JP4271922B2 - Antiglare antireflection film, polarizing plate, liquid crystal display device using the same, and method for producing antiglare antireflection film - Google Patents

Description

【０１１６】
＜防眩性反射防止フイルムの評価＞
得られた防眩性反射防止フイルムについて、以下の項目の評価を行った。結果を表２に示した。
【０１１７】
（１）表面粗さ （Ｒａ、Ｒｚ）
表面粗さは原子間力顕微鏡（ＡＦＭ：Ａｔｏｍｉｃ Ｆｏｒｃｅ Ｍｉｃｒｏｓｃｏｐｅ、ＳＰＩ３８００Ｎ、セイコーインスツルメント（株）製）にてＲａ、Ｒｚを測定し、Ｒｚ／Ｒａを計算した。
【０１１８】
（２）鏡面反射率
分光光度計Ｖ−５５０（日本分光（株）製）にアダプターＡＲＶ−４７４を装着して、３８０〜７８０ｎｍの波長領域において、入射角５°における出射角−５度の鏡面反射率を測定し、４５０〜６５０ｎｍの平均反射率を算出し、反射防止性を評価した。
（３）積分反射率
分光光度計Ｖ−５５０（日本分光（株）製）にアダプターＩＬＶ−４７１を装着して、３８０〜７８０ｎｍの波長領域において、入射角５°における積分反射率を測定し、４５０〜６５０ｎｍの平均反射率を算出した。
【０１１９】
（４）ヘイズ値
得られたフィルムのヘイズをヘイズメーターＭＯＤＥＬ １００１ＤＰ（日本電色工業（株）製）を用いて測定した。内部ヘイズは、防眩性層までを形成したフィルムに、該防眩性層に含まれるバインダ成分のみをオーバーコートして、表面粗さＲａが０．０１未満になったものについて測定されたヘイズ値である。表面ヘイズは、低屈折率層までを形成したフィルムのヘイズ値から、前記内部ヘイズ値を引いて算出した。
【０１２０】
（５）ブツ状故障
各フイルムの塗布層を設けた面の反対面（支持体面）を黒色インキで黒塗りし、塗布面側を上にして目視、光学顕微鏡（倍率：５０倍）による面状検査を行い、１平方メートルあたりの目視可能なぶつ状故障の内の樹脂粒子起因のもの（光学顕微鏡により確認）の数をカウントした。
【０１２１】
【表２】

【０１２２】
＜視認側偏光板の作製＞
延伸したポリビニルアルコールフイルムにヨウ素を吸着させて偏光膜を作製した。
作製した防眩性反射防止フイルム（Ａ−０１）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、防眩性反射防止フイルム（Ａ−０１）の透明支持体（トリアセチルセルロース）が偏光膜側となるように偏光膜の片側に貼り付けた。また、下記の光学補償フイルム（ＫＨ−０１）をセルロースアセテートフイルムが偏光膜側になるように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り付けた。偏光膜の透過軸と光学補償フイルム（ＫＨ−０１）の遅相軸とは平行になるように配置した。このようにして防眩性反射防止性偏光板（ＢＨＨＡ−０１）を作製した。
【０１２３】
＜光学補償フィルム（ＫＨ−０１）の作製＞
（セルロースアセテートドープ液の調製）
下記の組成物をミキシングタンクに投入し、加熱しながら攪拌して、各成分を溶解し、セルロースアセテートドープ溶液（ＣＡ）を調製した。
【０１２４】
｛セルロースアセテート溶液（ＣＡ）の組成｝
酢化度６０．９％のセルロースアセテート １００質量部
トリフェニルホスフェート（可塑剤） ８質量部
ビフェニルジフェニルホスフェート（可塑剤） ４質量部
メチレンクロライド（第１溶媒） ３００質量部
メタノール（第２溶媒） ５４質量部
１−ブタノール（第３溶媒） １１質量部
【０１２５】
（レターデーション上昇剤溶液の調製）
下記の組成物を別のミキシングタンクに投入し、加熱しながら攪拌して、各成分を溶解し、レターデーション上昇剤溶液（ＲＪ）を調製した。
【０１２６】
｛レターデーション上昇剤溶液（ＲＪ）の処方｝
下記のレターデーション上昇剤（スミソルブＴＭ１６５−Ｆ、住友化学製） ２５質量部
メチレンクロライド（第１溶媒） ８０質量部
メタノール（第２溶媒） ２０質量部
【０１２７】
【化１】

【０１２８】
（セルロースアセテートドープの作製）
下記の組成物をミキシングタンクに投入、攪拌して、ドープ（ＣＡＤ）を調製した。
【０１２９】
｛セルロースアセテートドープ（ＣＡＤ）処方｝
セルロースアセテート溶液（ＣＡ） ４８７質量部
レターデーション上昇剤溶液（ＲＪ） １５質量部
【０１３０】
レターデーション上昇剤の添加量は、セルロースアセテート１００質量部に対して、３．０質量部であった。
【０１３１】
（セルロースアセテートフイルムの作製）
得られたドープ（ＣＡＤ）を、バンド流延機を用いて流延した。バンド上での膜面温度が４０℃となってから、１分乾燥し、剥ぎ取った後、１４０℃の乾燥風で、残留溶剤量が０．３質量％のセルロースアセテートフイルム（厚さ：６０μｍ）を作製した。
作製したセルロースアセテートフイルム（ＣＡＦ−０１）について、光学特性を測定した結果、Ｒｅレターデーション値は５ｎｍ、Ｒthレターデーション値は８０ｎｍであった。
尚、光学特性は、エリプソメーター（Ｍ−１５０、日本分光（株）製）を用いて、波長５５０ｎｍにおけるＲｅレターデーション値およびＲthレターデーション値を測定した。
【０１３２】
作製したセルロースアセテートフイルム（ＣＡＦ−０１）を１．５Ｎの水酸化カリウム／（水／ＩＰＡ／ＰＧ＝１４／８６／１５ｖｏｌ％）を５ｃｃ／ｍ²塗布し、約１０秒間６０℃に保持した後、フイルム表面に残った水酸化カリウムを水洗し、乾燥した。このセルロースアセテートフイルムの表面エネルギーを接触角法により求めたところ、６３ｍＮ／ｍであった。
このセルロースアセテートフイルム上に、下記の組成の配向膜塗布液（ＨＭ）を＃１６のワイヤーバーコーターで２８ｍｌ／ｍ²塗布した。６０℃の温風で６０秒、さらに９０℃の温風で１５０秒乾燥した。
次に、セルロースアセテートフイルムの長手方向と平行な方向に、形成した膜にラビング処理を実施した。
【０１３３】
（配向膜塗布液の調製）
下記の組成物をミキシングタンクに投入し、加熱しながら攪拌して、各成分を溶解し、配向膜塗布液（ＨＭ）を調製した。
【０１３４】
｛配向膜塗布液（ＨＭ）の処方｝
下記の変性ポリビニルアルコール １０質量部
水 ３７１質量部
メタノール １１９質量部
グルタルアルデヒド（架橋剤） ０．５質量部
【０１３５】
【化２】

【０１３６】
（光学異方性層の形成）
ＳＵＳ製のタンク中に下記処方の化合物を投入溶解して光学異方性層塗布液を得た。
【０１３７】
｛光学異方性層塗布液処方｝
下記ディスコティック液晶性分子 ４２００質量部
エチレンオキサイド変成トリメチロールプロパントリアクリレート
（Ｖ＃３６０、大阪有機化学（株）製）） ４００質量部
セルロースアセテートブチレート
（ＣＡＢ５５１−０．２、イーストマンケミカル社製） ９２質量部
セルロースアセテートブチレート
（ＣＡＢ５３１−１、イーストマンケミカル社製） ２３質量部
光重合開始剤（イルガキュア−９０７、チバガイギー社製）１４０質量部
増感剤（カヤキュア−ＤＥＴＸ、日本化薬（株）製） ４５質量部
メチルエチルケトン １０１００質量部
【０１３８】
【化３】

【０１３９】
上記で形成された配向膜上に、上記光学異方性層塗布液を＃３．６のワイヤーバーで塗布した。これを１３０℃の恒温ゾーンで２分間加熱し、円盤状化合物を配向させた。次に、６０℃の雰囲気下で１２０Ｗ／ｃｍ高圧水銀灯を用いて、１分間ＵＶ照射し円盤状化合物を重合させた。その後、室温まで放冷した。このようにして、光学異方性層を形成し、光学補償フイルム（ＫＨ−０１）を作製した。
波長５５０ｎｍで測定した光学異方性層のＲｅレターデーション値は４３ｎｍであった。また、円盤面と第１透明支持体面との間の角度（傾斜角）は平均で４２゜であった。
【０１４０】
防眩性反射防止性偏光板（ＢＨＨＡ−０１）を作製したのと同様に、防眩性反射防止フイルム（Ａ−０２）〜（Ａ−０８）を用いて防眩性反射防止性偏光板（ＢＨＨＡ−０２）〜（ＢＨＨＡ−０８）を作製した。
【０１４１】
＜バックライト側偏光板の作製＞
延伸したポリビニルアルコールフイルムにヨウ素を吸着させて偏光膜を作製した。市販のトリアセチルセルロースフイルム（富士写真フイルム製、フジタックＴＤ８０）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、偏光膜の片側に貼り付けた。また、光学補償フイルム（ＫＨ−０１）にケン化処理を行い、ポリビニルアルコール系接着剤を用いて、セルロースアセテートフイルムが偏光膜側となるように反対側に貼り付けた。このようにしてバックライト側偏光板を作製した。
【０１４２】
＜液晶表示装置の作製＞
ＴＮ型液晶セルを使用した液晶表示装置（６Ｅ−Ａ３、シャープ（株）製）に設けられている一対の偏光板を剥がし、代わりに偏光板（ＢＨＨＡ−０１）〜（ＢＨＨＡ−０８）を、それぞれ光学補償フイルムが液晶セル側となるように粘着剤を介して、観察者側に貼り付けた。またバックライト側には、光学補償フイルムが液晶セル側となるように粘着剤を介してバックライト側偏光板を貼り付けた。観察者側の偏光板の透過軸と、バックライト側の偏光板の透過軸とは、Ｏモードとなるように配置した。
【０１４３】
＜液晶表示装置の評価＞
作製した液晶表示装置について、以下の項目の評価を行った。結果を表３に示した。
【０１４４】
（６）視野角
測定機（ＥＺ−Contrast１６０Ｄ、ＥＬＤＩＭ社製）を用いて、黒表示（Ｌ１）から白表示（Ｌ８）までの８段階で視野角を測定した。
視野角はコントラスト比が１０以上で階調反転のない範囲を求めた。黒側の階調反転はＬ１とＬ２との間の反転で判定した。
【０１４５】
（７）防眩性評価
ルーバーなしのむき出し蛍光灯（８０００ｃｄ／ｍ²）を映し、その反射像のボケの程度を以下の基準で評価した。
蛍光灯の輪郭が全くわからない ：◎
蛍光灯の輪郭がわずかにわかる ：○
蛍光灯がほとんどぼけない ：×
【０１４６】
【表３】

【０１４７】
表１〜表３に示された結果から以下のことが分かった。
本発明の防眩性反射防止フイルムは、ブツ状故障が極めて少なく、その防眩性反射防止フイルムを用いた偏光板を使用した表示装置の視野特性、外光の写りこみにくさ（防眩性）に非常に優れていることが確認できた。一方、比較例１０１の防眩性反射防止フイルムはブツ状故障はないものの白粉汚れが発生しており、防眩性反射防止フイルムとして使用することは不適であることが分かった。また、比較例１１１に示したその防眩性反射防止フイルムを用いた偏光板を使用した表示装置の視野特性、外光の写りこみにくさ（防眩性）が本発明よりも劣っていることが確認された。
【０１４８】
実施例２
＜防眩性層用塗布液の調製＞
防眩性層塗布液（ＢＧ−２）を、下記処方で仕込み、攪拌し調製した。
【０１４９】
｛防眩性層塗布液（ＢＧ−２）処方｝
デソライトＫＺ−７１１４Ａ、（ＪＳＲ（株）製、酸化ジルコニウム分散物含
有ハードコート塗布液（透光性樹脂）） １００質量部
ＤＰＨＡ、（日本化薬（株）製、ジペンタエリスリトールヘキサアクリレート
（透光性樹脂）） ５７質量部
ＭＸ１５０（綜研化学製、粒径１．５μｍ、屈折率１．４９、ポリメチルメタク
リレート系ビーズ（透光性微粒子）） １７質量部
ＭＸ３００（綜研化学製、粒径３．０μｍ、屈折率１．４９、ポリメチルメタク
リレート系ビーズ（透光性微粒子）） ７質量部
ＫＢＭ−５１０３（信越化学（株）製、屈折率１．４２、γ―アクリロキシプロ
ピルトリメトキシシラン） １質量部
メチルエチルケトン ３６質量部
メチルイソブチルケトン １４６質量部
【０１５０】
＜防眩性層の塗設、光拡散フイルムの作製＞
トリアセチルセルロースフイルム（富士写真フイルム（株）製、ＴＤ−８０Ｕ）上に、１．５μｍポリメチルメタクリレート系ビーズの塗布量が０．４ｇ／ｍ²になるように上記防眩性塗布液（ＢＧ−２）を塗工、溶剤乾燥後、１８０Ｗ／ｃｍの空冷メタルハライドランプ（アイグラフィックス（株）製）を用いて、照度５００ｍＷ／ｃｍ²、照射量５００ｍＪ／ｃｍ²の紫外線を照射して塗布層を硬化させ光拡散フイルム（Ｂ−０１）を作製した。このフイルムの防眩性層の乾燥膜厚は３．０μｍであった。透光性微粒子を含まない液を塗布、紫外線硬化して得られた塗膜の屈折率は１．６１であった。
【０１５１】
光拡散フイルム（Ｂ−０１）の防眩性層上に、上記低屈折率層用塗布液（ＴＫ−１）をバーコーターを用いて塗布し、８０℃で乾燥の後、さらに１２０℃で１０分間熱架橋し、厚さ０．０９８μｍの低屈折率層を形成し、防眩性反射防止フイルム（Ｂ−０１）を作製した。
【０１５２】
ポリメチルメタクリレート系ビーズの粒径、塗布量を変更し、防眩性層の乾燥膜厚を４．２μｍとなるよう変更し、表５に示す表面凹凸となるように、光拡散フイルム（Ｂ−０２）、（Ｂ−０６）〜（Ｂ−０８）を作製し、さらに防眩性反射防止フイルム（Ｂ−０２）、（Ｂ−０６）〜（Ｂ−０８）を作製した。塗布量は表４に示した。
【０１５３】
１．５μｍポリメチルメタクリレート系ビーズを３μｍシリカビーズ（日本触媒製、屈折率１．４４）に変更し、３．０μｍポリメチルメタクリレート系ビーズの粒径、塗布量を変更し、表５に示す表面凹凸となるように光拡散フイルム（Ｂ−０３）〜（Ｂ−０５）を作製し、さらに防眩性反射防止フイルム（Ｂ−０３）〜（Ｂ−０５）を作製した。塗布量は表４に示した。
【０１５４】
１．５μｍポリメチルメタクリレートビーズを添加せず、３．５μｍポリメチルメタクリレートビーズを架橋ポリスチレンビーズに変更し、防眩性層乾燥膜厚を３．０μｍとし、表５に示す表面凹凸となるように光拡散フイルム（Ｂ−０９）〜（Ｂ−１０）を作製し、さらに防眩性反射防止フイルム（Ｂ−０９）〜（Ｂ−１０）を作製した。塗布量は表４に示した。
【０１５５】
【表４】

