgF₂The antireflection layer proposed so far can be manufactured by a dry film forming method and a coating film forming method. As a dry film forming method, there are a sputtering method, a vacuum evaporation method, an ion plating method, a CVD method and a PVD method.
[0004]
In general, the dry film forming method is superior from the viewpoint of optical functions, but the coating film forming method has an advantage that the production is easy and inexpensive. As a coating type film forming method, a metal alkoxide represented by a titanium alkoxide or a silane alkoxide or the like is formed on a surface of a support (hereinafter, also referred to as a substrate, a substrate film, a substrate, or the like), dried, and heated. Methods of forming films of metal oxides, films of photopolymerizable monomers containing vinylidene fluoride or perfluoroalkylalkyl, and films of various metal oxides exhibiting various refractive indices and binder components have been carried out. Has been done.
[0005]
By the way, in an image display device such as a liquid crystal display device (LCD), a plasma display panel (PDP), an electroluminescence display (ELD), a cathode ray tube display device (CRT), a fluorescent display tube, and a field emission display, a display device is used. The antireflection layer on the surface preferably has a function as a protective layer.
[0006]
In recent years, these display devices are often mounted on devices used in various environments such as car navigation systems and mobile phones, and are required to have various durability such as heat resistance, moisture resistance, light resistance, and heat shock resistance. ing.
[0007]
For example, in forming a protective layer by an ion beam evaporation method, which is a dry film forming method, the physical property nanoindentation hardness (H) of the protective layer is set to about 2 GPa to 5 GPa, and a strain to fineness of less than 1% is less than 1%. There is a disclosure of providing a coated substrate having good wear resistance by providing a protective layer having a thickness of 1 μm to 100 μm having a crack (for example, see Patent Document 1).
[0008]
The function of the anti-reflection film as a protective layer is considered to depend on the physical properties of the material forming the protective layer. However, the anti-reflection layer using optical interference has a high refractive index layer and a low refractive index layer of about 100 nm. It must be formed of a thin film. Although it is common to use a material having a high hardness and / or elastic modulus as a material for forming the optical interference layer, an actual optical interference layer is formed of a thin film and thus has a hardness and a modulus when measured as a material. Are considered different. In particular, in the case of a film forming method involving a reaction such as a crosslinked polymer utilizing photopolymerization or thermal polymerization of a monomer or a metal oxide layer formed by a sol-gel method, the physical properties vary greatly depending on the film forming process and the film thickness. It is known, and actual adjustment of physical properties is difficult.
[0009]
[Patent Document 1]
Japanese Patent Publication No. 10-500609
[0010]
[Problems to be solved by the invention]
The object of the present invention is flatness, handleability, scratch resistance, pencil hardness, thermal cracks, antifouling properties, anti-reflection film showing excellent properties in all items of solvent resistance, polarized light using the film It is to provide a board and a display device.
[0011]
[Means for Solving the Problems]
The above object of the present invention has been achieved by the following constitutions 1 to 10.
[0012]
1. On at least one surface of the support, a hard coat layer of 1 μm to 20 μm, a high refractive index layer showing a refractive index higher than the refractive index of the hard coat layer, and a refractive index lower than the refractive index of the hard coat layer In the antireflection film having the low refractive index layers shown in this order, the high refractive index layer and the low refractive index layer are each formed by wet coating, and the nanoindentation hardness (H) of the surface of the outermost layer is 2 GPa to 4 GPa. And a nanoindentation elastic modulus (Er) of 10 GPa to 30 GPa.
[0013]
2. 2. The reflection according to item 1, wherein the hard coat layer has a nanoindentation hardness (H) of 0.8 GPa to 2.0 GPa and a nanoindentation elasticity (Er) of 6 GPa to 15 GPa. Prevention film.
[0014]
3. A middle refractive index layer having a refractive index between the hard coat layer and the high refractive index layer, between the hard coat layer and the high refractive index layer, wherein the middle refractive index layer is formed by wet coating. 3. The anti-reflection film according to the above 1 or 2, wherein
[0015]
4. The outermost surface layer forms an optical interference layer, and the amount of change (ΔH) in nanoindentation hardness (H) of the outermost surface layer before and after a heat resistance test at 90 ° C. for 72 hours is 0.3 GPa or less. The antireflection film according to any one of the above items 1 to 3, wherein:
[0016]
5. The anti-reflection film according to any one of the above items 1 to 4, wherein the outermost surface layer is a low refractive index layer.
[0017]
6. The nanoindentation hardness (H) of the surface of the low refractive index layer is 3 GPa to 4 GPa, and the nanoindentation elastic modulus (Er) is 15 GPa to 30 GPa. 2. The antireflection film according to claim 1.
[0018]
7. 7. The antireflection film according to 6, wherein the low-refractive-index layer contains a surface element, a vicinity of the surface, and a fluorine element in the inside of the layer in a range of 1 atomic% to 40 atomic%.
[0019]
8. 7. The antireflection film according to 6, wherein the low refractive index layer contains a fluorine element in the surface, near the surface, and inside the layer in a range of 5 atomic% to 30 atomic%.
[0020]
9. A polarizing plate, comprising the antireflection film according to any one of the above items 1 to 8.
[0021]
10. A display device, comprising: the antireflection film according to any one of Items 1 to 8 or the polarizing plate according to Item 9.
[0022]
Hereinafter, the present invention will be described in detail.
The present inventor has conducted intensive studies on the above problems, and as a result, as described in claim 1, a hard coat layer of 1 μm to 20 μm on at least one surface of the support, showing a higher refractive index than the support. In an antireflection film having a high refractive index layer and a low refractive index layer having a lower refractive index than the support in this order, the high refractive index layer and the low refractive index layer are formed by wet coating. Antireflection function by adjusting the nanoindentation hardness (H) of the surface of the index layer to a range of 2 GPa to 4 GPa and adjusting the nanoindentation elasticity (Er) to a range of 10 GPa to 30 GPa. It has become possible to provide an anti-reflection film having high protection function and high protection function and high durability.
[0023]
In addition, by providing the anti-reflection film or the polarizing plate having the anti-reflection film, a display device having a high anti-reflection function and exhibiting a high protection function and high durability was also found. .
[0024]
Specifically, the physical properties (thickness of the film, the refractive index of the support, etc.) of each layer (hard coat layer, high refractive index layer, low refractive index layer, etc.) of the antireflection film produced by the coating type film forming method. It was found that by adjusting the relationship, the nanoindentation hardness (H) of the low refractive index layer, the nanoindentation elastic modulus, and the like), an antireflection film having a function as a protective layer, particularly having significantly improved scratch resistance, was obtained. .
[0025]
Further, the present inventors have found that not only abrasion resistance but also antifouling property can be significantly improved by using a combination of a material constituting each layer of the antireflection film and a means for suppressing a change in physical properties. Was.
[0026]
<< Layer composition of antireflection film >>
The layer configuration of the antireflection film of the present invention will be described.
[0027]
In other words, the antireflection film of the present invention can also be referred to as a low-reflection laminate in which an optical interference layer is laminated. A low-reflection laminate in which an optical interference layer is laminated refers to a laminate of an optical interference layer in which a high refractive index layer and a low refractive index layer are sequentially laminated on at least one surface of the support from the support side (as described below). In some cases, an antireflection laminate in which the optical film thickness of the high-refractive-index layer and the low-refractive-index layer is set to λ / 4 or more with respect to light having the wavelength λ is published. ing.
[0028]
Here, one of the necessary conditions is that the optical interference layer has a film thickness larger than (λ / 4) of the wavelength (λ) of light to be used. For example, a layer having a film thickness on the order of nm is used. Cannot function as an optical interference layer because it is substantially transparent to light.
[0029]
Whether each of the constituent layers of the antireflection film of the present invention forms an optical interference layer depends on the thickness of each layer, and the above-mentioned medium refractive index layer, high refractive index layer, low refractive index layer, etc. The interference layer is formed. The hard coat layer, antiglare layer, antistatic layer and other layers (for example, antifouling layer, protective layer, etc.) described in the preferred layer constitution described below have a layer thickness of light. When the wavelength (λ) is λ / 4 or more, the layer can function as an optical interference layer. However, when the film thickness is, for example, a thin film of the order of nm, it is transparent to light. Thus, the function as the optical interference layer is not substantially exhibited. On the other hand, when the film thickness is larger than λ / 4, an optical interference layer can be formed.
[0030]
The optical film thickness is an amount defined by the product of the refractive index n of the layer and the film thickness d. The refractive index is largely 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 using measurement data of spectral reflectance described later.
[0031]
The antireflection film of the present invention includes a hard coat layer, a high refractive index layer having a refractive index higher than the refractive index of the support, and a refractive index lower than the refractive index of the support on at least one surface of the support. Low refractive index layers exhibiting a refractive index in this order.
[0032]
As the layer configuration of the antireflection film of the present invention, for example, on a transparent support (also referred to as a substrate, a substrate film, a substrate, etc.), the refractive index, film thickness, The layers are stacked in consideration of the number of layers, layer order, and the like.
[0033]
The antireflection layer is configured by combining at least a high refractive index layer having a refractive index higher than the refractive index of the support and a low refractive index layer having a refractive index lower than the refractive index of the support.
[0034]
As an example of the configuration of the antireflection layer, two layers of a high refractive index layer / a low refractive index layer or three layers having different refractive indices are formed from the upper side of the hard coat layer into a medium refractive index layer (substrate, hard coat layer). , A layer having a higher refractive index than the low refractive index layer and a lower refractive index than the high refractive index layer), a layer having a high refractive index, and a layer having a low refractive index. Stacking layers has also been proposed.
[0035]
Above all, it is preferable to apply the medium refractive index layer / high refractive index layer / low refractive index layer on the support having the hard coat layer in order of durability, optical characteristics, cost, productivity, and the like.
[0036]
Examples of preferred layer constitutions of the antireflection film of the present invention are shown below.
Support / hard coat layer / high refractive index layer / low refractive index layer
Support / hard coat layer / medium refractive index layer / high refractive index layer / low refractive index layer
Support / antiglare layer / hard coat layer / high refractive index layer / low refractive index layer
Support / antiglare layer / hard coat layer / medium refractive index layer / high refractive index layer / low refractive index layer
Support / antistatic layer / hard coat layer / medium refractive index layer / high refractive index layer / low refractive index layer
Antistatic layer / support / hard coat layer / medium refractive index layer / high refractive index layer / low refractive index layer
Support / antistatic layer / antiglare layer / hard coat layer / medium refractive index layer / high refractive index layer / low refractive index layer
Antistatic layer / support / antiglare layer / hard coat layer / medium refractive index layer / high refractive index layer / low refractive index layer
Antistatic layer / support / antiglare layer / hard coat layer / high refractive index layer / low refractive index layer / high refractive index layer / low refractive index layer
In the present invention, as long as the reflectance can be reduced by optical interference, the present invention is not particularly limited to the above-described layer configuration. Further, as the antistatic layer, conductive polymer particles or metal oxide fine particles (for example, SnO₂, ITO, etc.) is preferable, and the layer can be formed by coating or atmospheric pressure plasma treatment.
[0037]
As described above, the antireflection film of the present invention has a hard coat layer, an optical interference layer (a medium refractive index layer, a high refractive index layer, a low refractive index layer, etc.) on a support and, if necessary, an antistatic layer. Layers, antiglare layers, etc. are used, the thickness of the hard coat layer is adjusted in the range of 1 μm to 20 μm, and the nanoindentation hardness (H) of the surface of the outermost layer is 2 GPa to 4 GPa; It is an essential requirement that the nanoindentation elastic modulus (Er) be 10 GPa to 30 GPa.
[0038]
<< Nanoindentation hardness (H) and elastic modulus (Er) of the outermost layer >>
The nanoindentation hardness (H) and the elastic modulus (Er) of the outermost layer according to the present invention are defined as follows when the thickness of the outermost layer is 10 nm or less and when it exceeds 10 nm, respectively. Is done.
[0039]
(1) When the thickness of the outermost layer exceeds 10 nm
When the thickness of the outermost surface layer exceeds 10 nm, the nanoindentation hardness (H) and the elastic modulus (Er) of the outermost surface layer itself are determined by a measurement method described later.
[0040]
(2) When the thickness of the outermost surface layer is 10 nm or less
When the thickness of the outermost surface layer is 10 nm or less, it is difficult to determine the nanoindentation hardness (H) and the elastic modulus (Er) of the outermost surface layer by the measurement method described below. In the present invention, measurement is performed in the embodiment including the outermost surface layer and the lower layer of the outermost surface layer, and the obtained data is referred to as the nanoindentation hardness (H) and the elastic modulus (Er) of the outermost surface layer, respectively. Define.