【０１５６】
防眩性反射防止性偏光板（ＢＨＨＡ−０１）を作製したのと同様に、防眩性反射防止フイルム（Ｂ−０１）〜（Ｂ−１０）と光学補償フイルム（ＫＨ−０１）を用いて防眩性反射防止性偏光板（ＢＨＨＢ−０１）〜（ＢＨＨＢ−１０）を作製した。
得られた防眩性反射防止フイルム、作製した液晶表示装置について、実施例１と同じ項目について評価を行った。結果を表５、表６に示した。
【０１５７】
【表５】

【０１５８】
【表６】

【０１５９】
表４〜表６に示された結果から以下のことが分かった。
本発明の防眩性反射防止フイルムは、ブツ状故障が極めて少なく、その防眩性反射防止フイルムを用いた偏光板を使用した表示装置の視野特性、外光の写りこみにくさ（防眩性）に非常に優れていることが確認できた。一方、比較例２０１の防眩性反射防止フイルムはＲａ値、Ｒｚ／Ｒａ値が本発明の範囲を外れており、ブツ状故障が多数発生し、防眩性反射防止フイルムとして使用することは不適であった。また、比較例２０２の防眩性反射防止フイルムはブツ状故障はないものの白粉汚れが発生しており、防眩性反射防止フイルムとして使用することは不適であることが分かった。比較例２１１、２１２に示したその防眩性反射防止フイルムを用いた偏光板を使用した表示装置の視野特性、外光の写りこみにくさ（防眩性）が本発明よりも劣っていることが確認された。
【０１６０】
実施例３
＜防眩性層用塗布液の調製＞
防眩性層塗布液（ＢＧ−３）を下記処方で仕込み、攪拌し調製した。
【０１６１】
｛防眩性層塗布液（ＢＧ−３）処方｝
トリメチロールプロパントリアクリレート（透光性樹脂）） １００質量部
ＳＸ３５０Ｈ（綜研化学製、粒径３．０μｍ、屈折率１．６１、架橋ポリスチレ
ンビーズ（透光性微粒子）） １０質量部
ＳＸ５００Ｈ（綜研化学製、粒径５．０μｍ、屈折率１．６１、架橋ポリスチレ
ンビーズ（透光性微粒子）） １０質量部
ＫＢＭ−５１０３（信越化学（株）製、屈折率１．４２、γ―アクリロキシプロ
ピルトリメトキシシラン） １質量部
メチルエチルケトン ２４質量部
メチルイソブチルケトン ９６質量部
【０１６２】
＜防眩性層の塗設、光拡散フイルムの作製＞
トリアセチルセルロースフイルム（富士写真フイルム（株）製、ＴＤ−８０Ｕ）上に、３．５μｍ架橋ポリスチレンビーズの塗布量が０．４ｇ／ｍ²になるように上記防眩性層塗布液（ＢＧ−３）を塗工、溶剤乾燥後、１８０Ｗ／ｃｍの空冷メタルハライドランプ（アイグラフィックス（株）製）を用いて、照度５００ｍＷ／ｃｍ²、照射量５００ｍＪ／ｃｍ²の紫外線を照射して塗布層を硬化させ光拡散フイルム（Ｃ−０１）を作製した。このフイルムの防眩性層の乾燥膜厚は４．２μｍであった。透光性バインダーマトリックスの屈折率は１．５２であった。
【０１６３】
光拡散フイルム（Ｃ−０１）の防眩性層上に、上記低屈折率層用塗布液（ＴＫ−１）をバーコーターを用いて塗布し、８０℃で乾燥の後、さらに１２０℃で１０分間熱架橋し、厚さ０．０９８μｍの低屈折率層を形成し、防眩性反射防止フイルム（Ｃ−０１）を作製した。
【０１６４】
架橋ポリスチレンビーズの塗布量を変更し、表８に示す表面凹凸となるように、光拡散フイルム（Ｃ−０２）〜（Ｃ−０３）を作製し、さらに防眩性反射防止フイルム（Ｃ−０２）〜（Ｃ−０３）を作製した。塗布量は表７に示した。
【０１６５】
３．５μｍ架橋ポリスチレンビーズを３μｍシリカビーズ（屈折率１．４４）に変更し、塗布量を変更し、表８に示す表面凹凸となるように、光拡散フイルム（Ｃ−０４）を作製し、さらに防眩性反射防止フイルム（Ｃ−０４）を作製した。塗布量は表７に示した。
【０１６６】
３．５μｍ架橋ポリスチレンビーズを添加せず、５μｍ架橋ポリスチレンビーズをＰＭＭＡビーズ（屈折率１．４９）に変更し、表８に示す表面凹凸となるように光拡散フイルム（Ｃ−０５）を作製し、さらに防眩性反射防止フイルム（Ｃ−０５）を作製した。塗布量は表７に示した。
【０１６７】
【表７】

【０１６８】
防眩性反射防止性偏光板（ＢＨＨＡ−０１）を作製したのと同様に、防眩性反射防止フイルム（Ｃ−０１）〜（Ｃ−０５）と光学補償フイルム（ＫＨ−０１）を用いて防眩性反射防止性偏光板（ＢＨＨＣ−０１）〜（ＢＨＨＣ−０５）を作製した。
得られた防眩性反射防止フイルム、作製した液晶表示装置について、実施例１と同じ項目について評価を行った。結果を表８、表９に示した。
【０１６９】
【表８】

【０１７０】
【表９】

【０１７１】
表７〜表９に示された結果から以下のことが分かった。
本発明の防眩性反射防止フイルムは、ブツ状故障が極めて少なく、その防眩性反射防止フイルムを用いた偏光板を使用した表示装置の視野特性、外光の写りこみにくさ（防眩性）に非常に優れていることが確認できた。
【０１７２】
以上示した実施例から、Ｒａが０．０２〜１．０μｍの間にあり、Ｒｚ／Ｒａが３０以下の防眩性反射防止フイルムを設置した液晶表示装置は優れた視野角特性、防眩性を有することが確認された。
【０１７３】
【発明の効果】
本発明によれば、本発明の防眩性反射防止フィルムに、更に偏光子、および液晶性化合物からなる光学異方性層を設けることにより、視野角（特に下方向視野角）を拡大し、視角変化によるコントラスト低下、階調または黒白反転、および色相変化等がほとんど発生することがなく、しかも安価で、ブツ状の面状欠陥のない液晶表示装置を提供することができる。すなわち、液晶表示装置の品位、更には面状均一性にも優れた性能を付与できる防眩性反射防止フィルム、更には偏光板を得ることができる。
更に、上記性能に優れた偏光板を備えた液晶表示装置、画像表示装置を提供することができる。
【図面の簡単な説明】
【図１】防眩性反射防止フイルムの基本構成を示す断面模式図である。
【符号の説明】
１ 防眩性反射防止フイルム
２ 透明支持体
３ 防眩性層
４ 低屈折率層
５ 透光性微粒子（防眩性粒子）
６ 透光性微粒子（散乱粒子）[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a liquid crystal display element and an image display element used for image display such as a computer, a word processor, a plasma display, an organic EL display, and a television, and more particularly, an antiglare reflection having an antiglare layer for improving viewing angle characteristics. The present invention relates to various functional films such as a protective film, a polarizing plate protective film, a retardation film, and a viewing angle widening film, a polarizing plate using them, a liquid crystal display device, and an image display device.
[0002]
[Prior art]
The liquid crystal display device is composed of a polarizing plate and a liquid crystal cell.
At present, the problems in the display quality of the liquid crystal display device are an increase in viewing angle, prevention of reflection of external light, and elimination of surface defects.
Regarding the viewing angle, in the TN mode TFT liquid crystal display devices which are currently mainstream, an optical compensation film is inserted between the polarizing plate and the liquid crystal cell as described in Patent Documents 1 to 3, and the liquid crystal display device has a very wide viewing angle. Is realized. However, the liquid crystal display device still has a problem that gradation inversion in the lower direction of the panel occurs.
[0003]
With respect to this problem, Patent Document 4 (Patent No. 2822983) discloses a light diffusion means, Patent Document 5 (Japanese Patent Laid-Open No. 2001-33783) describes an optical axis conversion plate, and Patent Document 6 (Japanese Patent Laid-Open No. 2001-37883). -56461) proposes that the display quality is remarkably improved by providing an optical means for diffusing emitted light on the surface on the viewing side. However, the specific means described in these are light diffusing means having a highly controlled lens structure or diffractive structure, which is expensive and very difficult to mass-produce.
[0004]
On the other hand, as a light diffusing means that can be mass-produced inexpensively, a light diffusing film coated with a translucent resin containing translucent particles, for example, silicon dioxide (silica) or the like on the surface of a transparent support. The thing (for example, refer patent document 7) formed by apply | coating resin containing a filler is proposed. Furthermore, a surface-flattened diffusion film having a surface haze value of 3 or more and a surface roughness (Ra) of 0.2 μm or less (see Patent Document 8), an antiglare film that defines a surface haze value and an internal haze value ( Patent Document 9), antiglare film containing translucent fine particles having a particle size of 0.5 to 5 μm and a refractive index difference of 0.02 to 0.2 with translucent resin (see Patent Document 10) ), An antiglare film (see Patent Documents 11 and 12) containing two or more kinds of translucent fine particles having different particle sizes and refractive index differences from the translucent resin, centerline average roughness (Ra) and 10 An antiglare film (see Patent Document 13) that defines a point average roughness (Rz) is known.
[0005]
[Patent Document 1]
JP-A-8-50206
[Patent Document 2]
Japanese Patent Laid-Open No. 7-191217
[Patent Document 3]
European Patent 0911656A2
[Patent Document 4]
Japanese Patent No. 2822983
[Patent Document 5]
JP 2001-33783 A
[Patent Document 6]
JP 2001-56461 A
[Patent Document 7]
JP-A-6-18706
[Patent Document 8]
JP-A-11-160505
[Patent Document 9]
Japanese Patent Laid-Open No. 11-305010
[Patent Document 10]
JP 11-326608 A
[Patent Document 11]
JP 2000-121809 A
[Patent Document 12]
JP 2000-180611 A
[Patent Document 13]
JP 2000-338310 A
[0006]
[Problems to be solved by the invention]
However, it has been found that the use of the light diffusing layer described in these documents causes image blurring, and the improvement in display quality is insufficient. In addition, when an attempt was made to form a light diffusing layer by the coating described in these, there were lumpy surface defects on the entire surface of the film, and further improvements were desired.
[0007]
On the other hand, as countermeasures against reflection of external light, it is generally used to impart antiglare properties by surface unevenness or to provide antireflection properties by a low refractive index layer. When the light diffusing layer as described above is directly coated on a transparent substrate, it is very difficult to control the surface unevenness, and a film satisfying the antiglare property is not obtained. In addition, the antireflection layer is disposed on the outermost surface of the display that reduces the reflectivity by using the principle of optical interference in order to prevent contrast deterioration and image reflection due to reflection of external light. However, the conventional light diffusing film cannot solve the above-mentioned viewing angle problem, and a light diffusing film that is excellent in external light reflection and can solve the viewing angle problem is desired. It was.
[0008]
An object of the present invention is to provide an optically anisotropic layer comprising an antiglare antireflection film having an antiglare layer and a low refractive index layer, a polarizer (polarizing film), and a liquid crystalline compound on a transparent support. As a result, the viewing angle (especially the downward viewing angle) is expanded, contrast degradation due to changes in viewing angle, gradation or black-and-white reversal, hue change, etc. hardly occur, and it is inexpensive and has a rough surface defect. An object of the present invention is to provide an antiglare antireflection film and a polarizing plate using the same, which can provide a liquid crystal display device free from liquid crystal. That is, it is providing the anti-glare antireflection film and polarizing plate which can provide the performance which was excellent also in the quality of the liquid crystal display device, and also in planar uniformity.
A further object of the present invention is to provide a liquid crystal display device and an image display device provided with a polarizing plate having excellent performance.
[0009]
[Means for Solving the Problems]
  It has been found that the object of the present invention is achieved by a method for producing an antiglare antireflection film, a polarizing plate, a liquid crystal display device, an image display device and an antiglare antireflection film having the following constitution.
(1) Antiglare property having at least one antiglare layer in which translucent fine particles are dispersed in a translucent binder matrix and a low refractive index layer having a lower refractive index than the lower layer on a transparent support. The antireflective film has a refractive index of the translucent binder matrix in the antiglare layer in the range of 1.48 to 2.00, and a difference in refractive index between the translucent binder matrix and the translucent fine particles. Δn is 0.00 to 0.50, the internal haze value due to internal scattering of the antiglare layer is 30 to 80%, and the surface haze value due to surface irregularities of the antiglare layer is 7 to 25%. Yes, the total haze value is 40 to 90%, two or more kinds of translucent fine particles having different particle diameters are used, and at least one kind is transparent for imparting antiglare property having a particle diameter of 1.6 to 12 μm. 0.8 to 2.0 of the thickness of the antiglare layer, which is a light-sensitive fine particle Of a particle size, a is the particle least one confers internal scattering property, and the particle size of particles of particle size smaller than the thickness of the antiglare layer is 1.0～6.0Myuemu,The difference in refractive index between the translucent binder matrix and the translucent fine particles imparting the internal scattering property is 0.05 to 0.50, andAn antiglare antireflection film having a surface roughness Ra of 0.02 to 1.00 μm and an Rz / Ra of 30 or less.
[0011]
(2) In the polarizing plate in which both surfaces of the polarizer are sandwiched between protective films, at least one of the protective films is the above (1)A polarizing plate, which is the antiglare and antireflection film described above.
(3) In the polarizing plate in which both surfaces of the polarizer are sandwiched between protective films, the protective film has an optically anisotropic layer made of a liquid crystalline compound on one side, and the other protective film is the above (1).Or(2)A polarizing plate, which is the antiglare and antireflection film described above.
(4The liquid crystal compound is a discotic compound (above)3).
[0012]
(5) A liquid crystal display device, wherein the optically anisotropic layer side of the polarizing plate according to any one of (2) to (4) is disposed on a liquid crystal cell surface.
(6) The anti-glare antireflection film described in (1) above or the low refractive index layer side of the polarizing plate described in any one of (2) to (4) is disposed so as to be the outermost surface. A characteristic image display device.
(7) Antiglare property having at least one antiglare layer in which translucent fine particles are dispersed in a translucent binder matrix and a low refractive index layer having a lower refractive index than the lower layer on a transparent support. A method for producing an antireflection film, wherein the antiglare antireflection film has a refractive index of a translucent binder matrix in the antiglare layer in the range of 1.48 to 2.00, and the translucent binder The difference in refractive index Δn between the matrix and the light-transmitting fine particles is 0.00 to 0.50, the internal haze value due to internal scattering of the antiglare layer is 30 to 80%, and the antiglare layer has The surface haze value due to surface irregularities is 7 to 25%, the total haze value is 40 to 90%, two or more kinds of translucent fine particles having different particle diameters are used, and at least one kind has a particle size of 1.6 to It is a light-transmitting fine particle for imparting antiglare property of 12 μm And a particle size of 0.8 to 2.0 times the thickness of the antiglare layer, at least one kind of particles imparting internal scattering properties, and a particle size smaller than the thickness of the antiglare layer The particle size is 1.0-6.0 μm,The difference in refractive index between the translucent binder matrix and the translucent fine particles imparting the internal scattering property is 0.05 to 0.50, andThe surface roughness Ra is 0.02 to 1.00 μm, and Rz / Ra is 30 or less, and the coating solution for forming the antiglare layer contains two or more kinds of translucent fine particles having different particle diameters. And a solvent having a boiling point of 100 ° C. or higher contains 1 to 95% of the total solvent in the coating solution for forming the antiglare layer.An antiglare layer-forming coating solution is applied onto a transparent support, heated and dried, and then irradiated or heated to form an antiglare layer. Further, a low refractive index layer is formed on the antiglare layer. Apply a coating solution and irradiate or heat to form a low refractive index layerThe manufacturing method of the anti-glare antireflection film characterized by the above-mentioned.
[0013]
The present invention has found that the irregular defects on the antiglare antireflection film having the antiglare layer and the low reflectance layer are closely related to the local irregularities on the surface and correlate with the Rz / Ra value. After setting the Ra value of the antiglare layer to 0.02 to 1.00 μm and the Rz / Ra value to 30 or less, the low refractive index layer is formed into a uniform thin layer, whereby the Ra value of the film surface, Rz It has been found that a good antiglare antireflection film with few irregularities can be provided without substantially changing the / Ra value. Furthermore, it is possible to obtain a polarizing plate, a liquid crystal display device, and an image display device having excellent performances.
[0014]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, embodiments of the present invention will be described in detail.
One preferred form of the antiglare antireflection film of the present invention is an antiglare layer in which translucent fine particles are dispersed in a translucent binder matrix, and a low refractive index layer having a lower refractive index than the lower layer (that is, the antireflection layer). ) On the transparent support.
[0015]
[Anti-glare anti-reflection film]
As schematically shown in FIG. 1, the anti-glare antireflection film 1 of the present invention has a layer structure of an anti-glare layer 3 and a low refractive index layer 4 on a transparent support 2. . In the antiglare layer 3, antiglare imparting particles 5 that are translucent fine particles, or further, internal scattering imparting particles 6 that are translucent fine particles are dispersed.
In addition, the layer structure of the anti-glare antireflection film of the present invention is not limited to that shown in FIG. 1, and there are of course many variations. For example, a structure in which a smooth hard coat layer is provided under the antiglare layer to increase the film strength is also included.
[0016]
The surface irregularity of the antiglare antireflection film has a centerline average surface roughness (Ra) of 1. when measured at a reference length of 2.5 mm as defined in JIS-B-0601 and a cutoff value of 0.8 mm. 0 μm or less, preferably 0.8 μm or less, more preferably 0.5 μm or less, and particularly preferably 0.2 μm or less. However, if it is less than 0.02 μm, the film transportability deteriorates, which is not preferable. Further, the ratio (Rz / Ra value) of the ten-point average roughness (Rz) and Ra of the antiglare antireflection film surface of the present invention is 30 or less, preferably 25 or less, and preferably 20 or less. More preferably.
[0017]
The center line average roughness Ra is a parameter representing the average roughness of the surface irregularities, and the larger the value, the larger the average roughness of the surface. Rz is a parameter representing the size of local irregularities, and if the ratio of this value to the centerline average roughness (Rz / Ra value) is large, many projections due to locally large bumps exist, and Rz / Ra It has been found that the larger the is, the more planar defects are found when applied as a liquid crystal display device. Furthermore, it has been found that by making Rz / Ra 30 or less, it contributes greatly to uniform thin layer coating of the low refractive index layer.
[0018]
The surface roughness Ra of the string-proof antireflection film is as follows: (1) Addition amount of translucent fine particles imparting antiglare property and internal scattering property, (2) Particle size and thickness of antiglare layer, film Ratio and difference of particle size with respect to thickness, (3) material type of translucent fine particles and surface treatment state and dispersibility, (4) solvent composition of coating solution and affinity with translucent fine particles, (5) drying It can be controlled by conditions, (6) wet coating amount, (7) curing conditions for the ionizing radiation curable resin, and the like.
In order to increase the surface roughness Ra within the scope of the present invention, a large amount of translucent fine particles, particularly those having a large particle size with respect to the antiglare layer thickness, It can be effectively achieved by increasing the proportion and difference in particle size. Further, in order to keep the surface roughness Ra within a predetermined range, the dispersibility of the translucent fine particles is improved by performing a surface treatment on the translucent fine particles, and the solvent composition is difficult to penetrate into the transparent substrate (not dissolve). ) The composition can be appropriately used, such as slowing drying so that the coating layer can be sufficiently leveled (smoothed).
[0019]
On the other hand, in order to set the Rz / Ra value of the antiglare antireflection film to 30 or less, as a solvent of the coating solution for forming the antiglare layer, a solvent having a boiling point of 100 ° C. or more is used as a total solvent in the coating solution. It is preferable to adjust to include 1 to 95%, more preferably 3 to 80%, and in order to set the Rz / Ra value to 20 or less, a solvent having a boiling point of 100 ° C. or higher is 10 to 10% of all the solvents in the coating solution. It can be realized by setting it to 70%. If there is no solvent with a boiling point of 100 ° C. or higher, a brushed surface will occur during drying, the Rz / Ra value tends to increase, and if it exceeds 95%, the drying temperature must be increased, resulting in increased drying unevenness. It becomes unsuitable as an antireflection film.
[0020]
As a result of further investigation, even if the anti-glare anti-reflection film gives the same anti-glare property, the display power is turned off if each surface protrusion shape is different to express this total anti-glare property. At the time of black display of liquid crystal, it was found that the appearance of black tightening (in other words, whiteness) differs due to the difference in surface scattering. It has been found that when the protrusion inclination angle of the surface protrusion is large, the surface scattering property to a wide angle region becomes strong, so that the black tightening is impaired and whitish, and the high-class feeling is lost, which is not preferable. In particular, when black tightening is found to correlate well with the protrusion inclination angle (95% frequency), the angle is preferably 20 degrees or less, more preferably 15 degrees or less, and even more preferably 13 degrees or less. In addition, it was found that black tightening was good. Here, the “projection inclination angle (95% frequency)” means an angle having a frequency of 95% from the small angle side of the protrusion inclination angle distribution. Specifically, the surface inclination angle is within a certain range ( (100 points), and the 95th value when the angles are arranged in ascending order.
Further, the average surface protrusion inclination angle (corresponding to an angle of 50% frequency from the smaller angle of the protrusion inclination angle distribution), which correlates well with the antiglare property, is preferably 1 to 5 degrees, more preferably 1.5. -4.5 degrees, more preferably 2-4 degrees.
[0021]
By applying a low refractive index layer by an ordinary method on the anti-glare layer having a specific Ra and Rz / Ra value formed as described above, a uniform low refractive index layer is obtained. An antiglare antireflection film having good reflectance and antiglare property can be obtained without causing surface defects. More preferably, in order to obtain a uniform and thin low refractive index layer, the surface energy of the antiglare layer is 25 mN · m.^-1~ 70mN ・ m^-1It is preferable to make 50-100 mass% of the coating solvent of a low refractive index layer into the solvent which has a boiling point of 100 degrees C or less. The surface energy of the antiglare layer can be adjusted by adjusting the structure and amount of the fluorine-based and / or silicone-based surfactant.
[0022]
The antiglare antireflection film of the present invention thus formed preferably has a mirror surface average reflectance and an integrated reflectance of 450% to 650 nm of 2.5% or less, and preferably 2.2% or less. More preferred is 1.9% or less. When the specular reflectance exceeds 2.5%, the background reflection becomes clear, and the visibility when applied to the surface of the display device is lowered, which is not preferable. On the other hand, if the integrated reflectance exceeds 2.5%, the contrast is lowered, the display screen is whitened, and the display quality of the display device is lowered, which is not preferable.
[0023]
Regarding the haze value of the surface of the antiglare and antireflection film, the lower the surface haze value, the smaller the image blur and the more clear display can be obtained, which is preferable. However, if the surface haze value is too low, there will be a brilliant glow called reflection and surface glare (scintillation). On the other hand, if the haze value is too high, it becomes whitish (whitening; reduced black density), which is not preferable. Providing moderate surface irregularities on the anti-glare layer and providing anti-glare properties that prevent reflection by external light, the difference in refractive index between the translucent binder matrix and the translucent fine particles that impart anti-glare properties It is preferably zero or 0.50 or less, and the surface haze is preferably controlled to 7 to 25%, more preferably 10 to 20%. Methods for controlling the surface haze value include increasing the particle size ratio of the light-transmitting fine particles (anti-glare fine particles) imparted to the anti-glare layer thickness and anti-glare properties, increasing the concentration of the anti-glare fine particles, and anti-glare. The method of making the film thickness of a property layer thin is mentioned, These can be selected suitably and can be controlled.
[0024]
On the other hand, as for the internal scattering haze value of the antiglare antireflection film, the viewing angle is improved as the light emitted from the backlight is scattered internally by the antiglare layer on the viewing side in order to improve the viewing angle characteristics. Although the characteristics are improved, however, too much scattering is not preferable because back scattering increases, leading to a decrease in front luminance and a problem that image scattering deteriorates due to excessive scattering. Accordingly, the difference in refractive index between the light-transmitting binder matrix and the light-transmitting fine particles imparting internal scattering properties is preferably 0.05 to 0.50, and the internal scattering haze is preferably 30 to 80%. It is more preferable to set it as 70%, and it is especially preferable to set it as 40 to 60%. Methods for controlling the internal scattering haze include methods such as increasing the refractive index difference between the translucent binder matrix and the translucent fine particles, increasing the concentration of the translucent fine particles, and increasing the film thickness. The internal scattering haze can be controlled by appropriately selecting.
[0025]
The state in which the internal scattering haze and the surface haze exist is preferably 40% or more as the total haze value because the effect of improving the viewing angle is exhibited. The total haze value is more preferably 40 to 90%, further preferably 45 to 80%, and particularly preferably 50 to 70%.
In addition, haze value (cloudiness value) can be measured using HR-100 by Murakami Color Research Laboratory according to JIS-K-7105.
[0026]
[Transparent support]
As the transparent support of the antiglare antireflection film of the present invention, it is preferable to use a plastic film. Polymers that form plastic films include cellulose esters (eg, triacetyl cellulose, diacetyl cellulose, etc.), polyamides, polycarbonates, polyesters (eg, polyethylene terephthalate, polyethylene naphthalate, etc.), polystyrene, polyolefin, polysulfone, polyethersulfone, Examples include polyarylate, polyetherimide, polymethyl methacrylate, polyether ketone, norbornene-based resin (Arton: trade name, manufactured by JSR), amorphous polyolefin (ZEONEX: trade name, manufactured by Nippon Zeon), and the like. Of these, triacetyl cellulose, polycarbonate, polyethylene terephthalate, and polyethylene naphthalate are preferable, and triacetyl cellulose is particularly preferable. The light transmittance of the transparent support is preferably 80% or more, and more preferably 86% or more. The haze of the transparent support is preferably 2.0% or less, and more preferably 1.0% or less. The refractive index of the transparent support is preferably 1.4 to 1.7. The thickness is preferably 25 to 1000 μm.
[0027]
Various additives can be added to the transparent support. For example, various additives such as a plasticizer, an ultraviolet absorber, a deterioration preventing agent, a slipping agent, a peeling accelerator, and an infrared absorber are contained. These addition amounts can be added within a range that does not affect the light transmittance and mechanical properties, and are preferably 0.01 to 25%, and preferably 0.1 to 20% of the transparent support. Is more preferable.
In order to impart slipperiness, particles of an inert inorganic compound or an organic compound may be added to the transparent support. Inorganic compounds include SiO₂TiO₂, BaSO_Four, CaCO_Three, Talc, kaolin and the like. Also, those described in JIII Journal of Technical Disclosure 2001-1745, page 19 (published in 2001) can be used.
Moreover, you may implement surface treatment to a transparent support body. Examples of surface treatments can include existing treatments such as chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet irradiation treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, and ozone oxidation treatment. Chemical treatment, corona discharge treatment, flame treatment, ultraviolet irradiation treatment, and glow discharge treatment are preferably used.
In addition, when cellulose acetate is used as the support, the technology described in JIII Journal of Technical Disclosure (Publication No. 2001-1745, published on March 15, 2001) can be used.
[0028]
[Anti-glare layer]
The antiglare layer is composed of translucent fine particles for imparting antiglare properties and internal scattering properties and a translucent binder matrix holding the translucent fine particles. The translucent binder matrix is a coating, drying and curing coating solution containing binder resin and polymerization initiator, which will be described later, ultrafine particle filler added for refractive index adjustment and high strength, and other additives. is there.
The film thickness of the antiglare layer is preferably 1 to 10 μm, more preferably 2 to 7 μm, and further preferably 3 to 5 μm. If the film thickness is too thin, the surface hardness of the antiglare antireflection film will be lowered, and it will not be possible to contain light-transmitting fine particles in a preferred range. On the other hand, if the film thickness is too thick, The ratio of the binder component is increased, which causes undesirable effects such as poor applicability due to an increase in liquid viscosity. The definition of the thickness of the antiglare layer is that there is no translucent fine particles of the antiglare layer from the most antiglare layer side portion of the lower layer component of the antiglare layer (or the support component when there is no lower layer). The vertical distance between the thinnest points is used as a reference. The thickness of the antiglare layer can be examined with a cross-sectional TEM (transmission electron microscope).
[0029]
[Translucent fine particles]
The antiglare layer contains translucent fine particles for the purpose of imparting antiglare properties and internal scattering properties. In the present invention, “translucency” is defined as having a property of transmitting light or having a refractive index. Examples of the light-transmitting fine particles include inorganic compound particles and / or organic polymer (resin) particles.
The average particle size of the translucent fine particles is preferably 0.4 to 20 μm, more preferably 1.0 to 12 μm, and still more preferably 1.8 to 6.0 μm.
[0030]
Among them, the particle diameter of the light-transmitting fine particles (also referred to as anti-glare fine particles) for imparting anti-glare properties is preferably 0.8 to 20 μm, more preferably 1.6 to 12 μm, still more preferably. In particular, in order to form a convex shape on the surface of the antiglare layer, particles having a particle size that is approximately the same as or larger than the thickness of the antiglare layer are preferable. The particle size is more preferably 0.8 to 2.0 times the thickness of the conductive layer, and still more preferably 0.9 to 1.4 times the particle size. Further, the refractive index of the antiglare particles is preferably such that the difference from the refractive index of the translucent binder matrix is zero or 0.05 or less.
[0031]
  On the other hand, in order to cause internal scattering, particles imparting internal scattering properties (also referred to as scattering particles) have a particle size of 0.4 μm or more, and the refractive index is 0 different from the refractive index of the translucent binder matrix. 0.05 to 0.5 is preferable. If the difference in refractive index is less than 0.05, it is necessary to add a large amount of scattering particles in order to cause sufficient scattering, which is not preferable.
  Scattered particles are particles that impart antiglare properties.ChildThe particle | grains which do not contribute to glare-proof provision and may be embedded in an anti-glare layer may be sufficient. In order not to increase the antiglare property too much, the particle size is preferably smaller than the thickness of the antiglare layer, and the particle size is preferably 0.4 to 8.0 μm, more preferably 1.0 to The thickness is 6.0 μm, particularly preferably 1.8 to 4.0 μm.
[0032]
By using two or more kinds of translucent fine particles with different particle diameters and mixing them, the viewing angle characteristics related to display quality and the reflection of external light can be individually optimized. This is preferable because fine setting is possible depending on the mixing ratio of the light-transmitting fine particles, control is possible as compared with the case of one kind, and various designs can be facilitated.
[0033]