[0041]
For example, assuming that the outermost layer is a protective layer having a thickness of 10 nm or less and the lower layer of the protective layer is a low refractive index layer, the nanoindentation hardness (H) of the outermost layer in this case is The elastic modulus (Er) is measured as data over two layers of a protective layer and a low refractive index layer.
[0042]
The nanoindentation hardness (H) and the nanoindentation elasticity (Er) of the outermost surface layer of the antireflection film of the present invention are indispensable requirements to be adjusted in the range of 2 GPa to 4 GPa and 10 GPa to 30 GPa, respectively. If the hardness (H) is smaller than 2 GPa or the elastic modulus (Er) is smaller than 10 GPa, the scratch resistance is deteriorated. Further, when the hardness (H) is greater than 4 GPa or the elastic modulus (Er) is greater than 30 GPa, there is a problem that cracks are easily generated under heating conditions.
[0043]
The outermost layer of the antireflection film of the present invention is most preferably the low refractive index layer described above.
[0044]
<< Nanoindentation hardness (H) and elastic modulus (Er) of hard coat layer >>
The nanoindentation hardness (H) and the elastic modulus (Er) of the hard coat layer according to the present invention are measured at a press-in amount of 15% ± 3% or a press-in amount of 250 nm of the film thickness of the hard coat layer. In the present invention, when the value of 15% ± 3% of the thickness of the hard coat layer is 250 nm or more, the measurement is performed by setting the indentation amount to 250 nm.
[0045]
From the viewpoint of imparting sufficient scratch resistance to the hard coat layer according to the present invention and preventing the occurrence of cracks under heating conditions, the nanoindentation hardness (H) is adjusted to the range of 0.8 GPa to 2.0 GPa. In addition, it is preferable to adjust the elastic modulus (Er) in the range of 6 GPa to 15 GPa.
[0046]
<< Change in nanoindentation hardness (H) >>
The variation of the nanoindentation hardness (H) is preferably 0.3 GPa or less. More preferably, all the layers such as the hard coat layer, the high refractive index layer, and the low refractive index layer have a change in nanoindentation hardness (H) of 0.3 GPa or less. When the variation of the nanoindentation hardness (H) is 0.3 GPa or less, the chemical resistance is improved, and the chemical resistance after the heat resistance test and the moisture resistance test is improved.
[0047]
<< Measurement of nanoindentation hardness (H) and elastic modulus (Er) >>
The nanoindentation hardness (H) and the nanoindentation elastic modulus (Er) of the outermost surface layer and other constituent layers of the antireflection film of the present invention are measured by mounting Triboscope manufactured by Hysitron on Nanoscope III manufactured by Digital Instruments. did.
[0048]
For the measurement, a triangular pyramid-shaped diamond indenter called a Berkovich-type indenter (tip edge angle: 142.3 °) was used as an indenter.
[0049]
A triangular pyramid-shaped indenter was applied at right angles to the sample surface, a load was gradually applied, and after the maximum load was reached, the load was gradually returned to zero. The value P / A obtained by dividing the maximum load P at this time by the projected area A of the indenter contact portion was calculated as nanoindentation hardness (H). The nanoindentation elastic modulus (Er) was calculated using the following equation, where the slope S of the unloading curve was used.
[0050]
(formula)
Er = (S × √π) / (2√A) (π is pi)
In addition, the apparatus was calibrated and measured in advance so that the hardness obtained as a result of pushing the attached fused quartz as a standard sample was 9.5 ± 1.5 GPa.
[0051]
The details of the principle are described in Handbook of Micro / Nano Tribology (Bharat Bushan, CRC).
[0052]
The sample was prepared by dropping one drop of adhesive Aron Alpha manufactured by Toagosei Co., Ltd. on a slide glass, placing a film cut into a square of about 1 cm, and allowing to stand for 24 hours to cure.
[0053]
For the measurement of the outermost surface, the maximum load P was set in advance so that the maximum depth was 15 nm. Both loading and unloading were performed in 5 seconds. In the case of measuring the inner constituent layer, the constituent layer on the inner layer is scraped from the surface side to expose the layer, and the measurement can be performed in the same manner as in the case of the outermost surface layer.
[0054]
In the present invention, in order to remove the layer on the surface side, the same Berkovich type indenter is used to bring the sample into contact with the sample surface under a load that can be averagely cut out of a load of 1 μN to 30 μN, and to horizontally move at a speed of 2 μm / s. Scan in the direction.
[0055]
With this load and speed, a 2 μm × 2 μm area composed of 512 lines is repeatedly rubbed. Thereafter, the shape of the 10 μm × 10 μm area centered on the repeatedly rubbed 2 μm × 2 μm area was measured, and the level difference between the portion worn by rubbing and the portion not worn was accurately measured. When the thickness reached, the layer was stopped and the layer to be measured was exposed.
[0056]
For the rubbed 2 μm × 2 μm area, the maximum load P is set in advance so that the maximum depth is 15 nm, and at the maximum load, both the load and unload are indented in 5 seconds, and the internal The nanoindentation hardness (H) and the elastic modulus (Er) of the layer were each measured.
[0057]
Next, materials used for forming an optical interference layer such as a high refractive index layer, a medium refractive index layer, and a low refractive index layer according to the present invention will be described.
[0058]
《Organic titanium compound》
In the present invention, at least one of the antireflection layers is formed by applying and drying a coating solution containing a monomer, an oligomer, or a hydrolyzate of an organotitanium compound represented by the following general formula (1). Preferably, the layer has a ratio of 1.55 to 2.25.
[0059]
General formula (1) Ti (OR¹)₄
Where R¹Represents an aliphatic hydrocarbon group having 1 to 8 carbon atoms.
[0060]
R of the general formula (1)¹Is preferably an aliphatic hydrocarbon group having 1 to 8 carbon atoms, and is preferably an aliphatic hydrocarbon group having 1 to 4 carbon atoms. Further, the monomer, oligomer or hydrolyzate thereof of the organic titanium compound undergoes hydrolysis of the alkoxide group and reacts like -Ti-O-Ti- to form a crosslinked structure, thereby forming a cured layer.
[0061]
The monomer and oligomer of the organotitanium 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)₄And dimers to 10-mers. These can be used alone or in combination of two or more.
[0062]
Among them, Ti (On-C₃H₇)₄, Ti (OiC₃H₇)₄, Ti (On-C₄H₉)₄, Ti (On-C₃H₇)₄Dimer to 10-mer, Ti (On-C₄H₉)₄Particularly preferred are dimers to 10-mers.
[0063]
The monomer, oligomer or hydrolyzate of the organic titanium compound used in the present invention may account for 50.0% by mass to 98.0% by mass in the solid content contained in the antireflection layer coating solution. preferable.
[0064]
The solid content ratio is more preferably from 50% by mass to 90% by mass, and still more preferably from 55% by mass to 90% by mass. In addition, it is also preferable to add a polymer of an organotitanium compound (crosslinked by hydrolysis of the organotitanium compound in advance) to the coating composition.
[0065]
Further, in the present invention, the monomer of the above-mentioned organic titanium compound, a part of the oligomer or a complete hydrolyzate is contained in the coating solution, but the monomer and the oligomer of the organic titanium compound are self-condensed and cross-linked 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 carboxylates, organosilicon compounds having amino groups, and acid generators by light. (Photoacid generator). 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.
[0066]
《Slip agent》
It is preferable to add a slip agent to the low refractive index layer according to the present invention, and the scratch resistance can be improved by imparting a slip property. As the slip agent, silicone oil or a wax-like substance is preferably used. For example, a compound represented by the following general formula is preferable.
[0067]
General formula R₁COR₂
Where R₁Represents a saturated or unsaturated aliphatic hydrocarbon group having 12 or more carbon atoms. An alkyl group or an alkenyl group is preferable, and an alkyl group or an alkenyl group having 16 or more carbon atoms is more preferable. R₂Is -OM₁Group (M₁Represents an alkali metal such as Na or K), -OH group, -NH₂Group or -OR₃Group (R₃Represents a saturated or unsaturated aliphatic hydrocarbon group having 12 or more carbon atoms, preferably an alkyl group or an alkenyl group);₂Are -OH group, -NH₂Group or -OR₃Groups are preferred. 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 disclosed in JP-B-53-292, higher fatty acid amides disclosed in U.S. Pat. No. 4,275,146, JP-B-58-33541, UK patent No. 927,446 or JP-A-55-126238 and JP-A-58-90633, which are examples of higher fatty acid esters (fatty acids having 10 to 24 carbon atoms and fatty acids having 10 to 24 carbon atoms). Esters of alcohols) and metal salts of higher fatty acids as disclosed in U.S. Pat. No. 3,933,516, and dicarboxylic acids having up to 10 carbon atoms as disclosed in JP-A-51-37217. Polyester compounds comprising an acid and an aliphatic or cycloaliphatic diol; dicarboxylic acids disclosed in JP-A-7-13292 Mention may be made of oligo polyester or the like from the Le.
[0068]
The amount of the slip agent used in the low refractive index layer is 0.01 mg / m²-10mg / m²Is preferred.
[0069]
《Organic material for low refractive index layer》
The organic material for a low refractive index layer preferably used for the low refractive index layer according to the present invention will be described.
[0070]
As the organic material for a low refractive index layer (also referred to as an organic material for a low refractive index layer), an organic substance such as a polymer into which a fluorine atom is introduced is preferably used because the material itself has a low refractive index of 1.45 or less. I can do it. In addition, polyvinylidene fluoride (refractive index n = 1.40) is cited as a resin in which a solvent can be used because of its easy handling. When the above-mentioned polyvinylidene fluoride is used as the organic material for the low-refractive-index layer, the refractive index of the low-refractive-index layer is approximately 1.40, but in order to further lower the refractive index of the low-refractive-index layer. Is to add 10 to 300 parts by mass, preferably 100 to 200 parts by mass of an acrylate having a low refractive index such as trifluoroethyl acrylate (refractive index n = 1.32).
[0071]
This trifluoroethyl acrylate is a monofunctional type, so that the film strength of the low refractive index layer is not sufficient. Therefore, a polyfunctional acrylate, for example, dipentaerythritol hexaacrylate (abbreviation: ionizing radiation curable resin) is used. DPHA, tetrafunctional type) is desirably added. The film strength of DPHA increases as the amount of addition increases, but from the viewpoint of lowering the refractive index of the low refractive index layer, the amount of addition is preferably from 1 to 50 parts by mass, more preferably from 5 to 20 parts by mass. Parts.
[0072]
<< Fluorine element content of low refractive index layer >>
In the low refractive index layer according to the antireflection film of the present invention, the content of the elemental fluorine is preferably in the range of 1 atomic% to 40 atomic%, more preferably 5 atomic%, not only on the surface and near the surface but also inside the layer. It is in the range of 30 atomic%.
[0073]
By adjusting the fluorine element content within the above range, the antifouling property of the antireflection film surface is improved, and the scratch resistance is also improved.
[0074]
(Fluorine element content measurement)
Here, the measurement of the content of fluorine atoms on the surface of the layer, near the surface, and inside the layer is measured using an X-ray photoelectron spectroscopy (XPS) surface analyzer. Here, as for the measurement of fluorine atoms in the vicinity of the surface and inside the layer, composition analysis becomes possible by performing analysis in the depth direction described later.
[0075]
The XPS surface analyzer used in the present invention is not particularly limited, and any model can be used. In this embodiment, ESCALAB-200R manufactured by VG Scientific Inc. was used. The measurement was performed at an output of 600 W (acceleration voltage 15 kV, emission current 40 mA) using Mg as the X-ray anode. The energy resolution was set to be 1.5 to 1.7 eV when defined by the half width of the clean Ag3d5 / 2 peak.
[0076]
First, the range of the binding energy from 0 eV to 1100 eV was measured at a data acquisition interval of 1.0 eV to find out what element was detected.
[0077]
Next, with respect to all the detected elements, the data capturing interval was set to 0.2 eV, and a narrow scan was performed for the photoelectron peak giving the maximum intensity, and the spectrum of each element was measured. The obtained spectrum is COMMON DATA PROCESSING SYSTEM (Ver. 2.3 or later is preferable) manufactured by VAMAS-SCA-JAPAN in order to prevent the difference in the content calculation result due to the difference in the measurement device or computer. After the transfer to the above, processing was performed by the same software, and the value of the elemental composition was determined as an atomic concentration (atomic concentration).
[0078]
Before performing the quantitative processing, the Count Scale was calibrated for each element, and a 5-point smoothing processing was performed. In the quantitative processing, the peak area intensity (cps * eV) from which the background was removed was used. For the background treatment, a method according to Shirley was used.
[0079]
For the Shirley method, see D.S. A. Shirley, Phys. Rev .. , B5, 4709 (1972).
[0080]
(Depth direction composition analysis)
The composition distribution in the depth direction can be determined by depth direction analysis using an X-ray photoelectron spectrometer and ion etching together. The method of ion etching is not particularly limited, but it is preferable to use a rare gas such as helium, neon, argon, krypton, or xenon, or oxygen as an ion species. The preferred gas is argon. As the ion gun, either a discharge type or a duoplasmatron type may be used. It is preferable to use an ion gun with a differential pumping mechanism.
[0081]
The ion acceleration voltage for ion etching is preferably in the range of 1 kV to 5 kV, more preferably 2 kV to 4 kV.
[0082]
The amount of ions for etching is preferably 1 μA to 5 μA as a current value, more preferably 2 μA to 4 μA. The amount of ions is preferably measured using a Faraday cup. The ion amount can be adjusted by the filament current and the introduced gas amount.
[0083]
In the case of performing the depth direction analysis, it is necessary to make the area measured by the X-ray photoelectron spectrometer smaller than the area removed by ion etching. The ratio of the measurement area to the etching area is preferably in the range of 10% to 0.5%, more preferably 5% to 1%.
[0084]
The etching area is the raster size of the ion gun, and the measurement area can be limited by the X-ray irradiation area or the lens slit.
[0085]
The measurement of the content of fluorine atoms in the low refractive index layer according to the present invention is performed in a state where the extreme surface of the uppermost layer is removed by ion etching in order to remove the influence of bleed-out such as an activator added for improving coatability. Measure with Since the ion etching time differs depending on the layer to be measured, it is necessary to set conditions in advance so that the fluorine atoms inside the re-surface layer can be measured.
[0086]
<< Abrasion resistance (also called abrasion resistance) >>
It is preferable to add a surfactant, a softening agent, a soft leveling agent and the like to the low refractive index layer of the present invention, whereby the scratch resistance (scratch resistance) can be improved.
[0087]
Above all, addition of an anionic or nonionic surfactant is preferable, and for example, a dialkyl sulfosuccinate sodium salt, a nonionic surfactant emulsion of a 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, paint additive PC-700 (manufactured by Nichika Chemical Co., Ltd.) and the like.
[0088]
The preferable addition amount is 0.01% by mass to 3% by mass, more preferably 0.03% by mass to 1% by mass, based on the solid content contained in the coating solution for the low refractive index layer.
[0089]
《Particles》
The fine particles used in the present invention will be described.
[0090]
In the present invention, ZnO, TiO₂, Sb₂O₅, SnO₂, ITO, CeO₂, Y₂O₃, La₂O₃, ZrO₂, Al₂O₃It is preferable to contain fine particles having a mean particle size of 0.15 μm or less made of metal oxide such as 0.1 to 90.0 mass% in solid content ratio.
[0091]
The fine particles may be used alone or in combination of two or more metal oxides. Fine particles having a particle size in the range of 0.001 μm to 0.1 μm are more preferable. Thereby, it becomes possible to increase the nanoindentation hardness (H) and the nanoindentation elasticity (Er) of the surface of the outermost layer, and it is possible to improve the film strength of the antireflection film and to make it hard to be damaged. Become.
[0092]
The optical interference layer containing these titanium oxides is mainly used for a high refractive index layer, but may be formed as a medium refractive index layer by adjusting additives.
[0093]
As the binder component used together with the fine particles, the above-mentioned organic titanium compound, organic silane compound, and a hard coat composition described later can be used.
[0094]
《Organic silicon compound》
The organosilicon compound used in the present invention will be described.
[0095]
In the present invention, an organic compound represented by any of the following general formulas (2) to (5) is provided on a medium to high refractive index layer formed using a monomer, an oligomer of an organic titanium compound or a hydrolyzate thereof. It is preferable that a low-refractive-index layer having a refractive index of 1.35 or more and less than 1.55 formed by applying and drying a coating solution containing a silicon compound monomer, oligomer, or a mixture thereof is preferably laminated.
[0096]
General formula (2) Si (OR²)₄
General formula (3) Si-X₄
General formula (4) R³-Si (OR²)₃
General formula (5) R³-Si-X₃
Where R²Is an aliphatic hydrocarbon group having 1 to 4 carbon atoms, R³Represents a methyl group or an ethyl group, and X represents a halogen atom.
[0097]
Preferred organic silicon compounds include tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane and the like, and silicate oligomers are obtained by hydrolyzing these. 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) is converted into a hydrolyzate. Obtainable. Although the degree of hydrolysis can be appropriately adjusted depending on the amount of water used, it is 40% to 1000%, preferably 200% to 300% in the present invention. Here, the degree of hydrolysis was determined by adding a half of the theoretical amount of water required to hydrolyze all the alkoxyl groups, that is, half the number of alkoxyl groups in the hydrolyzable group, ie, tetraalkoxysilane. When the hydrolysis rate is 100%,
Hydrolysis rate (%) = (actual amount of water added / theoretical amount of hydrolysis) × 100
Is required.
[0098]
The silicate oligomer thus obtained usually contains about 2% to 10% of a monomer. In the present invention, it may be used in a monomer state or in an oligomer state, or a mixture of a monomer and an oligomer may be used.However, if a monomer is contained, storage stability is lacking, and viscosity increases during storage. However, since film formation may be difficult, it is preferable to remove the monomers by flash distillation or vacuum distillation so that the monomer content is 1% by mass or less, preferably 0.3% by mass or less. .
[0099]
In the present invention, a partial hydrolyzate obtained by adding a catalyst and water to tetraalkoxysilane as described above is used, but it is preferable to use a complete hydrolyzate. A solvent is added to the hydrolyzate, and then a cured hydrolyzate is obtained by, for example, adding the following curing catalyst and water. As such a solvent, it is preferable to use one or two types of methanol and ethanol, because they are inexpensive and the properties of the obtained film are excellent and the hardness is good. Isopropanol, n-butanol, isobutanol, octanol and the like can also be used, but the hardness of the obtained coating tends to be low. The amount of the solvent is 50 parts by mass to 400 parts by mass, preferably 100 parts by mass to 250 parts by mass with respect to 100 parts by mass of the partial hydrolyzate.
[0100]
(Curing catalyst)
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.
[0101]
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%.
[0102]
The coating composition for a low refractive index layer obtained in this manner is extremely stable, and 1 hour, 6 hours, 12 hours, 1 day, 3 days, and 7 days have elapsed since the start of hydrolysis. Can also be used.
[0103]
(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 solution to stand, and the standing time is a time during which the above-described 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, a carboxyl group, or the like. It may be present alone or in combination with the above silicate oligomer.
[0104]
Thus, the silicate oligomer of the organosilicon compound represented by the general formulas (2), (3), (4) and (5) is obtained.₂The content is 1 to 100%, preferably 10 to 99%. SiO₂If the content is less than 1%, no improvement in durability is observed, and the effect of the present invention is not exhibited.
[0105]
For the low refractive index layer, the above-mentioned alcohol-soluble acrylic resin or epoxy-based photocurable compound is preferably used.
[0106]
A low refractive index layer having a very thin film thickness has insufficient hardness, and the layer surface is vulnerable to scratches or scratches. In such a case, generally, a layer containing a light-irradiating crosslinkable ethylenically unsaturated compound that easily forms a cured film is generally used, but the crosslinkable ethylenically unsaturated compound is contained in the air. Since it is easily affected by oxygen and the film thickness is thin, polymerization of the ethylenically unsaturated compound is easily inhibited, and a tough low refractive index layer cannot be obtained by this method.
[0107]
In the present invention, the hardness is insufficient, the low refractive index layer containing an epoxy-based photocurable compound is weak to scratches and scratches, by irradiating light, the hardness is high, abrasions, tough against scratches It is preferable to form a low refractive index layer. Epoxy-based photocurable compounds are excellent photocurable compounds that can be rapidly polymerized because they are not easily affected by oxygen and can form a high hardness and tough film even with a thickness of about 50 to 200 nm. is there.
[0108]
The epoxy-based photocurable compound is a compound having two or more epoxy groups in a molecule, and is the same as the compound described in the section of the binder.
[0109]
Further, in the present invention, the low refractive index layer can contain fine particles of silicon oxide. It is preferable to contain silicon oxide fine particles having a particle size of 0.1 μm or less. In particular, 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 added. be able to. In addition, it is also possible to use silicon oxide fine particles whose surface is substituted with an alkyl group described in JP-A-2001-2799, and it is also easy to treat the above silicate oligomer with an alkylsilane coupling agent after hydrolysis. 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% by mass to 40% by mass.
[0110]
(solvent)
Solvents used in the coating solution for coating the antireflection layer 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; , Toluene, xylene and other aromatic hydrocarbons; ethylene glycol, propylene glycol, hexylene glycol and other glycols; ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, diethyl cellosolve, diethyl carbitol, Glycol ethers such as propylene glycol monomethyl ether; N-methylpyrrolidone, dimethylformamide, methyl lactate, ethyl lactate, water and the like, and these can be used alone or as a mixture of two or more. Particularly, by using at least one solvent having a boiling point of 120 ° C. to 180 ° C. at 1 atm and a vapor pressure of 2.3 kPa or less at 20 ° C. in the coating liquid, the curing rate is appropriately slowed down, It is possible to prevent white turbidity, eliminate coating unevenness, and improve the pot life of the coating liquid. Those having an ether bond in the molecule are particularly preferred, and glycol ethers are more preferred.
[0111]
The glycol ethers specifically include the following solvents, but are not particularly limited thereto. The boiling point at 1 atm and the vapor pressure at 20 ° C. are shown after the solvent name.
[0112]

Particularly preferably, the glycol ethers are propylene glycol mono (C1 to C4) alkyl ether and propylene glycol mono (C1 to C4) alkyl ether ester, specifically, propylene glycol monomethyl ether (PGME) and 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.
[0113]
Further, a middle to high refractive index layer and a low refractive index layer are applied to an antiglare layer having a center line average surface roughness Ra defined by JIS B 0601 of about 0.05 μm to 0.5 μm to prevent reflection. In the case of processing, in order to form a layer as uniform as possible on the fine irregularities of the antiglare layer, it is preferable to dry immediately after coating, and a solvent having a boiling point of 130 ° C. or less, preferably 100 ° C. or less, is used as a solvent. It is preferable to use a solvent containing at least 50% by mass, more preferably at least 50% by mass. These solvents are not particularly limited, but are appropriately selected from alcohols, ketones, hydrocarbons, ethers, esters and the like. Preferably, it can be selected from the solvents mentioned above.
[0114]
It is preferable to add various leveling agents, surfactants, and low surface tension substances such as silicone oil to the coating liquid for each layer. Specific examples of the silicone oil include the compounds shown in Table 1.
[0115]
[Table 1]

[0116]
These components have the effect of improving the coatability when a new coating liquid is applied to a layer that has been applied in advance during coating on a support or production of a laminate. When added to the outermost surface layer of the laminate, it not only improves the water repellency, oil repellency and antifouling properties of the coating film, but also exerts an effect on the scratch resistance of the surface. If these components are added in too large an amount, they may cause cissing at the time of coating. Therefore, it is preferable to add 0.01 to 3% by mass of the solid components in the coating solution.
[0117]
(Application method): Wet coating
For forming the high refractive index layer and the low refractive index layer among the layers of the antireflection film of the present invention, it is an essential requirement that a wet coating method be used. Also, as for the method of forming the middle refractive index layer and the hard coat layer, it is preferable to form the layer by a wet coating method.
[0118]
Here, specific examples of the wet coating method include dipping, spin coating, knife coating, bar coating, air doctor coating, blade coating, squeeze coating, reverse roll coating, gravure roll coating, spray coating, and die coating (curtain coating, etc.). And the like, and a coating method capable of continuous coating or thin film coating is preferably used.
[0119]
When coating the composition of each layer constituting the antireflection film of the present invention on a support, the thickness and the coating uniformity of the layer are controlled by adjusting the solid content concentration and the coating amount in the coating solution. be able to. Further, in order to improve the coating property of the composition, a trace amount of a surfactant or the like may be added to the coating solution.
[0120]
<< Support (also referred to as substrate film, substrate, substrate, etc.) >>
The support according to the present invention will be described.