The refractive index of the translucent fine particles should be selected in relation to the refractive index of the translucent binder matrix other than the translucent fine particles, and the refractive index and the preferred refractive index of the translucent binder matrix shown above. The range satisfying the difference is more preferably in the range of 1.40 to 1.80. Moreover, the higher the monodispersibility, the less the dispersion in the diffusion characteristics, and the easier the design of the haze is.
Specific examples of the light-transmitting fine particles include, for example, silica particles (for example, Nippon Shokubai Co., Ltd. Seahosta series refractive index = 1.43), alumina particles (for example, Sumitomo Chemical Co., Ltd. Sumiko Random series refractive index = 1). 64), TiO₂Particles of inorganic compounds such as particles, or polymethyl methacrylate particles (refractive index 1.49), acrylic-styrene copolymer particles (refractive index 1.55), cross-linked acrylic particles (for example, MX series manufactured by Soken Chemical Co., Ltd.) Ratio = 1.49), melamine particles (refractive index 1.57), crosslinked melamine particles, polycarbonate particles (refractive index 1.57), polyvinyl chloride particles (refractive index 1.60), benzoguanamine particles (refractive index 1. 68), cross-linked benzoguanamine particles (e.g., Nippon Shokubai Co., Ltd., Eposter series refractive index = 1.68), polystyrene particles (refractive index 1.60), cross-linked polystyrene particles (e.g., Soken Chemical Co., Ltd. SX series refractive index) = 1.61) and the like are preferred. Of these, crosslinked styrene particles are preferred. As the shape of the translucent fine particles, either a true sphere or an indefinite shape can be used, but a true spherical particle having a uniform surface protrusion shape is more preferable.
Further, two or more different kinds of translucent fine particles may be used in combination. Even if there are two or more kinds of material and two or more kinds of particle sizes, there is no limitation.
The preferable addition amount of translucent fine particles is 100 to 1000 mg / m in the antiglare layer.²And more preferably 300 to 800 mg / m²It is.
[0034]
[Translucent binder matrix]
The translucent binder matrix is a coating, drying and curing coating solution containing binder resin and polymerization initiator, which will be described later, ultrafine particle filler added for refractive index adjustment and high strength, and other additives. Yes, the refractive index of the translucent binder matrix is the refractive index of the antiglare layer that does not contain translucent fine particles for imparting antiglare properties and internal scattering properties, and imparts antiglare properties and internal scattering properties. Therefore, a layer excluding the light-transmitting fine particles can be prepared and evaluated.
[0035]
The refractive index of the translucent binder matrix is preferably 1.48 to 2.00, more preferably 1.50 to 1.90, and still more preferably 1.64 to 1.80. In order to make the refractive index within the above range, it is achieved by appropriately selecting the kind and amount ratio of the binder resin and the inorganic ultrafine particle filler which are the main constituent materials. When the refractive index is too small, the antireflection property is lowered. Furthermore, when this is too large, the tint of the reflected light of the antiglare film of the present invention becomes strong, which is not preferable.
[0036]
The difference in refractive index between the translucent binder matrix and the translucent fine particles is preferably 0.00 to 0.50. When the translucent fine particles are not given internal scattering properties, the difference in refractive index is preferably 0.00 to 0.05 so as not to have a light scattering effect. The difference in refractive index when the viewing angle characteristics are improved by providing the light-transmitting fine particles with internal scattering properties is preferably 0.05 to 0.50, more preferably 0.05 to 0.25, and 0 0.05 to 0.20 is most preferable. If the refractive index difference is larger than 0.50, the light scattering property is too high, and the entire film is whitened, which is not preferable.
[0037]
The magnitude of the refractive index of the translucent binder matrix and the translucent fine particles is not particularly limited, but in order to reduce the character blur, the refractive index of the string-proof layer is within the range of the refractive index difference described above. It is preferable to lower the rate, and in order to further reduce the reflectivity of the antiglare antireflection film, it is preferable to increase the refractive index of the antiglare layer, which is appropriately selected depending on the design concept.
[0038]
[Binder resin]
The binder resin used for the antiglare layer is preferably a polymer having a saturated hydrocarbon or polyether as the main chain, and more preferably a polymer having a saturated hydrocarbon as the main chain. The binder resin is preferably crosslinked. The polymer having a saturated hydrocarbon as the main chain is preferably obtained by a polymerization reaction of an ethylenically unsaturated monomer. In order to obtain a crosslinked binder resin, it is preferable to use a monomer having two or more ethylenically unsaturated groups.
In order to adjust the refractive index to increase the refractive index, at least one selected from an aromatic ring, a halogen atom other than fluorine, a sulfur atom, a phosphorus atom, and a nitrogen atom in the structure of this monomer. It is also preferred to include seed atoms.
[0039]
The monomer having an ethylenically unsaturated group preferably contains 2 to 10 polymerizable groups, and preferably 2 to 8 polyfunctional monomers. Specifically, esters of polyhydric alcohol and (meth) acrylic acid (eg, ethylene glycol di (meth) acrylate, 1,4-dichlorohexane diacrylate, pentaerythritol tetra (meth) acrylate), pentaerythritol tri ( (Meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1 , 3,5-cyclohexanetriol trimethacrylate, pentaerythritol hexa (meth) acrylate, 1,2,3-cyclohexanetetramethacrylate, polyurethane polyacrylate, Reester polyacrylate), derivatives of vinylbenzene (eg, 1,4-divinylbenzene, 4-vinylbenzoic acid-2-acryloylethyl ester, 1,4-divinylcyclohexanone), vinylsulfone (eg, divinylsulfone), acrylamide ( Examples include methylenebisacrylamide) and methacrylamide. Two or more of these monomers may be used in combination. Among these, trifunctional to octafunctional acrylates or methacrylates are preferable from the viewpoint of film hardness, that is, scratch resistance.
[0040]
Specific examples of the high refractive index monomer include bis (4-methacryloylthiophenyl) sulfide, vinyl naphthalene, vinyl phenyl sulfide, 4-methacryloxyphenyl-4′-methoxyphenyl thioether, and the like. Two or more of these monomers may be used in combination.
[0041]
Polymerization of the monomer having an ethylenically unsaturated group can be performed by irradiation with ionizing radiation and / or heating in the presence of a photo radical initiator and / or a thermal radical initiator.
Therefore, a coating liquid containing a monomer having an ethylenically unsaturated group, a photo radical initiator and / or a thermal radical initiator, translucent fine particles and inorganic ultrafine particle filler is prepared, and the coating liquid is placed on the transparent support. After application, it can be cured by ionizing radiation irradiation and / or polymerization reaction by heat to form an antiglare layer.
[0042]
Examples of the photoradical polymerization initiator include acetophenones, benzophenones, Michler's benzoylbenzoate, -amyloxime ester, tetramethylthiuram monosulfide, and thioxanthones.
In particular, photocleavable photoradical polymerization initiators are preferred. The photocleavable photoradical polymerization initiator is described in the latest UV curing technology (P.159, issuer; Kazuhiro Takashiro, publisher; Technical Information Association, Inc., published in 1991).
Examples of commercially available photocleavable photoradical polymerization initiators include Irgacure (651, 184, 907) manufactured by Ciba Geigy Japan.
In addition to the photopolymerization initiator, a photosensitizer may be used. Specific examples of the photosensitizer include n-butylamine, triethylamine, tri-n-butylphosphine, Michler's ketone and thioxanthone.
The radical polymerization initiator is preferably used in the range of 0.1 to 15 parts by mass, more preferably in the range of 1 to 10 parts by mass with respect to 100 parts by mass of the polyfunctional monomer.
[0043]
Various examples of compounds that generate an acid by the action of light are described in, for example, “Organic Materials for Imaging” p187-198, JP-A-10-282644, edited by the Society for Organic Electronics Materials (Bunshin Publishing). These known compounds can be used. Specifically, RSO_Three ^-(R represents an alkyl group or an aryl group), AsF₆ ^-, SbF₆ ^-, PF₆ ^-, BF_Four ^-Organic compounds such as diazonium salts, ammonium salts, phosphonium salts, iodonium salts, sulfonium salts, selenonium salts, arsonium salts and other onium salts substituted with a trihalomethyl group and S-triazine derivatives. Halides, o-nitrobenzyl esters of organic acids, benzoin esters, imino esters, disulfone compounds and the like can be mentioned. Preferred are onium salts, particularly preferred are sulfonium salts and iodonium salts. Known compounds that generate a base by the action of light can also be used, and specific examples include nitrobenzyl carbamates and dinitrobenzyl carbamates.
[0044]
The polymer having a polyether as the main chain is preferably a polyfunctional compound cationic ring-opening polymer containing two or more cationically polymerizable groups selected from an epoxy group and an oxetane group. The ring-opening polymerization of the polyfunctional compound can be performed by irradiation with ionizing radiation and / or heating in the presence of a photoacid generator and / or a thermal acid generator.
In particular, as the cationically polymerizable group-containing compound, an alicyclic polyepoxy compound having two or more epoxy groups in one molecule is contained, and the content of the alicyclic polyepoxy compound is based on the total mass of the epoxy compound. When an epoxy compound (a mixture of epoxy compounds) of 30% by mass or more, more preferably 50% by mass or more is used, the cationic polymerization rate, thick film curability, resolution, ultraviolet transmittance, etc. are further improved, and the resin The viscosity of the composition is lowered, and film formation is performed smoothly. Specific examples include compounds described in paragraph numbers [0084] to [0086] in the specification of JP-A-11-242101.
[0045]
As a compound containing an oxetanyl group, the number of oxetanyl groups contained in the molecule is 1 to 10, preferably 1 to 4. These compounds are preferably used in combination with an epoxy group-containing compound. Specific examples include the compounds described in paragraph numbers [0024] to [0025] in JP-A-2000-239309. Accordingly, a coating liquid containing a polyfunctional compound containing two or more cationically polymerizable groups selected from an epoxy group and an oxetane group, a photoacid generator and / or a thermal acid generator, translucent fine particles, and inorganic ultrafine particle fillers The coating solution is applied onto a transparent support and then cured by irradiation with ionizing radiation and / or a polymerization reaction by heat to form an antiglare layer.
[0046]
In place of, or in addition to, a monomer having two or more ethylenically unsaturated groups, a monomer having a crosslinkable functional group is used to introduce a crosslinkable functional group into the polymer, and by reaction of the crosslinkable functional group, A cross-linked structure may be introduced into the binder resin.
Examples of the crosslinkable functional group include isocyanate group, epoxy group, aziridine group, oxazoline group, formyl group, carbonyl group, hydrazine group, carboxyl group, methylol group and active methylene group. Vinylsulfonic acid, acid anhydride, cyanoacrylate derivative, melamine, etherified methylol, ester and urethane, and metal alkoxide such as tetramethoxysilane can also be used as a monomer for introducing a crosslinked structure. A functional group that exhibits crosslinkability as a result of the decomposition reaction, such as a block isocyanate group, may be used. That is, in the present invention, the crosslinkable functional group may not react immediately but may exhibit reactivity as a result of decomposition.
These binder resins having a crosslinkable functional group can form a crosslinked structure by heating after coating.
[0047]
[Ultrafine filler]
In order to adjust the refractive index of the translucent binder matrix, it is selected from silicon, titanium, zirconium, aluminum, indium, zinc, tin, antimony, etc. having an average particle size of 0.2 μm or less separately from the above translucent fine particles At least one metal oxide or ultrafine filler made of an organic polymer can be added. An inorganic ultrafine particle filler having a large refractive index difference from the binder resin is preferred. The average particle diameter is preferably 0.1 μm or less, more preferably 0.06 μm or less.
The shape of the ultrafine filler is not particularly limited, and for example, any of a spherical shape, a plate shape, a fiber shape, a rod shape, an indeterminate shape, a hollow shape, and the like are preferably used. This ultrafine filler can contribute to curling prevention and surface hardness improvement depending on the filling amount. When the antiglare layer contains an ultrafine particle filler, the refractive index of the translucent binder matrix is mainly determined by the refractive indexes of the binder resin and the inorganic ultrafine particle filler constituting the antiglare layer and the mixing ratio thereof. .
[0048]
As a specific example of the inorganic ultrafine particle filler, TiO₂(Refractive index; 2.3-2.7), ZrO₂(Refractive index; 2.05), Al₂O_Three(Refractive index; 1.63), Y₂O_Three(Refractive index; 1.87), La₂O_Three(Refractive index; 1.95), In₂O_ThreeZnO, SnO₂, Sb₂O_Three, ITO, SiO₂Etc. SiO₂TiO₂And ZrO₂Is particularly preferable among the inorganic ultrafine particle fillers in terms of handleability. The surface of the inorganic ultrafine particle filler is also preferably subjected to silane coupling treatment or titanium coupling treatment, and a surface treatment agent having a functional group capable of reacting with the binder species on the filler surface is preferably used.
The addition amount of these ultrafine particle fillers is preferably 10 to 90% of the total mass of the antiglare layer, more preferably 20 to 70%, and particularly preferably 30 to 50%. In addition, since such ultrafine particle filler has a particle size sufficiently smaller than the wavelength of light, scattering does not occur, and a composite in which the ultrafine particle filler is dispersed in a binder resin behaves as an optically uniform substance, The function of the ultrafine particle filler is different from that of translucent fine particles described later.
[0049]
[Other additives for translucent binder matrix]
These monomers having an ethylenically unsaturated group can be cured by a polymerization reaction by ionizing radiation or heat after being dissolved in a solvent, coated and dried together with various polymerization initiators and other additives.
The anti-glare layer of the present invention is anti-glare for either a fluorine-based surfactant or a silicone-based surfactant, or both of them, particularly in order to further ensure surface uniformity such as coating unevenness, drying unevenness, and point defects. It can contain in the coating composition for forming an adhesive layer. In particular, a fluorine-based surfactant is preferably used because an effect of improving surface defects such as coating unevenness, drying unevenness, and point defects of the antiglare antireflection film of the present invention appears in a smaller addition amount.
Preferable examples of the fluorosurfactant include perfluoroalkylsulfonic acid amide group-containing nonions such as 3M's Fluorard FC-431, Daifuku Ink's MegaFuck F-171, F-172, F- Perfluoroalkyl group-containing oligomers such as 173 and F-176PF. Examples of the silicone-based surfactant include polydimethylsiloxane in which a side chain or a main chain terminal is modified with various substituents such as oligomers such as ethylene glycol and propylene glycol.
[0050]
However, by using the surfactant as described above, the functional group containing F atoms and / or the functional group having Si atoms segregates on the surface of the antiglare layer, and thus the surface of the antiglare layer. When the energy is lowered and the low refractive index layer is overcoated on the antiglare layer, there may be a problem that the antireflection performance deteriorates. This is presumably because minute unevenness that cannot be detected by visual observation of the film thickness of the low refractive index layer deteriorates because the wettability of the coating composition used for forming the low refractive index layer deteriorates. In order to solve such a problem, the surface energy of the antiglare layer is preferably adjusted to 25 mN · m by adjusting the structure and addition amount of the fluorine-based and / or silicone-based surfactant.^-1~ 70mN ・ m^-1More preferably 35 mN · m^-1~ 70mN ・ m^-1It is effective to control. Further, as described later, it is effective that 50 to 100% by mass of the coating solvent for the low refractive index layer has a boiling point of 100 ° C. or less.
[0051]
[Anti-glare layer coating solution solvent]
The solvent of the coating solution for forming the antiglare layer is used for the expression of the antiglare property and the adhesiveness between the lower layer (transparent support) and the antiglare layer so that Rz / Ra is in a desired range. In order to achieve compatibility, it is preferable to use at least one solvent that dissolves the lower layer (transparent support) and at least one solvent that does not dissolve the lower layer (transparent support). For example, when a triacetyl cellulose support is used as the transparent support, at least one of the solvents that do not dissolve triacetyl cellulose may have a higher boiling point than at least one of the solvents that dissolve triacetyl cellulose. preferable. More preferably, the boiling point temperature difference between the solvent having the highest boiling point among the solvents not dissolving the triacetyl cellulose support and the solvent having the highest boiling point among the solvents dissolving the triacetyl cellulose support is 30 ° C. or more. And most preferably 50 degrees or more.
[0052]
As a solvent for dissolving triacetylcellulose, ethers having 3 to 12 carbon atoms: specifically, dibutyl ether, dimethoxymethane, dimethoxyethane, diethoxyethane, propylene oxide, 1,4-dioxane, 1,3 -Ketones having 3 to 12 carbon atoms such as dioxolane, 1,3,5-trioxane, tetrahydrofuran, anisole and phenetole: specifically, acetone, methyl ethyl ketone, diethyl ketone, dipropyl ketone, diisobutyl ketone, cyclopentanone , Cyclohexanone, methylcyclohexanone, methylcyclohexanone and the like, and esters having 3 to 12 carbon atoms: specifically, ethyl formate, propyl formate, n-pentyl formate, methyl acetate, ethyl acetate, methyl propionate, propion brewing ethyl , Acetic acid -Organic solvent having two or more functional groups such as pentyl and γ-butyrolactone: specifically, methyl 2-methoxyacetate, methyl 2-ethoxyacetate, ethyl 2-ethoxyacetate, ethyl 2-ethoxypropionate, Examples include 2-methoxyethanol, 2-propoxyethanol, 2-butoxyethanol, 1,2-diacetoxyacetone, acetylacetone, diacetone alcohol, methyl acetoacetate, and ethyl acetoacetate.
These can be used alone or in combination of two or more.
[0053]
As solvents that do not dissolve triacetyl cellulose, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, tert-butanol, 1-pentanol, 2-methyl-2-butanol, cyclohexanol, acetic acid Examples include isobutyl, methyl isobutyl ketone, 2-octanone, 2-pentanone, 2-hexanone, 2-heptanone, 3-pentanone, 3-heptanone and 4-heptanone.
These can be used alone or in combination of two or more.
[0054]
The mass ratio (A / B) of the total amount (A) of the solvent that dissolves triacetyl cellulose and the total amount (B) of the solvent that does not dissolve triacetyl cellulose is preferably 5/95 to 50/50, more preferably 10 /. It is 90-40 / 60, More preferably, it is 15 / 85-30 / 70.
[0055]
[How to create an antiglare layer]
The antiglare antireflection film of the present invention can be formed by the following method, and an antiglare layer is one of them, but is not limited to this method.
First, a coating solution containing components for forming each layer is prepared. Next, the coating liquid for forming the antiglare layer is reverse gravure method (classified as gravure coating method, micro gravure coating method, etc.), dip coating method, air knife coating method, curtain coating method, roller coating The coating is applied onto a transparent support by a method, a wire bar coating method and an extrusion coating method (see US Pat. No. 2,681,294), and is heated and dried. A micro gravure coating method is particularly preferred. Thereafter, the monomer for forming the antiglare layer is polymerized and cured by light irradiation or heating. Thereby, an anti-glare layer is formed.
[0056]
The micro gravure coating method used when coating each layer of the antiglare antireflection film of the present invention is a gravure roll having a diameter of about 20 to 50 mm and engraved with a gravure pattern on the entire circumference, below the support. And while rotating the gravure roll reversely with respect to the conveyance direction of the support, the surplus coating liquid is scraped off from the surface of the gravure roll by a doctor blade, and the upper surface of the support is in a free state. The coating method is characterized in that the coating liquid is transferred to the lower surface of the support at the position and applied.
[0057]
[Low refractive index layer]
The low refractive index layer of the present invention will be described below.
The refractive index of the low refractive index layer of the antiglare antireflection film of the present invention is preferably in the range of 1.38 to 1.49, more preferably 1.38 to 1.44.
Furthermore, the low refractive index layer preferably satisfies the following formula (I) in order to achieve a low reflectance.
[0058]
m · λ / 4 × 0.7 <n₁d₁<M ・ λ / 4 × 1.3 ・ Formula (I)
[0059]
Where m is a positive odd number and n₁Is the refractive index of the low refractive index layer and d₁Is the film thickness (nm) of the low refractive index layer. Further, λ is a wavelength and is a value in the range of 500 to 550 nm.
In addition, satisfy | filling said numerical formula (I) means that m (positive odd number, usually 1) which satisfy | fills numerical formula (I) exists in the said wavelength range.
[0060]
The material for forming the low refractive index layer of the present invention will be described below.
For the low refractive index layer, as a low refractive index binder, a fluorinated polymer that crosslinks by heat or ionizing radiation having a dynamic friction coefficient of 0.03 to 0.15, a contact angle with water of 90 to 120 degrees, and for improving film strength An inorganic ultrafine particle filler is preferably used.
[0061]
Examples of the crosslinkable fluorine-containing polymer used in the low refractive index layer include a perfluoroalkyl group-containing silane compound (for example, (heptadecafluoro-1,1,2,2-tetradecyl) triethoxysilane), and other fluorine-containing monomers. And a fluorine-containing polymer having a monomer for providing a crosslinkable group as a structural unit.
Specific examples of the fluorine-containing monomer unit include, for example, fluoroolefins (for example, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, hexafluoroethylene, hexafluoropropylene, perfluoro-2,2-dimethyl-1,3-dioxole, etc. ), (Meth) acrylic acid partial or fully fluorinated alkyl ester derivatives (for example, Biscoat 6FM (manufactured by Osaka Organic Chemicals) and M-2020 (manufactured by Daikin)), fully or partially fluorinated vinyl ethers, and the like.
As a monomer for imparting a crosslinkable group, in addition to a (meth) acrylate monomer having a crosslinkable functional group in the molecule like glycidyl methacrylate, it has a carboxyl group, a hydroxyl group, an amino group, a sulfonic acid group, etc. ) Acrylate monomers (for example, (meth) acrylic acid, methylol (meth) acrylate, hydroxyalkyl (meth) acrylate, allyl acrylate, etc.). It is known from JP-A-10-25388 and JP-A-10-147739 that the latter can introduce a crosslinked structure after copolymerization.
[0062]
Further, not only a polymer having the above-mentioned fluorine-containing monomer as a structural unit but also a copolymer with a monomer not containing a fluorine atom may be used. There are no particular limitations on the monomer units that can be used in combination. For example, olefins (ethylene, propylene, isoprene, vinyl chloride, vinylidene chloride, etc.), acrylic esters (methyl acrylate, methyl acrylate, ethyl acrylate, acrylic acid 2) -Ethylhexyl), methacrylates (methyl methacrylate, ethyl methacrylate, butyl methacrylate, ethylene glycol dimethacrylate, etc.), styrene derivatives (styrene, divinylbenzene, vinyltoluene, α-methylstyrene, etc.), vinyl ethers (methyl) Vinyl ether), vinyl esters (vinyl acetate, vinyl propionate, vinyl cinnamate, etc.), acrylamides (N-tertbutylacrylamide, N-cyclohexylacrylamide, etc.), methacrylamides, Krilo nitrile derivatives and the like can be mentioned.
[0063]
The average particle size of the ultrafine particle filler (L) used for the low refractive index layer is preferably 0.001 to 0.2 μm, and more preferably 0.001 to 0.05 μm. The particle diameter of the filler is preferably as uniform (monodispersed) as possible.
The ultrafine particle filler (L) preferably has a low refractive index and may be an organic ultrafine particle filler (L) or an inorganic ultrafine particle filler (L). To inorganic ultrafine filler (L).
The addition amount of the ultrafine filler (L) is preferably 5 to 70% by mass of the total mass of the low refractive index layer, more preferably 10 to 50% by mass, and particularly preferably 15 to 30% by mass.
[0064]
The inorganic ultrafine particle filler (L) is preferably amorphous. The inorganic ultrafine filler (L) is preferably made of a metal oxide, nitride, sulfide or halide, more preferably a metal oxide or metal halide, and a metal oxide or metal fluoride. Most preferably. As metal atoms, Mg, Ca, Ba, Al, Zn, Fe, Cu, Ti, Sn, In, W, Y, Sb, Mn, Ga, V, Nb, Ta, Ag, Si, B, Bi, Mo Ce, Cd, Be, Pb and Ni are preferable, and Mg, Ca, B and Si are more preferable. An inorganic compound containing two kinds of metals may be used. Particularly preferred inorganic compounds include silicon dioxide and magnesium fluoride.
[0065]
The inorganic ultrafine filler (L) is preferably used after being subjected to a surface treatment. The surface treatment method includes physical surface treatment such as plasma discharge treatment and corona discharge treatment and chemical surface treatment using a coupling agent, but the use of a coupling agent is preferred. As the coupling agent, an organoalkoxymetal compound (eg, titanium coupling agent, silane coupling agent) including the compound of the general formula (1) described later is preferably used. When the inorganic ultrafine filler is silica, silane coupling treatment is particularly effective.
The compound of the general formula (1) may be used as a surface treatment agent for the inorganic ultrafine filler (L) of the low refractive index layer in order to perform a surface treatment before the preparation of the layer coating solution. It may be added as an additive at the time of preparation and contained in the layer.
[0066]
As a solvent of the coating solution used for forming the low refractive index layer, an organic solvent is preferable, and ketones (for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methylcyclohexanone, etc.), esters (for example, ethyl formate, Ethyl acetate, butyl acetate, methyl propionate, ethylene glycol monomethyl ether monoacetate, etc.), alcohols (eg, methanol, ethanol, isopropyl alcohol, butanol, ethylene glycol, ethylene glycol monomethyl ether, etc.), hydrocarbons (eg, hexane) , Octane, cyclohexane, petroleum ether, ligroin, benzene, toluene, xylene, etc.), ethers (eg, diisopropyl ether, dipropyl ether, dibutyl ether, Tylene glycol dimethyl ether, tetrahydrofuran, 1,4-dioxane, etc.), halogenated hydrocarbons (eg, dichloromethane, chloroform, methyl chloroform, 1,2-dichloroethane, trichloroethylene, etc.), cyano compounds (eg, acetonitrile, propionitrile). Etc.), amides (for example, formamide, dimethylformamide, dimethylacetamide, etc.), γ-butyrolactone, and the like. These solvents can be used alone or in combination of two or more solvents. Of these, ketones and esters are preferred.
[0067]
When mixing and using a solvent, it is preferable that the solvent whose boiling point is 100 degrees C or less is 50 to 100%, More preferably, it is 80 to 100%, More preferably, it is 90 to 100%. When the solvent having a boiling point of 100 ° C. or less is 50% or less, the drying speed becomes very slow, the coating surface state is deteriorated, and the coating film thickness is uneven, so the optical properties such as reflectance are also deteriorated, It is not preferable. In the present invention, by using a coating solution containing a large amount of a solvent having a boiling point of 100 ° C. or less, it is possible to more effectively achieve thin layer uniform coating of the low refractive index layer.
[0068]
The coating solution for a low refractive index layer of the present invention is prepared by diluting the low refractive index layer component according to the present invention with the solvent having the above composition. The concentration of the coating solution is preferably adjusted appropriately in consideration of the viscosity of the coating solution, the specific gravity of the low refractive index layer material, etc., but is preferably 0.1 to 20% by mass, more preferably 1 to 10% by mass. is there.
[0069]
The low refractive index layer is formed by applying a low refractive index layer coating solution on the antiglare layer and irradiating or heating it to form the low refractive index layer. Thus, the antiglare antireflection film of the present invention having a low refractive index layer having a uniform thickness along the surface irregularities on the antiglare layer having surface irregularities can be obtained.