[0121]
The support according to the present invention may be easily manufactured, have a hard coat layer or other layers (such as an antiglare layer or an intermediate layer) easily adhered, be optically isotropic, or be optically isotropic. It is preferably transparent. Any material having these properties may be used. For example, cellulose ester films, polyester films, polycarbonate films, polyarylate films, polysulfone (including polyethersulfone) films, polyethylene terephthalate, polyethylene naphthalate Polyester film, polyethylene film, polypropylene film, cellophane, cellulose diacetate film, cellulose acetate butyrate film, polyvinylidene chloride film, polyvinyl alcohol film, ethylene vinyl alcohol film, syndiotactic polystyrene film, polycarbonate film, norbornene resin System film, polymethylpentene film, polyetherketone film, Polyether ketone imide film, a polyamide film, a fluororesin film, a nylon film, there may be mentioned polymethyl methacrylate film or an acrylic film or the like, but are not limited to. Among these, a cellulose triacetate film, a polycarbonate film, and a polysulfone (including polyether sulfone) are preferable. In the present invention, a cellulose triacetate film or a cellulose acetate propionate film is particularly preferable in terms of production, cost, transparency, and the like. It is preferable in terms of properties, adhesiveness, and the like.
[0122]
《Cellulose ester film》
From the viewpoint of obtaining a laminate having a low reflectance, it is preferable to use a cellulose ester film as the substrate. As the cellulose ester, cellulose acetate, cellulose acetate butyrate (CAB), and cellulose acetate propionate (CAP) are preferable, and among them, cellulose acetate butyrate (CAB) and cellulose acetate propionate (CAP) are preferably used.
[0123]
In particular, when the substitution degree of the acetyl group is X and the substitution degree of the propionyl group or the butyryl group is Y, the high refractive index layer and the low refractive index layer are formed on a support having a mixed fatty acid ester of cellulose in which X and Y are in the following ranges. An antireflection film provided with a refractive index layer is preferably used.
[0124]
2.3 ≦ X + Y ≦ 3.0
0.1 ≦ Y ≦ 1.2
In particular,
2.5 ≦ X + Y ≦ 2.85
It is preferable that 0.3 ≦ Y ≦ 1.2.
[0125]
When a cellulose ester is used as the support according to the present invention, the cellulose as a raw material of the cellulose ester is not particularly limited, and examples thereof include cotton linters, wood pulp (derived from softwood, broadleaf), and kenaf. Cellulose esters obtained therefrom can be mixed and used at an arbitrary ratio. When the acylating agent is an acid anhydride (acetic anhydride, propionic anhydride, butyric anhydride), these cellulose esters use an organic acid such as acetic acid or an organic solvent such as methylene chloride, and use a solvent such as sulfuric acid. It can be obtained by reacting with a cellulose raw material using a protic catalyst.
[0126]
The acylating agent is acid chloride (CH₃COCl, C₂H₅COCl, C₃H₇In the case of (COCl), the reaction is carried out using a basic compound such as an amine as a catalyst. Specifically, it can be synthesized with reference to the method described in JP-A-10-45804 and the like. Further, the cellulose ester according to the present invention is obtained by mixing and reacting the above-mentioned acylating agents in accordance with the respective degrees of substitution. In the cellulose ester, these acylating agents react with hydroxyl groups of cellulose molecules. Cellulose molecules are composed of a large number of linked glucose units, and the glucose unit has three hydroxyl groups. The number of acyl groups derived from these three hydroxyl groups is called the degree of substitution (mol%). For example, cellulose triacetate has an acetyl group bonded to all three hydroxyl groups of a glucose unit (actually, 2.6 to 3.0).
[0127]
As the cellulose ester according to the present invention, cellulose acetate propionate, cellulose acetate butyrate, or a mixed fatty acid ester of cellulose bonded with a propionate group or a butyrate group in addition to an acetyl group such as cellulose acetate propionate butyrate. Particularly preferably used. The butyryl group forming butyrate may be linear or branched.
[0128]
Cellulose acetate propionate containing a propionate group as a substituent has excellent water resistance and is useful as a film for a liquid crystal image display device.
[0129]
The method for measuring the degree of substitution of the acyl group can be measured according to ASTM-D817-96.
[0130]
The cellulose ester having a number average molecular weight in the range of 70,000 to 250,000 has a high mechanical strength when molded and has an appropriate dope viscosity at the time of preparing a coating solution, and more preferably 80,000. １５０150,000.
[0131]
Here, the number average molecular weight of the cellulose ester can be measured using a GPC (gel permeation chromatography) method known to those skilled in the art.
[0132]
《Film formation》
These cellulose esters are prepared by pressurizing a cellulose ester solution (dope), which is generally referred to as a casting method, onto a casting support of an endless metal belt or a rotating metal drum for infinite transfer, as described below. It is manufactured by a method of casting a dope from a die and forming a film. As an organic solvent used for preparing these dopes, it is preferable to dissolve a cellulose ester and to have a moderate boiling point. For example, methylene chloride, methyl acetate, ethyl acetate, amyl acetate, acetone, tetrahydrofuran, 1,3- Dioxolan, 1,4-dioxane, cyclohexanone, ethyl formate, 2,2,2-trifluoroethanol, 2,2,3,3-tetrafluoro-1-propanol, 1,3-difluoro-2-propanol, 1, 1,1,3,3,3-hexafluoro-2-methyl-2-propanol, 1,1,1,3,3,3-hexafluoro-2-propanol, 2,2,3,3,3- Examples thereof include pentafluoro-1-propanol, nitroethane, and 1,3-dimethyl-2-imidazolidinone. Organic halogen compounds such as Renkuroraido, dioxolane derivatives, methyl acetate, ethyl acetate, preferred organic solvents are acetone (i.e., good solvent), and as.
[0133]
Further, as shown in the film forming step below, when the solvent is dried from the web (dope film) formed on the casting support in the solvent evaporation step, it is used from the viewpoint of preventing foaming in the web. The boiling point of the organic solvent to be obtained is preferably from 30 to 80 ° C. For example, the boiling points of the above-mentioned good solvents are methylene chloride (boiling point 40.4 ° C), methyl acetate (boiling point 56.32 ° C), and acetone (boiling point 56 0.3 ° C.), ethyl acetate (boiling point 76.82 ° C.) and the like.
[0134]
Among the good solvents described above, methylene chloride and methyl acetate which are excellent in solubility are preferably used, and it is particularly preferable that methylene chloride is contained in an amount of 50% by mass or more based on the total organic solvent.
[0135]
In addition to the above organic solvent, it is preferable to contain 0.1% to 30% by mass of an alcohol having 1 to 4 carbon atoms. Particularly preferably, the alcohol is contained in an amount of 5% by mass to 30% by mass. In these methods, after the dope described above is cast on a casting support, the solvent (evaporation) begins to evaporate, and when the alcohol ratio increases, the web (dope film) gels to make the web strong and peel off from the casting support. It is also used as a gelling solvent to facilitate the dissolution, and when these proportions are small, it also has a role to promote the dissolution of the cellulose ester of the non-chlorine organic solvent.
[0136]
Examples of the alcohol having 1 to 4 carbon atoms include methanol, ethanol, n-propanol, iso-propanol, n-butanol, sec-butanol and tert-butanol.
[0137]
Among these solvents, ethanol is preferred because the dope has good stability, a relatively low boiling point, good drying properties, and no toxicity. Preferably, a solvent containing 5% to 30% by mass of ethanol with respect to 70% to 95% by mass of methylene chloride is used. To avoid solvents containing halogens due to environmental restrictions, methyl acetate can be used instead of methylene chloride. At this time, the dope may be prepared by a cooling dissolution method.
[0138]
《Plasticizer》
When a cellulose ester is used for the support of the antireflection film of the present invention, the cellulose ester preferably contains a plasticizer. The plasticizer is not particularly limited, but includes a phosphate ester plasticizer, a phthalate ester plasticizer, a trimellitate ester plasticizer, a pyromellitic acid plasticizer, a glycolate plasticizer, and a citrate ester plasticizer. Plasticizers, polyester plasticizers and the like are preferably used.
[0139]
Phosphate plasticizers include triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, octyl diphenyl phosphate, diphenyl biphenyl phosphate, trioctyl phosphate, and tributyl phosphate.Phthalate plasticizers include diethyl phthalate, dimethoxy In the case of trimellitic acid plasticizers such as ethyl phthalate, dimethyl phthalate, dioctyl phthalate, dibutyl phthalate, di-2-ethylhexyl phthalate, butyl benzyl phthalate, diphenyl phthalate and dicyclohexyl phthalate, tributyl trimellitate, triphenyl trimellitate and triethyl Pyromellitic ester plasticizers such as trimellitate include tetrabutyl pyromellitate and Glycolate plasticizers such as rupyromellitate and tetraethyl pyromellitate include triacetin, tributyrin, ethylphthalylethyl glycolate, methylphthalylethyl glycolate, and butylphthalylbutyl glycolate; Citrate, tri-n-butyl citrate, acetyl triethyl citrate, acetyl tri-n-butyl citrate, acetyl tri-n- (2-ethylhexyl) citrate and the like can be preferably used. Examples of other carboxylic esters include butyl oleate, methylacetyl ricinoleate, dibutyl sebacate, and various trimellitates.
[0140]
As the polyester-based plasticizer, a copolymer of a glycol and a dibasic acid such as an aliphatic dibasic acid, an alicyclic dibasic acid, or an aromatic dibasic acid can be used. The aliphatic dibasic acid is not particularly limited, but adipic acid, sebacic acid, phthalic acid, terephthalic acid, 1,4-cyclohexyldicarboxylic acid and the like can be used. As the glycol, ethylene glycol, diethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, 1,4-butylene glycol, 1,3-butylene glycol, 1,2-butylene glycol, or the like can be used. These dibasic acids and glycols may be used alone or in combination of two or more.
[0141]
In particular, cellulose compounds having additives such as epoxy compounds, rosin compounds, phenol novolak type epoxy resins, cresol novolak type epoxy resins, ketone resins, and toluenesulfonamide resins described in JP-A-2002-146044 are also preferably used. .
[0142]
Specifically, rosin and rosin derivatives include those having the following structural formulas.
[0143]
Embedded image

[0144]
Among the above compounds, KE-604 and KE-610 are commercially available from Arakawa Chemical Industries, Ltd. with acid numbers 237 and 170, respectively. Similarly, Arakawa Chemical Industries, Ltd. sells KE-100 and KE-356 as esterified products of a mixture of abietic acid, dehydroabietic acid, and parastric acid at an acid value of 8 and 0, respectively. In addition, a mixture of abietic acid, dehydroabietic acid, and parastric acid is commercially available from Harima Kasei Co., Ltd. as G-7 and Hartol RX having acid numbers of 167 and 168, respectively.
[0145]
Examples of the epoxy resin used in the present invention include those having the following structure.
[0146]
Embedded image

[0147]
Araldide EPN1179 and Araldide AER260 are commercially available from Asahi Ciba.
[0148]
Examples of the ketone resin include those having the following structures.
[0149]
Embedded image

[0150]
Hiluck 110 and Hiluck 110H are commercially available products of Hitachi Chemical Co., Ltd.
Examples of the paratoluenesulfonamide resin include those having the following structures, and are commercially available as toplers from Fujiamido Chemical Co., Ltd.
[0151]
Embedded image

[0152]
These plasticizers are preferably used alone or in combination.
The use amount of these plasticizers is preferably 1% by mass to 20% by mass based on the cellulose ester in terms of film performance, processability, and the like.
[0153]
《Optical properties of the support》
The optical properties of the support include, as optical anisotropy, a retardation value (R₀) Is preferably from 0 nm to 1000 nm, and has a retardation value (R_t) Is preferably from 0 nm to 300 nm depending on the application.
[0154]
Further, as wavelength dispersion characteristics, R (600) / R (450) is preferably from 0.7 to 1.3, and particularly preferably from 1.0 to 1.3. Here, R (450) and R (600) are in-plane retardation values (R) of light having wavelengths of 450 nm and 600 nm, respectively.₀).
[0155]
《Hard coat layer》
The hard coat layer according to the present invention will be described.
[0156]
As the hard coat layer according to the present invention, a photocurable resin layer or a thermosetting resin layer is preferably used. In the present invention, a photocurable resin layer is provided as a hard coat layer on a support (also referred to as a substrate), and an optical interference layer (a medium refractive index layer, a high refractive index layer, a low refractive index layer, etc.) is provided thereon. Is preferred.
[0157]
Here, an example in which a photocurable resin is used, particularly a photocurable resin layer for hard coat processing will be described.
[0158]
The hard coat layer according to the present invention may be provided directly on the support, or may be provided on another layer such as an antistatic layer or an undercoat layer.
[0159]
When a photocurable resin layer is provided as the hard coat layer, it is preferable to contain a photocurable resin that is cured by irradiation with light such as ultraviolet rays. As the photocurable resin, those similar to the aforementioned photocurable resins (for example, a layer formed using an epoxy-based photocurable compound) can be used. The light source of light, the irradiation amount, the photoinitiator and the photosensitizer, the amount of use thereof, and the like are the same as described above.