[0070]
[Abrasion resistance]
Applying, drying and curing the compound of the following general formula (1) in the coating solution of at least one of the antiglare layer and the low refractive index layer of the antiglare antireflection film of the present invention. Is preferable from the viewpoint of imparting scratch resistance.
[0071]
General formula (1)
(R¹) M-Si (OR²) N
[0072]
In general formula (1), R¹Represents a substituted or unsubstituted alkyl group or aryl group. R²Represents a substituted or unsubstituted alkyl group or acyl group. m represents an integer of 0 to 3. n represents an integer of 1 to 4. However, the sum of m and n is 4.
[0073]
The compound represented by the general formula (1) will be described.
In the general formula (1), R¹Represents a substituted or unsubstituted alkyl group or aryl group. Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, hexyl, t-butyl, sec-butyl, hexyl, decyl, hexadecyl and the like. The alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 6 carbon atoms. Examples of the aryl group include phenyl and naphthyl, and a phenyl group is preferable.
[0074]
Although there is no restriction | limiting in particular as a substituent, Halogen (fluorine, chlorine, bromine, etc.), a hydroxyl group, a mercapto group, a carboxyl group, an epoxy group, an alkyl group (methyl, ethyl, i-propyl, propyl, t-butyl etc.), Aryl groups (phenyl, naphthyl, etc.), aromatic heterocyclic groups (furyl, pyrazolyl, pyridyl, etc.), alkoxy groups (methoxy, ethoxy, i-propoxy, hexyloxy, etc.), aryloxy (phenoxy, etc.), alkylthio groups (methylthio) , Ethylthio etc.), arylthio groups (phenylthio etc.), alkenyl groups (vinyl, 1-propenyl etc.), alkoxysilyl groups (trimethoxysilyl, triethoxysilyl etc.), acyloxy groups (acetoxy, acryloyloxy, methacryloyloxy etc.), Alkoxycarbonyl group Bonyl, ethoxycarbonyl, etc.), aryloxycarbonyl groups (phenoxycarbonyl, etc.), carbamoyl groups (carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N-methyl-N-octylcarbamoyl, etc.), acylamino groups (acetylamino) Benzoylamino, acrylamino, methacrylamino and the like.
Of these, more preferred are a hydroxyl group, a mercapto group, a carboxyl group, an epoxy group, an alkyl group, an alkoxysilyl group, an acyloxy group, and an acylamino group, and particularly preferred are an epoxy group and a polymerizable acyloxy group (acryloyloxy, methacryloyloxy). ) And a polymerizable acylamino group (acrylamino, methacrylamino). These substituents may be further substituted.
[0075]
R²Represents a substituted or unsubstituted alkyl group or acyl group. For the details of the alkyl group, acyl group and substituent, R¹This is the same as described in. R²Is preferably an unsubstituted alkyl group or an unsubstituted acyl group, and particularly preferably an unsubstituted alkyl group.
m represents an integer of 0 to 3. n represents an integer of 1 to 4. The sum of m and n is 4. R¹Or R²When there are multiple, there are multiple R¹Or R²May be the same or different. m is preferably 0, 1, 2 and particularly preferably 1.
[0076]
In addition to the compound of the general formula (1), it is also preferable to include a coupling-reactive silyl group-containing polymer. Specific examples of these compounds include, for example, paragraph numbers [0010] to [0047] in JP-A-11-52103, paragraph numbers [0013] to [0043] in JP-A-11-106704, Examples thereof include compounds described in paragraphs [0015] to [0026] of Kai 2000-275403.
[0077]
The appropriate addition amount of the compound of the general formula (1) is preferably 1 to 300% by mass, more preferably 3 to 200% by mass, and most preferably 5 to 100% by mass based on the total solid content of the layer containing the compound. .
[0078]
[Medium refractive index layer and high refractive index layer]
In order to further improve the antireflection performance, a medium refractive index layer and a high refractive index layer described in JP-A No. 2000-47004 and the like can be provided below the low reflectance layer. Similarly to the low refractive index layer, these medium refractive index layer and high refractive index layer can be applied uniformly in a thin layer, thereby substantially reducing the Ra value and Rz / Ra value of the antiglare layer. Without change, it is possible to provide a good anti-glare antireflection film with few irregularities.
[0079]
As an organic material for forming a layer having a higher refractive index than the above low refractive index layer, a thermoplastic film (eg, polystyrene, polystyrene copolymer, polycarbonate, aromatic ring other than polystyrene, heterocyclic ring, alicyclic ring) A polymer having a group or a polymer having a halogen group other than fluorine); a composition having a low thermal refractive index layer (eg, a film composition using a melamine film, a phenol film, or an epoxy film as a curing agent); urethane forming property Compositions (eg, combinations of alicyclic or aromatic isocyanates and polyols); and radical polymerizable compositions (modified films capable of radical curing by introducing double bonds into the above compounds (polymers, etc.)) Or a composition containing a prepolymer). A material having high film-forming properties is preferred. For the layer having a higher refractive index, inorganic fine particles dispersed in an organic material can also be used. As the organic material to be used above, those having a refractive index lower than that in the case where the organic fine particles are used alone because inorganic fine particles generally have a high refractive index can be used. As such materials, in addition to the above-mentioned organic materials, acrylic copolymers, vinyl copolymers, polyesters, alkyd coatings, fibrous polymers, urethane coatings, various curing agents that cure these, and curability Examples thereof include various organic materials that are transparent and stably disperse inorganic fine particles, such as a composition having a functional group.
[0080]
Further organically substituted silicon-based compounds can be included therein. These silicon-based compounds are compounds represented by the following general formula or hydrolysis products thereof.
: R^a _mR^b _n SiZ_(4-mn)(Where R^aAnd R^bRepresents an alkyl group, an alkenyl group, an allyl group, or a hydrocarbon group substituted with halogen, epoxy, amino, mercapto, methacryloyl or cyano, respectively, Z represents an alkoxyl group, an alkoxyalkoxyl group, a halogen atom to an acyloxy group Represents a selected hydrolyzable group, and m and n are 0, 1 or 2, respectively, under the condition that m + n is 1 or 2. )
[0081]
Preferable inorganic compounds of inorganic fine particles dispersed in these include oxides of metal elements such as aluminum, titanium, zirconium and antimony. These compounds are commercially available in particulate form, ie as a colloidal dispersion in powder or water and / or other solvents. These are further mixed and dispersed in the above organic material or organosilicon compound.
[0082]
As a material for forming a layer having a higher refractive index than the above, an inorganic material that can be dispersed in a solvent with a film-forming property or that is in a liquid state can be given. For example, organic acid salts, alkoxides of various elements (for example, titanium tetraethoxide, titanium tetrapropoxide, titanium tetrabutoxide, aluminum triethoxide, aluminum tripropoxide, aluminum tributoxide, antimony triethoxide, antimony riboxide) , Zirconium tetrabutoxide, zirconium tetrapropoxide, zirconium tetrabutoxide, etc.), β-diketones or β-ketoester metal chelate compounds (for example, paragraph numbers [0071] to [0083] of JP-A No. 2000-275403) And an inorganic polymer mainly composed of carbon zirconyl ammonium or zirconium. In addition to the above-mentioned, various alkyl silicates or hydrolysates thereof, particulate silica, particularly silica gel dispersed in a colloidal form, etc. are used as those having a relatively low refractive index but can be used in combination with the above compounds. be able to.
[0083]
The refractive index of the high refractive index layer is generally 1.70 to 2.20. The refractive index can be obtained by measurement using an Abbe refractometer or estimation from the reflectance of light from the layer surface. The thickness of the high refractive index layer is preferably 5 nm to 10 μm, more preferably 10 nm to 1 μm, and most preferably 30 nm to 0.5 μm. The haze of the high refractive index layer is preferably 5% or less, more preferably 3% or less, and most preferably 1% or less. The specific strength of the high refractive index layer is preferably H or more, more preferably 2H or more, and most preferably 3H or more, with a pencil hardness of 1 kg.
[0084]
The refractive index of the middle refractive index layer is adjusted to be a value between the refractive index of the low refractive index layer and the refractive index of the high refractive index layer. The refractive index of the middle refractive index layer is preferably 1.50 to 1.70.
It is particularly preferable that inorganic fine particles and a polymer are used for the high refractive index layer, and the middle refractive index layer is formed by adjusting the refractive index to be lower than that of the high refractive index layer. The haze of the medium refractive index layer is preferably 3% or less.
[0085]
[Other functional layers]
The antireflection film may further be provided with a hard coat layer, a moisture proof layer, an antistatic layer, an undercoat layer or a protective layer. The hard coat layer is provided for imparting scratch resistance to the transparent support. The hard coat layer also has a function of strengthening the adhesion between the transparent support and the layer thereon. The hard coat layer can be formed using an acrylic polymer, a urethane polymer, an epoxy polymer, a silicon polymer, or a silica compound. A pigment may be added to the hard coat layer. The acrylic polymer is preferably synthesized by a polymerization reaction of a polyfunctional acrylate monomer (eg, polyol acrylate, polyester acrylate, urethane acrylate, epoxy acrylate). Examples of the urethane polymer include melamine polyurethane. As the silicon-based polymer, a cohydrolyzate of a silane compound (eg, tetraalkoxysilane, alkyltrialkoxysilane) and a silane coupling agent having a reactive group (eg, epoxy, methacryl) is preferably used. Two or more kinds of polymers may be used in combination. As the silica compound, colloidal silica is preferably used. The strength of the hard coat layer is a pencil hardness with a 1 kg load, preferably H or higher, more preferably 2H or higher, and most preferably 3H or higher. On the transparent support, in addition to the hard coat layer, an adhesive layer, a shield layer, a sliding layer and an antistatic layer may be provided. The shield layer is provided to shield electromagnetic waves and infrared rays.
[0086]
[Smooth hard coat layer]
In the antiglare antireflection film of the present invention, a so-called smooth hard coat layer having no antiglare property for the purpose of improving the film strength is also preferably used, and is coated between the transparent support and the antiglare layer. . A smooth hard coat layer may be applied and cured by the same method before applying the antiglare layer.
The material used for the smooth hard coat layer is the same as that mentioned in the anti-glare layer except that the light-transmitting fine particles for imparting anti-glare properties are not used, and the resin binder or the resin binder It is formed from a mixture of inorganic ultrafine particle fillers.
In the smooth hard coat layer of the present invention, silica and alumina are preferable as the inorganic ultrafine particle filler in terms of strength and versatility, and silica is particularly preferable. The inorganic ultrafine particle filler is preferably subjected to silane coupling treatment on the surface, and a surface treatment agent having a functional group capable of reacting with the binder species on the filler surface is preferably used.
[0087]
The amount of these inorganic ultrafine particle fillers added is preferably 10 to 90% of the total mass of the hard coat layer, more preferably 20 to 70%, and particularly preferably 30 to 50%. The film thickness of the smooth hard coat layer is preferably 1 to 10 μm, more preferably 2 to 7 μm, and still more preferably 3 to 5 μm.
[0088]
The antiglare antireflection film of the present invention is a display for various image display devices such as various liquid crystal display devices (LCD), plasma display panels (PDP), electroluminescence displays (ELD), and cathode ray tube display devices (CRT). It can be used as an element.
As a specific example thereof, for example, the present invention can be applied to a polarizing plate used in a liquid crystal display device. That is, it is preferable to use it as a protective film for the polarizer (polarizing film) of the polarizing plate from the viewpoint of reducing the cost, making the polarizing plate thin and light, and effectively using resources.
As a preferred embodiment of the polarizing plate of the present invention, an optically anisotropic layer made of a liquid crystalline compound is provided on one protective film of a polarizer, and the antiglare antireflection film of the present invention is used as the other protective film. As a result, the liquid crystal cell of the liquid crystal display device can be optically compensated.
[0089]
More specifically, when the antiglare antireflection film of the present invention is used as one side of a surface protective film of a polarizing film, TN (Twisted Nematic), STN (Super Twisted Nematic), VA (Vertically Aligned), IPS ( In-Plane Switching), FLC (Ferroelectric Liquid Crystal), AFLC (Anti-ferroelectric Liquid Crystal), OCB (Optically Compensatory Bend), HAN (Hybrid Aligned Nematic), GH (Guest-Host), ASM (Axially Symmetric Aligned Microcell) It can be preferably used for a transmissive, reflective, or transflective liquid crystal display device of the mode. In particular, for TN mode and IPS mode liquid crystal display devices, as described in JP-A-2001-100043, an optical compensation film having a viewing angle widening effect is applied to two protective films on the back and front of a polarizing film. By using it on the surface opposite to the antireflection film of the present invention, a polarizing plate having an antireflection effect and a viewing angle widening effect can be obtained with the thickness of one polarizing plate, which is particularly preferable.
[0090]
When used in a transmissive or transflective liquid crystal display device, it is used in combination with a commercially available brightness enhancement film (a polarized light separation film having a polarization selective layer, such as D-BEF manufactured by Sumitomo 3M Co., Ltd.). Thus, a display device with higher visibility can be obtained. Further, by combining with a λ / 4 plate, it can be used to reduce reflected light from the surface and the inside as a polarizing plate for reflective liquid crystal or a surface protective plate for organic EL display. Furthermore, the antireflection layer of the present invention can be formed on a transparent support such as PET or PEN, and applied to an image display device such as a plasma display panel (PDP) or a cathode ray tube display device (CRT).
[0091]
As another specific example, an image display device such as PDP or CRT can be used by attaching the transparent support side of the antiglare antireflection film of the present invention to the image display surface of the image display device.
[0092]
[Polarizer]
The polarizing plate with the antiglare antireflection film of the present invention is formed by using the antiglare antireflection film as at least one of the two protective films of the polarizing layer. By using the antiglare antireflection film of the present invention on the outermost surface, reflection of outside light is prevented, and a polarizing plate having high definition aptitude, excellent antifouling property, scratch resistance, etc. Can do. In addition, since the antiglare antireflection film also serves as a protective film in the polarizing plate of the present invention, the manufacturing cost can be reduced, and the weight and resources can be saved.
[0093]
When the antiglare antireflection film of the present invention is used in a liquid crystal display device, it is preferably disposed on the outermost surface of the display by providing an adhesive layer on one side. When the transparent support is triacetylcellulose, triacetylcellulose is used as a protective film for protecting the polarizing layer of the polarizing plate. Therefore, the antiglare antireflection film of the present invention can be used as it is for the protective film.
The slow axis of the film (for example, cellulose acetate film) which is a protective film and the transmission axis of the polarizer are arranged so as to be substantially parallel.
[0094]
The polarizing plate with the antiglare and antireflection film of the present invention is obtained by forming an antiglare and antireflection layer on a transparent support, then surface-treating it, and bonding it to a polarizing film. A known method can be used for the surface treatment. An example is alkali saponification. The alkali saponification treatment is a method of saponifying the back surface of the film by immersing it in an alkali solution at least once, and the surface on which the anti-glare antireflection film of the antiglare antireflection film is formed with an alkali solution. It can be carried out by a method in which only the back surface of the film is saponified by applying to the opposite surface, heating, washing with water and / or neutralizing.
[0095]
[Polarizing film]
Any polarizing film can be applied as the polarizing film, and examples thereof include an iodine-based polarizing film, a dye-based polarizing film using a dichroic dye, and a polyene-based polarizing film. The iodine-based polarizing film and the dye-based polarizing film can be generally produced using a polyvinyl alcohol film. Further, the polarizing film can be produced either by a conventional production method or by oblique stretching.
[0096]
[Other films constituting polarizing plate]
In the polarizing plate of the present invention, it has been stated that an antiglare antireflection film can be used as one of protective films that can be disposed on both sides of the polarizing film. An optical compensation film composed of an optically anisotropic layer in which the orientation of the discotic liquid crystal is fixed can be used.
[0097]
[Liquid crystal compounds]
The liquid crystal compound used in the present invention may be a rod-like liquid crystal or a discotic liquid crystal, and they may be a polymer liquid crystal, a low molecular liquid crystal, or a liquid crystal compound in which a low molecular liquid crystal is crosslinked and does not exhibit liquid crystal properties. Can do.
As rod-shaped liquid crystals, azomethines, azoxys, cyanobiphenyls, cyanophenyl esters, benzoic acid esters, cyclohexanecarboxylic acid phenyl esters, cyanophenylcyclohexanes, cyano-substituted phenylpyrimidines, alkoxy-substituted phenylpyrimidines, phenyl Dioxanes, tolanes and alkenylcyclohexylbenzonitriles are preferably used. The rod-like liquid crystallinity includes a metal complex. A liquid crystal polymer containing rod-like liquid crystalline molecules in the repeating unit can also be used as the rod-like liquid crystal. In other words, the rod-like liquid crystal may be bonded to a (liquid crystal) polymer.
For rod-shaped liquid crystals, quarterly review of chemical review, volume 22, chemistry of liquid crystals (1994), Chapter 4, Chapter 7 and Chapter 11 of the Chemical Society of Japan, third part of the 142nd Committee of the Japan Society for the Promotion of Science Chapters and Japanese Patent Application Laid-Open No. 2000-304932.
[0098]
Most preferred as the liquid crystalline compound of the present invention is a discotic liquid crystal.
Examples of the discotic liquid crystal of the present invention include C.I. Destrade et al., Mol. Cryst. 71, 111 (1981), benzene derivatives described in C.I. Destrode et al. (Mol. Cryst. 122, p. 141 (1985), hysics lett, A, p. 78, p. 82 (1990)). The cyclohexane derivatives described in the research report of Kohne et al. (Angew. Chem. 96, 70 (1984)) M.M. Lehn et al. (J. Chem. Commun., 1794 (1985)), J. Chem. Examples include azacrown-type and phenylacetylene-type macrocycles described in a research report of Zhang et al. (J. Am. Chem. Soc. 116, 2655 (1994)). The discotic liquid crystal generally has a structure in which these are used as a mother nucleus at the center of a molecule, and a linear alkyl group, an alkoxy group, a substituted benzoyloxy group, etc. are radially substituted as the linear chain, and the liquid crystallinity is improved. Show. However, the molecule itself is not limited to the above description as long as the molecule itself has negative uniaxiality and can give a certain orientation. Further, in the present invention, the term “formed from a discotic compound” does not require that the final product is the above-mentioned compound. For example, the low-molecular discotic liquid crystal has a group that reacts with heat, light, or the like. As a result, it may be polymerized or cross-linked by reaction with heat, light or the like, resulting in high molecular weight and loss of liquid crystallinity. Preferred examples of the discotic liquid crystal are described in JP-A-8-50206.
[0099]
[Optically anisotropic layer]
The optically anisotropic layer of the present invention is a layer having negative birefringence composed of a compound having a discotic structural unit, and the angle of the surface of the discotic structural unit with respect to the transparent support surface is such that the depth of the optically anisotropic layer is It is preferable to change in the vertical direction.
[0100]
The tilt angle of the surface of the discotic structural unit generally increases or decreases in the depth direction of the optical anisotropic layer and with an increase in the distance from the bottom surface of the optical anisotropic layer. The tilt angle preferably increases with increasing distance. Further, the change in the inclination angle includes continuous increase, continuous decrease, intermittent increase, intermittent decrease, change including continuous increase and continuous decrease, and intermittent change including increase and decrease. it can. The intermittent change includes a region where the inclination angle does not change in the middle of the thickness direction. Even if the inclination angle includes a region that does not change, it is preferable that the inclination angle increases or decreases as a whole. Further, it is preferable that the inclination angle increases as a whole, and it is particularly preferable that the inclination angle changes continuously.
[0101]
The optically anisotropic layer is generally formed by applying a solution obtained by dissolving a discotic compound and other compounds in a solvent onto an alignment film, drying it, and then heating it to a discotic nematic phase formation temperature, and then aligning it (discotic nematic). Obtained by maintaining the phase) and cooling. Alternatively, the optically anisotropic layer is formed by applying a solution obtained by dissolving a discotic compound and another compound (for example, a polymerizable monomer, a photopolymerization initiator) in a solvent onto the alignment film, drying, and then discotic nematic. It is obtained by heating to the phase formation temperature, followed by polymerization (by irradiation with UV light, etc.) and further cooling. The discotic nematic liquid crystal phase-solid phase transition temperature of the discotic liquid crystalline compound used in the present invention is preferably from 70 to 300 degrees, particularly preferably from 70 to 170 degrees.
[0102]
For example, the tilt angle of the discotic unit on the support side can be generally adjusted by selecting a discotic compound or a material for the alignment film, or by selecting a rubbing treatment method. The inclination angle of the discotic unit on the surface side (air side) is generally selected from the discotic compound or other compounds (eg, plasticizer, surfactant, polymerizable monomer and polymer) used together with the discotic compound. Can be adjusted. Furthermore, the degree of change in the tilt angle can be adjusted by the above selection.
[0103]
As the plasticizer, surfactant and polymerizable monomer, any compound is used as long as it has compatibility with the discotic compound and can change the tilt angle of the liquid crystalline discotic compound or does not inhibit the alignment. Can also be used. Among these, polymerizable monomers (eg, compounds having a vinyl group, a vinyloxy group, an acryloyl group, and a methacryloyl group) are preferable. The above compound is generally used in an amount of 1 to 50% by mass (preferably 5 to 30% by mass) based on the discotic compound. Furthermore, a polyfunctional acrylate is mentioned as an example of a preferable polymerizable monomer. The number of functional groups is preferably 3 or more, and more preferably 4 or more. Most preferred is a hexafunctional monomer. A preferred example of the hexafunctional monomer is dipentaerythritol hexaacrylate. It is also possible to use a mixture of these polyfunctional monomers having different numbers of functional groups.
[0104]
Any polymer can be used as the polymer as long as it is compatible with the discotic compound and can change the tilt angle of the liquid crystalline discotic compound. Examples of polymers include cellulose esters. Preferred examples of the cellulose ester include cellulose acetate, cellulose acetate propionate, hydroxypropyl cellulose, and cellulose acetate butyrate. The polymer is generally 0.1 to 10% by mass (preferably 0.1 to 8% by mass, particularly 0.1 to 5% by mass) based on the discotic compound so as not to inhibit the alignment of the liquid crystalline discotic compound. ).
The optical compensation sheet of the present invention is an optical compensation sheet comprising a cellulose acetate film, an alignment film provided thereon, and a discotic liquid crystal formed on the alignment film, and a rubbing comprising a polymer in which the alignment film is crosslinked. Processed membrane.
[0105]
【Example】
The present invention is illustrated below by examples, but the present invention is not limited to these examples.
[0106]
Example 1
<Preparation of coating solution for antiglare layer>
An antiglare layer coating solution (BG-1) was prepared according to the following formulation and stirred to prepare.
[0107]
{Prescription of antiglare layer coating solution (BG-1)}
Desolite Z7526 (manufactured by JSR Corporation, refractive index 1.51, silica fine particle dispersion
Material-containing hard coat liquid (translucent resin)) 100 parts by mass
SX130H (manufactured by Soken Chemical Co., Ltd., particle size 1.3 μm, refractive index 1.61, crosslinked polystyrene
Renbeads (translucent fine particles)) 25 parts by mass
SX350H (manufactured by Soken Chemical Co., Ltd., particle size 3.5 μm, refractive index 1.61, cross-linked polystyrene
Renbeads (translucent fine particles)) 6 parts by mass
KBM-5103 (manufactured by Shin-Etsu Chemical Co., Ltd., refractive index 1.42, γ-acryloxypro)
Pyrtrimethoxysilane) 1 part by mass
Methyl ethyl ketone 32 parts by mass
128 parts by mass of methyl isobutyl ketone
[0108]
<Coating of anti-glare layer, production of light diffusion film>
On the triacetyl cellulose film (manufactured by Fuji Photo Film Co., Ltd., TD-80U), the coating amount of the anti-glare layer coating solution (BG-1) is 1.1 g / m with 1.3 μm crosslinked polystyrene beads.²After coating and solvent drying, an illuminance of 500 mW / cm using a 180 W / cm air-cooled metal halide lamp (manufactured by iGraphics)², Irradiation amount 500mJ / cm²The light-irradiating film (A-01) was produced by curing the coating layer by irradiating UV rays. The dry film thickness of the antiglare layer of this film was 3.2 μm. The refractive index of the translucent binder matrix was 1.51.
[0109]
<Preparation of coating solution for low refractive index layer>
The raw materials were prepared according to the following formulation, stirred, and then filtered through a polypropylene filter having a pore size of 1 μm to prepare a coating solution for low refractive index layer (TK-1).
[0110]
{Prescription of coating liquid for low refractive index layer (TK-1)}
JN-7228 (made by JSR, refractive index 1.42, thermally crosslinkable fluorine-containing polymer)
100 parts by weight
MEK-ST (manufactured by Nissan Chemical Co., Ltd., average particle size 10-20 nm, solid content concentration 30w
t%, SiO₂Sol methyl ethyl ketone dispersion) 9 parts by mass
56 parts by mass of methyl ethyl ketone
KBM-5103 (manufactured by Shin-Etsu Chemical Co., Ltd., refractive index 1.42, γ-acryloxypro)
Pyrtrimethoxysilane) 17 parts by mass
[0111]
On the anti-glare layer of the light diffusion film (A-01), the low refractive index layer coating solution (TK-1) is applied using a bar coater, dried at 80 ° C., and further 10 ° C. at 120 ° C. The film was thermally crosslinked for minutes to form a low refractive index layer having a thickness of 0.098 μm, and an antiglare and antireflection film (A-01) was produced.
[0112]
The particle size and the coating amount of the crosslinked polystyrene beads were changed, the dry film thickness of the antiglare layer was changed to 4.2 μm, and the light diffusion film (A-02) was formed so as to have the surface irregularities shown in Table 2. To (A-04) were prepared, and anti-glare antireflection films (A-02) to (A-04) were further prepared. The coating amount is also shown in Table 1.
[0113]
Change 1.3μm crosslinked polystyrene beads to 3μm silica beads (refractive index 1.44), change the particle size of 3.5μm crosslinked polystyrene beads, and change the antiglare layer dry film thickness to 4.2μm. Then, light diffusion films A-05 to A-06 were prepared so as to have surface irregularities shown in Table 1, and antiglare and antireflection films A-05 to A-06 were further prepared. The coating amount is shown in Table 1.
[0114]
Without adding 1.3 μm cross-linked polystyrene beads, the 3.5 μm cross-linked polystyrene beads are changed to PMMA particles, the antiglare layer dry film thickness is changed to 4.2 μm, and the surface irregularities shown in Table 1 are obtained. In addition, light diffusion films A-07 to A-08 were prepared, and antiglare and antireflection films A-07 to A-08 were further prepared. The coating amount is shown in Table 1.
[0115]
[Table 1]