[0160]
(Refractive index and thickness of hard coat layer)
The hard coat layer according to the present invention preferably has a refractive index in the range of 1.45 to 1.65 from the viewpoint of optical design for imparting low reflection to the antireflection film of the present invention. In addition, from the viewpoint of imparting sufficient durability and impact resistance to the anti-reflection film, and considering appropriate flexibility, economy at the time of production, etc., the thickness of the hard coat layer is 1 μm to 20 μm. The range is preferably, and more preferably, 1 μm to 10 μm.
[0161]
The photocurable resin layer is a light irradiation such as an ultraviolet ray or an electron beam (in the present invention, "light" means various electromagnetic waves such as an electron beam, a neutron beam, an X ray, an alpha ray, an ultraviolet ray, a visible ray, an infrared ray, Are defined as light) and a resin containing as a main component a resin cured through a crosslinking reaction or the like. Typical examples of the photocurable resin include an ultraviolet curable resin and an electron beam curable resin, and may be a resin that is cured by irradiation with light other than ultraviolet light or an electron beam. 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.
[0162]
Specific examples of ultraviolet-curable acrylic urethane resin, ultraviolet-curable polyester acrylate-based resin, ultraviolet-curable epoxy acrylate-based resin, ultraviolet-curable polyol acrylate-based resin, or ultraviolet-curable epoxy resin are described in the section of the binder. Can be mentioned.
[0163]
Further, the photoreaction initiator can also be used as a photosensitizer. 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. The amount of the photoreaction initiator or the photosensitizer contained in the ultraviolet-curable resin composition excluding the solvent component volatilized after coating and drying is preferably 2.5 to 6% by mass of the composition.
[0164]
Examples of the resin monomer include, as a monomer having one unsaturated double bond, general monomers such as methyl acrylate, ethyl acrylate, butyl acrylate, vinyl acetate, benzyl acrylate, cyclohexyl acrylate, and styrene. Examples of the monomer having two or more unsaturated double bonds include ethylene glycol diacrylate, propylene glycol diacrylate, divinylbenzene, 1,4-cyclohexane diacrylate, 1,4-cyclohexyldimethyl adiacrylate, and the above-mentioned trimethylolpropane triacrylate. Acrylate, pentaerythritol tetraacrylic ester and the like can be mentioned.
[0165]
Further, an ultraviolet absorber may be included in the ultraviolet-curable resin composition to such an extent as not to hinder photocuring of the ultraviolet-curable resin composition. As the ultraviolet absorber, those similar to the ultraviolet absorber which may be used for the base material can be used.
[0166]
In order to enhance the heat resistance of the cured layer, an antioxidant that does not inhibit 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-t-3-methylphenol), 4,4'-butylidenebis (6-t-butyl-3-methylphenol), 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, 2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) mesitylene, di-octadecyl-4- Hydroxy-3,5-di-t-butylbenzyl phosphate and the like can be mentioned.
[0167]
As the ultraviolet curable resin, for example, ADEKA OPTOMER KR, BY series KR-400, KR-410, KR-550, KR-566, KR-567, BY-320B (all manufactured by Asahi Denka Kogyo KK) ), 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, SCR900 (these are Dainichi Seika Industries ( )), KRM7033, KRM7039, KRM7130, KRM7131, UVECRYL29201, UVECRYL29202 (hereafter, 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, Incorporated). 340 Clear (China Paint Co., Ltd.), Sunrad H-601 (Sanyo Chemical Industry Co., Ltd.), SP-1509, SP-1507 (all manufactured by Showa Polymer Co., Ltd.), RCC-15C (Grace Co., Ltd.) Japan Co., Ltd.), Aronix M-6100, M-8030, M-8060 (all manufactured by Toagosei Co., Ltd.), or other commercially available products.
[0168]
The solid content of the coating composition for the photocurable resin layer is preferably 10 to 95% by mass, and an appropriate concentration is selected depending on the coating method.
[0169]
As a light source for forming a cured film layer of the photocurable resin by a photocuring reaction, any light source that generates ultraviolet light can be used. Specifically, the light sources described in the section of the light can be used. Irradiation conditions are different for each lamp, but the irradiation light amount is 20 mJ / cm²〜１０10000 mJ / cm²Is more preferable, and more preferably 50 mJ / cm²~ 2000mJ / cm²It is. From the near-ultraviolet region to the visible region, it can be used by using a sensitizer having an absorption maximum in that region.
[0170]
The solvent for coating the photocurable resin layer can be appropriately selected from, for example, hydrocarbons, alcohols, ketones, esters, glycol ethers, and other solvents, or can be used as a mixture. Preferably, a solvent containing propylene glycol mono (C1 to C4) alkyl ether or propylene glycol mono (C1 to C4) alkyl ether ester in an amount of 5% by mass or more, more preferably 5% by mass to 80% by mass or more is used.
[0171]
Known methods such as a gravure coater, a spinner coater, a wire bar coater, a roll coater, a reverse coater, an extrusion coater, and an air doctor coater can be used as a method of applying the photocurable resin composition coating liquid. The coating amount is suitably from 0.1 μm to 30 μm in wet film thickness, and preferably from 0.5 μm to 15 μm. The coating speed is preferably in the range of 10 m / min to 60 m / min.
[0172]
After the photocurable resin composition is coated and dried, it is irradiated with ultraviolet rays. The irradiation time is preferably 0.5 seconds to 5 minutes, and the curing efficiency and working efficiency of the ultraviolet curable resin is more preferably 3 seconds to 2 minutes. preferable.
[0173]
In this way, a cured coating layer can be obtained. However, in order to provide an antiglare property to the surface of the liquid crystal display panel, prevent adhesion to other substances, and enhance abrasion resistance, etc., the cured coating layer is used. Inorganic or organic fine particles may be added to the coating composition for use.
[0174]
For example, examples of the inorganic fine particles include silicon oxide, titanium oxide, aluminum oxide, tin oxide, zinc oxide, calcium carbonate, barium sulfate, talc, kaolin, and calcium sulfate.
[0175]
The organic fine particles include polymethacrylate methyl acrylate resin powder, acrylic styrene resin powder, polymethyl methacrylate resin powder, silicon resin powder, polystyrene resin powder, polycarbonate resin powder, benzoguanamine resin powder, and melamine resin. Powder, polyolefin-based resin powder, polyester-based resin powder, polyamide-based resin powder, polyimide-based resin powder, polyfluoroethylene-based resin powder, and the like can be given. These can be used in addition to the ultraviolet curable resin composition. The average particle size of these fine particle powders is 0.01 μm to 10 μm, and the amount used is 0.1 to 20 parts by mass with respect to 100 parts by mass of the ultraviolet curable resin composition. Is desirable. In order to impart an antiglare effect, it is preferable to use fine particles having an average particle size of 0.1 μm to 1 μm in an amount of 1 to 15 parts by mass based on 100 parts by mass of the ultraviolet-curable resin composition.
[0176]
By adding such fine particles to the ultraviolet curable resin, an antiglare layer having a preferable unevenness having a center line average surface roughness Ra of 0.1 μm to 0.5 μm can be formed. When such fine particles are not added to the ultraviolet-curable resin composition, the center line average surface roughness Ra is less than 0.05 μm, more preferably 0.002 μm to less than 0.04 μm. A coat layer can be formed. On these hard coat layers and the like, a high refractive index layer (preferably 1.6 to 2.3), a low refractive index layer (preferably 1.35 to 1.5) and the like are further provided. An anti-reflection layer can also be formed. Alternatively, it is preferable to further provide a middle refractive index layer.
[0177]
In addition, as a component that functions as an anti-blocking agent, ultrafine particles having a volume average particle diameter of 0.005 μm to 0.1 μm and the same components as described above are used in an amount of 0.1 to 5 parts by mass per 100 parts by mass of the resin composition. Parts by mass can also be used.
[0178]
<< Back of antireflection film (also called back of support) >>
On the back surface of the antireflection film of the present invention, 1 to 500 protrusions having a height of 0.1 μm to 10 μm / 0.01 mm²Is preferably provided, and more preferably 10 to 400 pieces / 0.01 mm²And particularly preferably 15 to 300 / 0.01 mm²It is.
[0179]
This not only can prevent the occurrence of blocking even if the film is once wound up into a roll during the application of each optical interference layer, but also can significantly reduce unevenness in application when the next optical interference layer is applied. . Although the cause of the coating unevenness has not been completely elucidated, it is assumed that one of the causes is related to peeling charging when the film wound in a roll is sent to the coating step.
[0180]
As means for providing the protrusions on the back surface, fine particles are added to the support base material film to form 1 to 500 protrusions having a height of 0.1 μm to 10 μm on the back surface / 500 mm / 0.01 mm.²Can be included. At this time, the base film may have a multilayer structure, and fine particles may be contained only in the surface layer.
[0181]
The type of fine particles to be added may be an organic compound or an inorganic compound, for example, silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, calcium carbonate, kaolin, talc, calcined calcium silicate, hydrated calcium silicate, aluminum silicate , Magnesium silicate, calcium phosphate, and other inorganic fine particles and crosslinked polymer fine particles. Among them, silicon dioxide is preferable because the haze of the film can be reduced. The average particle size of the secondary particles of the fine particles is 0.1 to 10 μm, and the content thereof is preferably 0.04 to 0.3% by mass based on the cellulose ester of the base material. Fine particles such as silicon dioxide are often surface-treated with an organic substance, but this is preferable because the haze of the film can be reduced. Preferred organic substances for the surface treatment include halosilanes, alkoxysilanes (especially alkoxysilanes having a methyl group), silazane, siloxane and the like. The larger the average particle size of the fine particles, the greater the matting effect, and the smaller the average particle size, the more excellent the transparency. Therefore, the average primary particle size of the fine particles is preferably 5 nm to 50 nm, more preferably 7 nm to 16 nm. It is. Examples of fine particles of silicon dioxide include AEROSIL (Aerosil) 200, 200V, 300, R972, R972V, R974, R202, R812, OX50, and TT600 manufactured by Aerosil Co., Ltd., and preferably AEROSIL (Aerosil) 200V. R972, R972V, R974, R202, and R812. Two or more of these fine particles may be used in combination. When two or more kinds are used in combination, they can be used by mixing at an arbitrary ratio. In this case, fine particles having different average particle diameters and materials, for example, AEROSIL (Aerosil) 200V and R972V can be used in a mass ratio of 0.1: 99.9 to 99.9: 0.1.
[0182]
In the present invention, the fine particles may be contained and dispersed together with the cellulose ester, other additives and an organic solvent during the preparation of the dope, but may be dispersed in a sufficiently dispersed state such as a fine particle dispersion separately from the cellulose ester solution. Is preferably prepared. In order to disperse the fine particles, it is preferable that the fine particles are dipped in an organic solvent in advance and then finely dispersed by a disperser having a high shearing force (high-pressure disperser). Thereafter, it is preferable that the dope is dispersed in a larger amount of an organic solvent, combined with the cellulose ester solution, and mixed with an in-line mixer to form a dope. In this case, an ultraviolet absorber may be added to the fine particle dispersion to form an ultraviolet absorber liquid.
[0183]
Further, by coating a layer containing fine particles on the back surface side of the antireflection film having the optical interference layer, 1 to 500 protrusions having a height of 0.1 μm to 10 μm are formed on the back surface / 500 protrusions / 0.01 mm.²Having an anti-reflection film (also referred to as a low-reflection laminate).
[0184]
《Curl characteristics》
The curl characteristics of the antireflection film of the present invention will be described.
[0185]
When only one surface of the film is subjected to surface processing, or when both surfaces are subjected to different types or different degrees of surface processing, a curling phenomenon that the film is rounded easily occurs. Curling is inconvenient because it is difficult to handle when producing a polarizing plate using the curl.
[0186]
In order to prevent curling, an anti-curl layer can be provided on the side opposite to the hard coat layer. That is, the curling degree is balanced by giving a property of being rounded with the surface on which the anti-curl layer is provided inside. The anti-curl layer is preferably coated also as a blocking layer. In this case, the coating composition may contain the above-mentioned inorganic fine particles and / or organic fine particles for imparting an anti-blocking function. (This layer is also called a back coat layer.)
The application of the anti-curl function is specifically performed by applying a composition containing a solvent that dissolves or swells the substrate. The solvent to be used may include a solvent that is not dissolved, in addition to a solvent to be dissolved or a mixture of solvents to be swollen. These are performed using a composition and a coating amount in which these are mixed at a ratio appropriately selected depending on the curl degree of the resin film and the type of the resin.
[0187]
When it is desired to enhance the curl prevention function, it is effective to increase the mixing ratio of the solvent to be dissolved or the solvent to be swollen, and to decrease the ratio of the solvent not to be dissolved. Preferably, the mixing ratio is (solvent to be dissolved or swelled) :( solvent not to be dissolved) = 10: 0 to 1: 9. Examples of the solvent to be dissolved or swelled contained in such a mixed composition include, for example, benzene, toluene, xylene, dioxane, acetone, methyl ethyl ketone, N, N-dimethylformamide, methyl acetate, ethyl acetate, trichloroethylene, methylene chloride, Examples include ethylene chloride, tetrachloroethane, trichloroethane, and chloroform. Examples of the solvent that does not dissolve include methanol, ethanol, n-propyl alcohol, i-propyl alcohol, and n-butanol.
[0188]
It is preferable to apply these coating compositions to the surface of the base material using a gravure coater, dip coater, reverse roll coater, extrusion coater, or the like, and it is particularly preferable that the thickness be 5 to 30 μm.
[0189]
The coating composition can contain a resin. Examples of the resin used here include a vinyl chloride / vinyl acetate copolymer, a vinyl chloride resin, a vinyl acetate resin, a copolymer of vinyl acetate and vinyl alcohol, Partially hydrolyzed vinyl chloride / vinyl acetate copolymer, vinyl chloride / vinylidene chloride copolymer, vinyl chloride / acrylonitrile copolymer, ethylene / vinyl alcohol copolymer, chlorinated polyvinyl chloride, ethylene / vinyl chloride copolymer Coalesce, vinyl polymer or copolymer such as ethylene / vinyl acetate copolymer, nitrocellulose, cellulose acetate propionate, diacetyl cellulose, cellulose acetate butyrate, cellulose ester resin such as cellulose acetate propionate resin, Maleic and / or acrylic acid Polymer, acrylate copolymer, acrylonitrile / styrene copolymer, chlorinated polyethylene, acrylonitrile / chlorinated polyethylene / styrene copolymer, methyl methacrylate / butadiene / styrene copolymer, acrylic resin, polyvinyl acetal resin, polyvinyl Butyral resin, polyester polyurethane resin, polyether polyurethane resin, polycarbonate polyurethane resin, polyester resin, polyether resin, polyamide resin, amino resin, rubber resin such as styrene / butadiene resin, butadiene / acrylonitrile resin, silicone resin, fluorine resin Examples of the resin include, but are not limited to, resins. As the acrylic resin, Acrypet MD, VH, MF, V (all manufactured by Mitsubishi Rayon Co., Ltd.), Hyperl M-4003, M-4005, M-4006, M-4202, M-5000, M-5001, M-4501 (manufactured by Negami Kogyo Co., Ltd.), Dianal BR-50, BR-52, BR-53, BR-60, BR-64, BR-73, BR-75, BR-77, BR- 79, BR-80, BR-82, BR-83, BR-85, BR-87, BR-88, BR-90, BR-93, BR-95, BR-100, BR-101, BR-102, BR-105, BR-106, BR-107, BR-108, BR-112, BR-113, BR-115, BR-116, BR-117, BR-118 (all manufactured by Mitsubishi Rayon Co., Ltd.) and the like Used by It is. Particularly preferably, a cellulose ester resin such as diacetyl cellulose or cellulose acetate propionate is used.
[0190]
The order of applying the anti-curl layer may be before or after applying the optically functional layer (for example, an antistatic layer or a hard coat layer, an optical interference layer, etc.) on the opposite side of the substrate. When the layer also functions as an anti-blocking layer, it is preferable to apply the layer first.
[0191]
"Polarizer"
The polarizing plate of the present invention will be described.
[0192]
The polarizing plate of the present invention can be manufactured by a general method. For example, there is a method in which the optical compensation film of the present invention is subjected to alkali saponification treatment, and then immersed and stretched in an iodine solution to be bonded to both surfaces of a polarizing film using a completely saponified polyvinyl alcohol aqueous solution. The alkali saponification treatment refers to a treatment in which a cellulose ester film is immersed in a high-temperature strong alkaline solution in order to improve the wettability of the aqueous adhesive and improve the adhesiveness.
[0193]
Further, in the polarizing plate of the present invention, the light transmission axis of the polarizer containing a dichroic substance and the stretching direction in the width direction at the time of casting and forming the optical compensation film to be bonded to the polarizer are substantially the same. It is preferable to be bonded so as to be parallel. Note that, in the present invention, orthogonal means that the axes are substantially orthogonal as described above, and that the directions are identical means that the directions of the axes are substantially parallel. Is shown. Here, “substantially parallel” means that the angle between the respective axes is within ± 10 °, preferably within ± 3 °, more preferably within ± 1 °, and particularly preferably ± 0 °. Represents
[0194]
As the polarizer used for the polarizing plate of the present invention, a conventionally known polarizer can be used. For example, a film made of a hydrophilic polymer such as polyvinyl alcohol and stretched by treating with a dichroic dye such as iodine, or a film obtained by treating and orienting a plastic film such as vinyl chloride is used. The polarizer thus obtained is bonded to a cellulose ester film.
[0195]
At this time, the optical compensation film of the present invention is used for at least one of the cellulose ester films. On the other side, another cellulose ester film can be used. On the other side, a cellulose ester film manufactured for the optical compensation film of the present invention may be used, or a commercially available cellulose ester film (Konica Cat KC8UX2MW, KC4UX2MW, KC5UN (manufactured by Konica Corporation)) may be used. Can be used as a polarizing plate protective film on the other side. The polarizing plate protective film used on the surface side of the display device preferably has an antiglare layer, a clear hard coat layer, an antireflection layer, an antistatic layer, and an antifouling layer. The antireflection layer (silicon oxide layer, titanium oxide layer), antistatic layer, and antifouling layer are preferably provided by a method such as coating, sputtering, CVD, atmospheric pressure plasma CVD, and vacuum deposition.
[0196]
《Liquid crystal display device》
The polarizing plate of the present invention obtained as described above is arranged on both sides of the liquid crystal cell and bonded to produce the liquid crystal display of the present invention.
[0197]
Further, at the time of producing the polarizing plate, it is preferable to bond the optical compensation film of the present invention so that the slow axis of the optical compensation film is parallel to the transmission axis of the polarizer. As a result, light leakage at the time of black display is remarkably improved, and even in a large-screen liquid crystal display device of 15 inches or more, preferably 19 inches or more, there is no white spot at the periphery of the screen, and the effect is small. It is maintained for a long time, and a remarkable effect is particularly recognized in a VA liquid crystal display device.
[0198]
An optically anisotropic layer using a liquid crystal compound can be further formed on the optical compensation film of the present invention, if necessary, and a liquid crystal display device employing various driving methods such as TN, VA, OCB, and HAN can be used. The viewing angle characteristics can be optimized.
[0199]
【Example】
Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited thereto.
[0200]
Example 1
<< Preparation of antireflection film 1 >>
Antireflection film 1 was produced as follows. The refractive index and the thickness of the optical interference layers such as the hard coat layer, the high refractive index layer, the low refractive index layer, and the middle refractive index layer of the produced antireflection film were measured by the following methods.
[0201]
(Refractive index, film thickness)
The refractive index and film thickness of each refractive index layer, hard coat layer, etc. were determined from the measurement results of spectral reflectance of a spectrophotometer for a sample in which each layer was applied alone.
[0202]
Using a U-4000 spectrophotometer (manufactured by Hitachi, Ltd.), after roughening the back surface on the measurement side of the sample, light absorption treatment is performed with black spray to prevent light reflection on the back surface. Then, the reflectance in the visible light region (400 nm to 700 nm) is measured under the condition of 5 ° regular reflection.
[0203]
<< Preparation of hard coat layer >>
The following hard coat layer composition (C-1) was dried on one surface of a cellulose triacetate film (Konica Cat KC8UX2MW, manufactured by Konica Corporation, refractive index: 1.49, degree of substitution of acetyl group: 2.88) having a thickness of 80 μm. It was applied to a thickness of 3.5 μm and dried at 80 ° C. for 1 minute. Next, use a high-pressure mercury lamp (80 W) for 150 mJ / cm.²And a hard coat layer was prepared.
[0204]
Hard coat layer thickness: 3.5 μm
Refractive index of hard coat layer: 1.50
(Hard coat layer composition (C-1))
Dipentaerythritol hexaacrylate
120 parts by mass of monomer
40 parts by mass of dimer
More than trimer 40 parts by mass
Diethoxybenzophenone (UV photoinitiator) 20 parts by mass
330 parts by mass of propylene glycol monomethyl ether
330 parts by mass of ethyl acetate
<< Preparation of high refractive index layer >>
Next, the following high refractive index layer composition H-1 was applied on the hard coat layer by a die coater, and dried at 80 ° C. and 0.1 m / sec for 1 minute. After drying, ultraviolet light was applied using a high-pressure mercury lamp (80 W) to 130 mJ / cm.²Irradiation and curing resulted in the formation of a high refractive index layer.
[0205]
Thickness of high refractive index layer: 72 nm
Refractive index of high refractive index layer: 1.70
(High refractive index layer composition (H-1))
Titanium oxide fine particle dispersion (solid content: 15%, manufactured by CI Kasei Kogyo Co., Ltd.
(RTSPNB15WT% -G0) 330 parts by mass
Di-i-propoxy bis (acetylacetonato) titanium
(Orgatics TC100 manufactured by Matsumoto Pharmaceutical Company Limited) 5 parts by mass
Dipentaerythritol hexaacrylate monomer 40 parts by mass
Irgacure 184 10 parts by mass
Linear dimethyl silicone-EO block copolymer
(FZ-2207 manufactured by Nippon Unicar) 1 part by mass
Propylene glycol monomethyl ether 1470 parts by mass
2660 parts by mass of isopropyl alcohol
490 parts by mass of methyl ethyl ketone
<< Preparation of low refractive index layer >>
On the obtained high refractive index layer, the following low refractive index layer composition (L-1) was applied using a die coater, and dried at 80 ° C. and 0.1 m / sec for 1 minute. After drying, ultraviolet light was applied using a high-pressure mercury lamp (80 W) to 130 mJ / cm.²Irradiation and curing were performed to form a low-refractive-index layer, and further heat-cured at 120 ° C. for 5 minutes to produce an antireflection film 1 having a low-refractive-index layer.
[0206]
Thickness of low refractive index layer: 100 nm
Low refractive index layer refractive index: 1.44
(Preparation of Tetraethoxysilane Hydrolyzate A)
29 g of tetraethoxysilane and 55 g of ethanol were mixed, and 16 g of a 1.6% by mass aqueous solution of acetic acid was added thereto, followed by stirring at 25 ° C. for 20 hours to prepare a tetraethoxysilane hydrolyzate A.
[0207]
(Preparation of low refractive index layer composition (L-1))
230 parts by mass of tetraethoxysilane hydrolyzate A
γ-methacryloxypropyltrimethoxysilane
(KBM503 :: manufactured by Shin-Etsu Chemical Co., Ltd.) 6 parts by mass
Linear dimethyl silicone-EO block copolymer
(FZ-2207: manufactured by Nippon Unicar)
3% by mass of 10% propylene glycol monomethyl ether solution
Propylene glycol monomethyl ether 380 parts by mass
380 parts by mass of isopropyl alcohol
<< Preparation of antireflection film 2 >>
In the preparation of the antireflection film 1, the same applies except that the thickness of the hard coat layer was changed to 7.0 μm, and the nanoindentation hardness (H) and the elastic modulus (Er) were adjusted as described in Table 1. Thus, an antireflection film 2 was produced.
[0208]
<< Preparation of antireflection film 3 >>
In the preparation of the antireflection film 2, the hard coat layer composition was changed to the following hard coat layer composition (C-2), and the nanoindentation hardness (H) and the elastic modulus (Er) were as shown in Table 1. An antireflection film 3 was produced in the same manner except that the adjustment was performed as described above.
[0209]
<Hard coat layer composition (C-2)>
Dipentaerythritol hexaacrylate
120 parts by mass of monomer
40 parts by mass of dimer
More than trimer 40 parts by mass
Diethoxybenzophenone (UV photoinitiator) 20 parts by mass
Propylene glycol monomethyl ether 110 parts by mass
Ethyl acetate 110 parts by mass
<< Preparation of antireflection film 4 >>
An anti-reflection film 4 was produced in the same manner as in the production of the anti-reflection film 3 except that the thickness of the hard coat layer was changed to 15 μm.
[0210]
<< Preparation of antireflection film 5 >>
An antireflection film 5 was produced in the same manner as in the production of the antireflection film 3, except that the hard coat layer composition was changed to the following hard coat layer composition (C-3).