[0116]
<Evaluation of antiglare and antireflection film>
About the obtained anti-glare antireflection film, the following items were evaluated. The results are shown in Table 2.
[0117]
(1) Surface roughness (Ra, Rz)
For the surface roughness, Ra and Rz were measured with an atomic force microscope (AFM: Atomic Force Microscope, SPI3800N, manufactured by Seiko Instruments Inc.), and Rz / Ra was calculated.
[0118]
(2) Specular reflectance
A spectrophotometer V-550 (manufactured by JASCO Corporation) is equipped with an adapter ARV-474, and in the wavelength region of 380 to 780 nm, the specular reflectance at an incident angle of 5 ° at an incident angle of 5 ° is measured. An average reflectance of 450 to 650 nm was calculated, and antireflection properties were evaluated.
(3) Integral reflectance
An adapter ILV-471 is attached to a spectrophotometer V-550 (manufactured by JASCO Corporation), and an integrated reflectance at an incident angle of 5 ° is measured in a wavelength region of 380 to 780 nm, and an average reflection of 450 to 650 nm. The rate was calculated.
[0119]
(4) Haze value
The haze of the obtained film was measured using a haze meter MODEL 1001DP (manufactured by Nippon Denshoku Industries Co., Ltd.). The internal haze was measured for a film in which an antiglare layer was formed and only a binder component contained in the antiglare layer was overcoated and the surface roughness Ra was less than 0.01. Value. The surface haze was calculated by subtracting the internal haze value from the haze value of the film formed up to the low refractive index layer.
[0120]
(5) Sprout failure
The opposite surface (support surface) of the surface on which the coating layer of each film is provided is painted black with black ink, and the surface of the coating surface is visually observed with an optical microscope (magnification: 50 times). The number of visible faulty faults due to resin particles (confirmed by an optical microscope) was counted.
[0121]
[Table 2]