[0211]
(Hard coat layer composition (C-3))
Dipentaerythritol hexaacrylate
90 parts by mass of monomer
35 parts by mass of dimer
More than trimer 35 parts by mass
Acrylic resin (Dianal BR108,
Mitsubishi Rayon Co., Ltd.) 20 parts by mass
Diethoxybenzophenone (UV photoinitiator) 20 parts by mass
Propylene glycol monomethyl ether 110 parts by mass
Ethyl acetate 110 parts by mass
<< Preparation of antireflection film 6 >>
An antireflection film 6 was produced in the same manner as in the production of the antireflection film 3 except that the hard coat layer composition was changed to the following hard coat layer composition (C-4).
[0212]
<Hard coat layer composition (C-4)>
KRX-574-7 (Asahi Denka Kogyo Co., Ltd. hard coat agent) 100 parts by mass
Propylene glycol monomethyl ether 50 parts by mass
Ethyl acetate 50 parts by mass
<< Preparation of antireflection film 7 >>
In the production of the antireflection film 3, the low refractive index layer composition (L-1) was changed to the following low refractive index layer composition (L-2), and ultraviolet rays were irradiated at 500 mJ / cm.²An antireflection film 7 was produced in the same manner except that the film was irradiated and cured.
[0213]
(Low refractive index layer composition (L-2))
Obstar JN7200 (F-based polymer: JSR Corporation) 10 parts by mass
MIBK 490 parts by mass
<< Preparation of antireflection film 8 >>
In the production of the antireflection film 1, the thickness of the hard coat layer was changed to 0.5 μm, and the nano indentation hardness (H) and the elastic modulus (Er) of each of the hard coat layer and the low refractive index layer were changed. An anti-reflection film 8 was produced in the same manner except that the composition was changed as shown in Table 1.
[0214]
<< Preparation of antireflection film 9 >>
In the preparation of the antireflection film 3, the thickness of the hard coat layer was changed to 22 μm, and the nano indentation hardness (H) and the elastic modulus (Er) of each of the hard coat layer and the low refractive index layer were shown in Table 1. The anti-reflection film 9 was produced in the same manner except for changing as described in (1).
[0215]
<< Preparation of antireflection film 10 >>
In the production of the antireflection film 3, the high refractive index layer composition (H-2) and the low refractive index layer composition (L-1) were formed on the hard coat layer as follows using an extrusion coater. Except for the above, an antireflection film 10 was produced in the same manner.
[0216]
(Production of high refractive index layer)
The following high refractive index layer composition (H-2) was applied on the hard coat layer by a die coater, and dried at 80 ° C. and 0.1 m / sec for 1 minute. After drying, ultraviolet light was applied using a high-pressure mercury lamp (80 W) to 130 mJ / cm.²Irradiation, further heat treatment at 120 ° C. for 5 minutes, again using a high-pressure mercury lamp (80 W) to emit ultraviolet rays at 130 mJ / cm.²Irradiation and heat treatment were performed at 120 ° C. for 5 minutes to form a high refractive index layer.
[0217]
Thickness of high refractive index layer: 72 nm
Refractive index of high refractive index layer: 1.70
<High refractive index layer composition (H-2)>
50 parts by mass of tetra (n) butoxytitanium
γ-methacryloxypropyltrimethoxysilane
(KBM503 manufactured by Shin-Etsu Chemical Co., Ltd.) 34 parts by mass
Acrylic resin (Dianal BR102,
15 parts by mass (Mitsubishi Rayon Co., Ltd.)
Linear dimethyl silicone-EO block copolymer
(FZ-2207: manufactured by Nippon Unicar) 1 part by mass
Propylene glycol monomethyl ether 1470 parts by mass
2940 parts by mass of isopropyl alcohol
490 parts by mass of methyl ethyl ketone
Next, the above low refractive index layer composition (L-1) was applied with a die coater and dried at 80 ° C. and 0.1 m / sec for 1 minute. After drying, ultraviolet light was applied using a high-pressure mercury lamp (80 W) to 130 mJ / cm.²Irradiation and curing to form a low refractive index layer, further heat treatment at 120 ° C. for 5 minutes, again using a high pressure mercury lamp (80 W) to emit ultraviolet rays at 130 mJ / cm.²Irradiation and heat treatment were performed at 120 ° C. for 5 minutes to produce an antireflection film 10 having a low refractive index layer.
[0218]
Thickness of low refractive index layer: 100 nm
Refractive index of low refractive index layer: 1.44
Further, the content of the elemental fluorine over the surface, near the surface, and inside the layer of the low refractive index layer as the outermost surface layer was determined as follows.
[0219]
<< Measurement of content of fluorine element in low refractive index layer >>
For the measurement of the fluorine element content of the low refractive index layer according to the present invention, the above-mentioned X-ray photoelectron spectroscopy (XPS) surface analyzer was used. The analysis was performed on the surface, near the surface, and further inside the layer by composition analysis (elemental fluorine analysis).
[0220]
The analysis of the inside of the layer, that is, the composition analysis in the depth direction was performed while the surface layer was shaved by ion etching. Hereinafter, specific conditions of ion etching will be described.
[0221]
Ion etching: using EX05 ion gun manufactured by VG Scientific
Etching ions: Argon, adjustable through a variable leak valve
Ion amount: 3 μA
Acceleration voltage: 3 kV
The area of the ion etching was performed by setting MAGNIFICTION of Physical Imaging Unit to 5.
[0222]
Lens mode: Set to SXA-1 (analysis diameter 1 mmφ)
The etching time was 60 seconds. After 10 seconds from the etching, the composition was analyzed. Further, the edging and the measurement were repeated twice, and the average of the measured values of three times was obtained.
[0223]
Physical property values (thickness, refractive index, nanoindentation hardness (H), elastic modulus (Er)), layer formation method, F content (fluorine atom content) of the constituent layers of antireflection films 1 to 10 prepared above ) Are shown in Table 2.
[0224]
[Table 2]

[0225]
Each of the obtained antireflection films 1 to 10 was evaluated as follows.
《Flatness》
Each of the antireflection films 1 to 10 was placed on a table on which a black velvet cloth was stuck, and the flatness was visually observed, and the rank was evaluated as follows.
[0226]
◎: Very good flatness
：: good flatness
Δ: Some unevenness is observed
×: Many irregularities are observed
《Handling》
The handling of the film was evaluated for the possibility of nail breaks and cracks.
[0227]
○: It is hard to make a nail break mark
Δ: Some traces of nail break remain, but cracks hardly occur
×: Traces of nail breaks are likely to remain and cracks are likely to occur.
《Scratch resistance》
Place the film on a smooth table, 1 cm on # 0000 steel wool²The film surface was rubbed 20 times with a load of 200 g per unit, and the number of scratches generated in a range of 1 cm in the direction perpendicular to the rubbing direction was visually counted and evaluated according to the following criteria.
[0228]
◎: 0
○: 1 to 5
△: 5 to 20
×: 20 or more
"Pencil hardness"
A pencil hardness test based on JIS K 5400 was performed. However, the load was set at 500 g.
[0229]
《Anti-fouling properties》
Fingerprints were applied to the anti-reflection treated surface with a finger, and it was checked whether the fingerprint could be wiped off with a Bencott.
[0230]
◎: Wipe the unit very much
○: Can be wiped off
×: Wipe remaining
《Solvent resistance》
The antireflection-treated surface was strongly rubbed with a bencot impregnated with methyl ethyl ketone, and a change in the state of the antireflection-treated surface was observed.
[0231]
○: No change
Δ: film peeling slightly occurs
×: changes in appearance such as film peeling
《Heat crack》
The anti-reflection film was put into a thermostat at 100 ° C. and maintained for 400 hours. Then, a black tape was attached to the back of the anti-reflection treated surface, and the anti-reflection treated surface was observed with a microscope (20 × objective lens, 10 × eyepiece). The occurrence of cracks was visually evaluated as follows.
[0232]
○: No crack
Δ: Weak and short cracks occur
×: Long cracks occur
Table 3 shows the obtained results.
[0233]
[Table 3]

[0234]
From Table 3, as compared with the comparison, the antireflection film of the present invention has excellent properties in all the items of flatness, handleability, scratch resistance, pencil hardness, heat crack, antifouling property, and solvent resistance. It is clear to show.
[0235]
Example 2
<< Preparation of antireflection film 11 >>
In the production of the anti-reflection film 3 of Example 1, the anti-reflection film was formed in the same manner except that a medium refractive index layer, a high refractive index layer, and then the low refractive index layer were provided on the hard coat layer as described below. 11 was produced.
[0236]
(Preparation of middle refractive index layer)
The following medium refractive index layer composition M-1 was applied on the hard coat layer of the antireflection film 3 with a die coater, and dried at 80 ° C. and 0.1 m / sec for 1 minute. After drying, ultraviolet light was applied using a high-pressure mercury lamp (80 W) to 130 mJ / cm.²Irradiated and cured to form a medium refractive index layer.
[0237]
Medium refractive index layer thickness: 86 nm
Refractive index of medium refractive index layer: 1.64
(Medium refractive index layer composition (M-1))
45 parts by mass of tetra (n) butoxytitanium
γ-methacryloxypropyltrimethoxysilane
(Shin-Etsu Chemical, KBM503) 39 parts by mass
Acrylic resin (Dianal BR102,
15 parts by mass (Mitsubishi Rayon Co., Ltd.)
Linear dimethyl silicone-EO block copolymer
(Nippon Unicar FZ-2207) 1 part by mass
Propylene glycol monomethyl ether 1470 parts by mass
2940 parts by mass of isopropyl alcohol
490 parts by mass of methyl ethyl ketone
(Production of high refractive index layer)
Next, the following high refractive index layer composition H-3 was applied on the middle refractive index layer with a die coater, and dried at 80 ° C. and 0.1 m / sec for 1 minute. After drying, ultraviolet light was applied using a high-pressure mercury lamp (80 W) to 130 mJ / cm.²Irradiation and heat treatment were performed at 120 ° C. for 5 minutes to form a high refractive index layer.
[0238]
Thickness of high refractive index layer: 80 nm
Refractive index of high refractive index layer: 1.87
(High refractive index layer composition H-3)
89 parts by mass of tetra (n) butoxytitanium
γ-methacryloxypropyltrimethoxysilane
(KBM503 Shin-Etsu Chemical Co., Ltd.) 5 parts by mass
Acrylic resin (Dianal BR102,
Mitsubishi Rayon Co., Ltd.) 5 parts by mass
Linear dimethyl silicone-EO block copolymer
(FZ2207, manufactured by Nippon Unicar) 1 part by mass
Propylene glycol monomethyl ether 1470 parts by mass
2940 parts by mass of isopropyl alcohol
490 parts by mass of methyl ethyl ketone
<< Preparation of low refractive index layer >>
Next, the low refractive index layer composition L-1 was applied on the high refractive index layer using a die coater, and dried at 80 ° C. and 0.1 m / sec for 1 minute. After drying, ultraviolet light was applied using a high-pressure mercury lamp (80 W) to 130 mJ / cm.²Irradiation and curing were performed to form a low-refractive-index layer, followed by heat curing at 120 ° C. for 5 minutes to produce an antireflection film 11 having a low-refractive-index layer.
[0239]
Thickness of low refractive index layer: 100 nm
Refractive index of low refractive index layer: 1.44
<< Preparation of antireflection film 12 >>
An anti-reflection film 12 was produced in the same manner as in the production of the anti-reflection film 11, except that the following low-refractive index layer composition (L-3) was used for producing the low-refractive index layer.
[0240]
<Preparation of hydrolyzate B>
14 g of trifluoropropyltrimethoxysilane (KBM7103, manufactured by Shin-Etsu Chemical Co., Ltd.) and 78 g of ethanol were mixed, and 7.5 g of a 4.0% by mass aqueous solution of acetic acid was added thereto, followed by stirring at 25 ° C. for 20 hours. A trifluoropropyltrimethoxysilane hydrolyzate B was prepared.
[0241]
<< Low refractive index layer composition (L-3) >>
520 parts by mass of tetraethoxysilane hydrolyzate A
Trifluoropropyltrimethoxysilane hydrolyzate B 50 parts by mass
γ-methacryloxypropyltrimethoxysilane
(KBM503, manufactured by Shin-Etsu Chemical Co., Ltd.) 6 parts by mass
Linear dimethyl silicone-EO block copolymer
(Nippon Unicar: FZ-2207) 10% propylene
Glycol monomethyl ether solution 50 parts by mass
Propylene glycol monomethyl ether 1200 parts by mass
1200 parts by mass of isopropyl alcohol
Thickness of low refractive index layer: 100 nm
Refractive index of low refractive index layer: 1.43
The content of elemental fluorine in the low refractive index layer is 5%.
[0242]
<< Preparation of antireflection film 13 >>
In the production of the antireflection film 11, an antireflection film 13 was produced in the same manner except that a medium refractive index layer, a high refractive index layer, and then a low refractive index layer were provided on the hard coat layer as described below.
[0243]
(Medium refractive index layer)
The following medium refractive index layer composition M-2 was applied on the hard coat layer using a die coater, and dried at 80 ° C. and 0.1 m / sec for 1 minute. After drying, ultraviolet light was applied using a high-pressure mercury lamp (80 W) to 130 mJ / cm.²Irradiated and cured to form a medium refractive index layer.
[0244]
(Medium refractive index layer composition M-2)
Titanium oxide fine particle dispersion with solid content of 15%
RTSPNB15WT% -G0) 270 parts by mass
Di-i-propoxy bis (acetylacetonato) titanium
(Orgatics TC100: manufactured by Matsumoto Pharmaceutical Company Limited) 5 parts by mass
Dipentaerythritol hexaacrylate
(KAYARAD DPHA: Nippon Kayaku Co., Ltd.) 40 parts by mass
Irgacure 184 10 parts by mass
Linear dimethyl silicone-EO block copolymer
(FZ-2207, manufactured by Nippon Unicar) 1 part by mass
Propylene glycol monomethyl ether 1470 parts by mass
2,720 parts by mass of isopropyl alcohol
490 parts by mass of methyl ethyl ketone
Medium refractive index layer thickness: 86 nm
Refractive index of medium refractive index layer: 1.64
(Production of high refractive index layer)
Next, the following high refractive index layer composition H-4 was applied on the middle refractive index layer with a die coater, and dried at 80 ° C. and 0.1 m / sec for 1 minute. After drying, ultraviolet light was applied using a high-pressure mercury lamp (80 W) to 130 mJ / cm.²Irradiation and heat treatment were performed at 100 ° C. for 1 minute to form a high refractive index layer.
[0245]
(High refractive index layer composition H-4)
Titanium oxide fine particle dispersion (solid content: 15%, manufactured by CI Kasei Kogyo Co., Ltd.
RTSPNB15WT% -G0) 530 parts by mass
Tetra (n) butoxytitanium 10 parts by mass
γ-methacryloxypropyltrimethoxysilane
(KBM503 Shin-Etsu Chemical Co., Ltd.) 10 parts by mass
Linear dimethyl silicone-EO block copolymer
(FZ-2207 manufactured by Nippon Unicar) 1 part by mass
Propylene glycol monomethyl ether 1470 parts by mass
2490 parts by mass of isopropyl alcohol
490 parts by mass of methyl ethyl ketone
Thickness of high refractive index layer: 80 nm
Refractive index of high refractive index layer: 1.85
Next, after forming a low-refractive-index layer using the low-refractive-index layer composition (L-2) used for producing the anti-reflective film 12, an aging treatment is performed at 65 ° C. for 120 hours, and the anti-reflective film 13 is formed. Got.
[0246]
<< Preparation of antireflection film 14 >>
An antireflection film 14 was produced in the same manner as in the production of the antireflection film 13 except that the following low refractive index composition (L-3) was used for producing the low refractive index layer.
[0247]
Thickness of low refractive index layer: 100 nm
Refractive index of low refractive index layer: 1.43
The content of elemental fluorine in the low refractive index layer is 5%.
[0248]
<< Preparation of antireflection film 15 >>
An antireflection film 15 was produced in the same manner as in the production of the antireflection film 13 except that a low refractive index layer was produced using the following low refractive index composition (L-4).
[0249]
(Preparation of hydrolyzate C)
5 g of heptadecatrifluorodecyltrimethoxysilane (KBM7803, manufactured by Shin-Etsu Chemical Co., Ltd.) and 80 g of ethanol were mixed, and 12 g of a 2.5% by mass aqueous solution of acetic acid was added thereto, followed by stirring at 25 ° C. for 20 hours. Heptadecatrifluorodecyltrimethoxysilane hydrolyzate C (also simply referred to as hydrolyzate C) was prepared.
[0250]
(Preparation of low refractive index layer composition (L-4))
720 parts by mass of tetraethoxysilane hydrolyzate A
Heptadecatrifluorodecyl-
140 parts by mass of trimethoxysilane hydrolyzate C
γ-methacryloxypropyltrimethoxysilane
(KBM503, manufactured by Shin-Etsu Chemical Co., Ltd.) 9 parts by mass
Linear dimethyl silicone-EO block copolymer
(Manufactured by Nippon Unicar, FZ-2207)
10% propylene glycol monomethyl ether solution 7 parts by mass
1760 parts by mass of propylene glycol monomethyl ether
1760 parts by mass of isopropyl alcohol
Thickness of low refractive index layer: 100 nm
Refractive index of low refractive index layer: 1.42
The content of elemental fluorine in the low refractive index layer is 25%.
[0251]
<< Preparation of antireflection film 16 >>
An anti-reflection film 16 was produced in the same manner as in the production of the anti-reflection film 13 except that a low-refractive index layer was produced using the following low-refractive index composition (L-5).
[0252]
(Preparation of low refractive index layer composition (L-5))
560 parts by mass of tetraethoxysilane hydrolyzate A
Heptadecatrifluorodecyl-
420 parts by mass of trimethoxysilane hydrolyzate C
γ-methacryloxypropyltrimethoxysilane
(KBM503, manufactured by Shin-Etsu Chemical Co., Ltd.) 9 parts by mass
Linear dimethyl silicone-EO block copolymer
(FZ-2207 manufactured by Nippon Unicar)
10% propylene glycol monomethyl ether solution 7 parts by mass
Propylene glycol monomethyl ether 1700 parts by mass
1,700 parts by mass of isopropyl alcohol
Thickness of low refractive index layer: 100 nm
Refractive index of low refractive index layer: 1.41
The content of the fluorine element in the low refractive index layer is 45%.
[0253]
Measure physical properties (thickness, refractive index, nanoindentation hardness (H), elastic modulus (Er)), layer formation method, F content (fluorine atom content), etc. of constituent layers of antireflection films 11 to 16 Further, each antireflection film was subjected to a heat treatment at 90 ° C. for 72 hours, the nanoindentation elasticity Er (Gpa) was measured, and the change (ΔEr) before and after the heat treatment was determined. Table 4 shows the obtained results.
[0254]
[Table 4]

[0255]
Next, the obtained antireflection films 11 to 16 were evaluated in the same manner as in Example 1. However, the following evaluation was separately performed for the thermal crack.
[0256]
《Heat crack》
After heat treatment of the antireflection film at 100 ° C. (put in a constant temperature bath at 100 ° C. and hold for 400 hours), a black tape is stuck on the back of the antireflection treated surface, and the antireflection treated surface is microscope (20 × objective lens, eyepiece) (× 10) and the occurrence of cracks was confirmed.
[0257]
Further, after the anti-reflection film was heat-treated at 120 ° C. (put in a thermostat at 120 ° C. and held for 24 hours), a black tape was stuck on the back of the anti-reflection treatment surface, and the anti-reflection treatment surface was microscope (20 × objective lens, Observation was performed with an eyepiece (10 times), and the occurrence of cracks was evaluated.
[0258]
◎: No crack generation even at 120 ° C. heat treatment
：: No cracks at 100 ° C heat treatment
Δ: Weak and short cracks occur
×: Long cracks occur
In the present invention, ○ and ◎ are practical.
[0259]
Table 5 shows the obtained evaluation results.
[0260]
[Table 5]

[0261]
From Table 5, as compared with the comparison, the antireflection film of the present invention has excellent properties in all items of flatness, handleability, scratch resistance, pencil hardness, heat crack, antifouling property, and solvent resistance. It is clear to show.
[0262]
Example 3
<< Preparation of Polarizing Plates 1 to 10 >>
Iodine is adsorbed on the stretched polyvinyl alcohol film to prepare a polarizing film, and the antireflection films 1 to 6 of the present invention of Example 1 and the antireflection films 7 to 10 of the comparative example are prepared using a polyvinyl alcohol-based adhesive. Each was attached to one side of the polarizing film. On the other side, a commercially available cellulose triacetate film (Konica Cat KC8UX2MW, manufactured by Konica Corp.) was saponified, and bonded to the opposite side of the polarizing film using a polyvinyl alcohol-based adhesive. To 10 were produced.
[0263]
When the visibility evaluation (visual evaluation) of the obtained polarizing plates 1 to 10 was performed, the antireflection film of the present invention was compared with the polarizing plates 7 to 10 produced using the comparative antireflection films 7 to 10, respectively. The polarizing plates 1 to 6 of the present invention produced using each of Nos. 1 to 6 have high visibility, are free from failure (failure such as entrapment of bubbles or foreign matter), and can be cut even for a large screen. The yield was high.
[0264]
[Table 6]

[0265]
Example 4
<< Preparation of liquid crystal panels 1-10 >>
A liquid crystal panel for performing a viewing angle measurement was manufactured as described below, and characteristics as a liquid crystal display device were evaluated.
[0266]
The polarizing plates on both sides of the Fujitsu 15-type display VL-150SD, which had been bonded in advance, were peeled off, and the polarizing plates 1 to 6 of the present invention and the comparative polarizing plates 7 to 10 prepared above were respectively attached to the glass surface of the liquid crystal cell. A bonded product was produced.
[0267]
At that time, the polarizing plate was bonded in such a manner that the surface of a commercially available cellulose triacetate film (Konica Cat KC8UX2MW, manufactured by Konica Corporation) was on the liquid crystal cell side, and that the polarizing plate was bonded in advance. The liquid crystal panels 1 to 10 were produced so that the absorption axis was directed in the same direction as the plate.
[0268]
The visibility of the obtained liquid crystal panels 1 to 10 was evaluated as described below. As compared with the comparison, the liquid crystal panels of the present invention were all 〜 to ◎ and excellent in visibility. I understood.
[0269]
《Visibility evaluation》
The liquid crystal panel (liquid crystal display device) was visually observed, and the visibility in the oblique direction was evaluated as follows.
[0270]
：: Black appears dark and sharp, and no white spots on the image are observed
：: Black appears and is clear, but slight white spots are observed in the image
Δ: There is no blackening, the sharpness is slightly low, and white spots on the image are observed.
×: no blackness, low sharpness, worried about white spots on the image
In the present invention, ○ and ◎ are practical.
[0271]
【The invention's effect】
According to the present invention, in all items of flatness, handleability, scratch resistance, pencil hardness, heat crack, antifouling property, and solvent resistance, an antireflection film showing excellent properties, polarized light using the antireflection film A board and a display device can be provided.

Claims (10)

On at least one surface of the support, a hard coat layer of 1 μm to 20 μm, a high refractive index layer showing a refractive index higher than the refractive index of the hard coat layer, and a refractive index lower than the refractive index of the hard coat layer In the antireflection film having the low refractive index layer shown in this order,
The high refractive index layer and the low refractive index layer are each formed by wet coating, the surface of the outermost layer has a nanoindentation hardness (H) of 2 GPa to 4 GPa, and a nanoindentation elastic modulus (Er). An antireflection film having a pressure of 10 GPa to 30 GPa. The nanoindentation hardness (H) of the hard coat layer is 0.8 GPa to 2.0 GPa, and the nanoindentation elastic modulus (Er) is 6 GPa to 15 GPa. Anti-reflection film. A middle refractive index layer having a refractive index between the hard coat layer and the high refractive index layer between the hard coat layer and the high refractive index layer, wherein the middle refractive index layer is formed by wet coating; The antireflection film according to claim 1, wherein the antireflection film is formed. The outermost surface layer forms an optical interference layer, and the amount of change (ΔH) in nanoindentation hardness (H) of the outermost surface layer before and after a heat resistance test at 90 ° C. for 72 hours is 0.3 GPa or less. The anti-reflection film according to claim 1, wherein: The antireflection film according to any one of claims 1 to 4, wherein the outermost surface layer is a low refractive index layer. The nanoindentation hardness (H) of the surface of the low refractive index layer is 3 GPa to 4 GPa, and the nanoindentation elastic modulus (Er) is 15 GPa to 30 GPa. 2. The antireflection film according to claim 1. The anti-reflection film according to claim 6, wherein the low refractive index layer contains a fluorine element in a range of 1 atomic% to 40 atomic% on the surface, near the surface, and inside the layer. The antireflection film according to claim 6, wherein the low refractive index layer contains a fluorine element in a range of 5 atomic% to 30 atomic% on the surface, near the surface, and inside the layer. A polarizing plate comprising the antireflection film according to claim 1. A display device comprising the anti-reflection film according to claim 1 or the polarizing plate according to claim 9.