[0122]
<Preparation of viewing side polarizing plate>
A polarizing film was prepared by adsorbing iodine to a stretched polyvinyl alcohol film.
The produced antiglare antireflection film (A-01) is subjected to saponification treatment, and a transparent support (triacetylcellulose) of the antiglare antireflection film (A-01) is polarized using a polyvinyl alcohol-based adhesive. It was affixed on one side of the polarizing film so as to be on the film side. Also, the following optical compensation film (KH-01) was attached to the opposite side of the polarizing film using a polyvinyl alcohol-based adhesive so that the cellulose acetate film was on the polarizing film side. The transmission axis of the polarizing film and the slow axis of the optical compensation film (KH-01) were arranged in parallel. In this manner, an antiglare antireflection polarizing plate (BHHA-01) was produced.
[0123]
<Preparation of optical compensation film (KH-01)>
(Preparation of cellulose acetate dope)
The following composition was put into a mixing tank and stirred while heating to dissolve each component to prepare a cellulose acetate dope solution (CA).
[0124]
{Composition of cellulose acetate solution (CA)}
100 parts by mass of cellulose acetate having an acetylation degree of 60.9%
8 parts by mass of triphenyl phosphate (plasticizer)
Biphenyldiphenyl phosphate (plasticizer) 4 parts by mass
300 parts by mass of methylene chloride (first solvent)
Methanol (second solvent) 54 parts by mass
1-butanol (third solvent) 11 parts by mass
[0125]
(Preparation of retardation increasing agent solution)
The following composition was put into another mixing tank and stirred while heating to dissolve each component to prepare a retardation increasing agent solution (RJ).
[0126]
{Formulation of retardation increasing agent solution (RJ)}
25 parts by mass of the following retardation increasing agent (Sumisolv TM165-F, manufactured by Sumitomo Chemical)
80 parts by mass of methylene chloride (first solvent)
Methanol (second solvent) 20 parts by mass
[0127]
[Chemical 1]

[0128]
(Production of cellulose acetate dope)
The following composition was put into a mixing tank and stirred to prepare a dope (CAD).
[0129]
{Cellulose acetate dope (CAD) formulation}
Cellulose acetate solution (CA) 487 parts by mass
Retardation increasing agent solution (RJ) 15 parts by mass
[0130]
The addition amount of the retardation increasing agent was 3.0 parts by mass with respect to 100 parts by mass of cellulose acetate.
[0131]
(Production of cellulose acetate film)
The obtained dope (CAD) was cast using a band casting machine. After the film surface temperature on the band reached 40 ° C., the film was dried for 1 minute, peeled off, and then dried with 140 ° C. air and the residual solvent amount was 0.3% by mass of cellulose acetate film (thickness: 60 μm). ) Was produced.
As a result of measuring optical characteristics of the produced cellulose acetate film (CAF-01), the Re retardation value was 5 nm and the Rth retardation value was 80 nm.
In addition, the optical property measured the Re retardation value and Rth retardation value in wavelength 550nm using the ellipsometer (M-150, JASCO Corporation make).
[0132]
The produced cellulose acetate film (CAF-01) is 1.5 N potassium hydroxide / (water / IPA / PG = 14/86/15 vol%) is 5 cc / m.²After coating and holding at 60 ° C. for about 10 seconds, the potassium hydroxide remaining on the film surface was washed with water and dried. The surface energy of this cellulose acetate film was determined by a contact angle method and found to be 63 mN / m.
On this cellulose acetate film, an alignment film coating solution (HM) having the following composition is 28 ml / m with a # 16 wire bar coater.²Applied. Drying was performed with warm air of 60 ° C. for 60 seconds, and further with warm air of 90 ° C. for 150 seconds.
Next, the formed film was rubbed in a direction parallel to the longitudinal direction of the cellulose acetate film.
[0133]
(Preparation of alignment film coating solution)
The following composition was put into a mixing tank and stirred while heating to dissolve each component to prepare an alignment film coating solution (HM).
[0134]
{Formulation of alignment film coating solution (HM)}
10 parts by mass of the following modified polyvinyl alcohol
371 parts by weight of water
119 parts by mass of methanol
Glutaraldehyde (crosslinking agent) 0.5 parts by mass
[0135]
[Chemical formula 2]

[0136]
(Formation of optically anisotropic layer)
A compound having the following formulation was charged and dissolved in a SUS tank to obtain an optically anisotropic layer coating solution.
[0137]
{Optical anisotropic layer coating solution formulation}
4200 parts by mass of the following discotic liquid crystalline molecules
Ethylene oxide modified trimethylolpropane triacrylate
(V # 360, Osaka Organic Chemical Co., Ltd.)) 400 parts by mass
Cellulose acetate butyrate
(CAB551-0.2, manufactured by Eastman Chemical Co.) 92 parts by mass
Cellulose acetate butyrate
(CAB531-1, manufactured by Eastman Chemical Co.) 23 parts by mass
140 parts by mass of photopolymerization initiator (Irgacure-907, manufactured by Ciba Geigy)
Sensitizer (Kayacure-DETX, Nippon Kayaku Co., Ltd.) 45 parts by mass
Methyl ethyl ketone 10100 parts by mass
[0138]
[Chemical 3]

[0139]
On the alignment film formed as described above, the optically anisotropic layer coating solution was applied with a wire bar of # 3.6. This was heated in a constant temperature zone of 130 ° C. for 2 minutes to orient the discotic compound. Next, UV irradiation was performed for 1 minute using a 120 W / cm high pressure mercury lamp in an atmosphere of 60 ° C. to polymerize the discotic compound. Then, it stood to cool to room temperature. Thus, an optically anisotropic layer was formed, and an optical compensation film (KH-01) was produced.
The Re retardation value of the optically anisotropic layer measured at a wavelength of 550 nm was 43 nm. The angle (tilt angle) between the disk surface and the first transparent support surface was 42 ° on average.
[0140]
In the same manner as the antiglare antireflection polarizing plate (BHHA-01) was produced, the antiglare antireflection polarizing plate (A-02) to (A08) was used. BHHA-02) to (BHHA-08) were prepared.
[0141]
<Preparation of backlight-side polarizing plate>
A polarizing film was prepared by adsorbing iodine to a stretched polyvinyl alcohol film. A commercially available triacetylcellulose film (Fuji Photo Film, Fujitac TD80) was saponified and attached to one side of the polarizing film using a polyvinyl alcohol adhesive. Further, the optical compensation film (KH-01) was subjected to saponification treatment and attached to the opposite side using a polyvinyl alcohol adhesive so that the cellulose acetate film was on the polarizing film side. In this way, a backlight side polarizing plate was produced.
[0142]
<Production of liquid crystal display device>
A pair of polarizing plates provided in a liquid crystal display device (6E-A3, manufactured by Sharp Corporation) using a TN type liquid crystal cell is peeled off, and instead of polarizing plates (BHHA-01) to (BHHA-08), Each optical compensation film was attached to the viewer side via an adhesive so that the optical compensation film was on the liquid crystal cell side. On the backlight side, a backlight side polarizing plate was attached via an adhesive so that the optical compensation film was on the liquid crystal cell side. The transmission axis of the polarizing plate on the viewer side and the transmission axis of the polarizing plate on the backlight side were arranged to be in the O mode.
[0143]
<Evaluation of liquid crystal display device>
About the produced liquid crystal display device, the following items were evaluated. The results are shown in Table 3.
[0144]
(6) Viewing angle
Using a measuring machine (EZ-Contrast 160D, manufactured by ELDIM), the viewing angle was measured in 8 stages from black display (L1) to white display (L8).
The viewing angle was determined in a range where the contrast ratio was 10 or more and there was no gradation inversion. Black-side gradation inversion was determined by inversion between L1 and L2.
[0145]
(7) Anti-glare evaluation
Bare fluorescent light without louver (8000 cd / m²) And the degree of blur of the reflected image was evaluated according to the following criteria.
I do not know the outline of the fluorescent lamp at all: ◎
Slightly understand the outline of the fluorescent lamp: ○
Fluorescent lamp is hardly blurred: ×
[0146]
[Table 3]

[0147]
The following was found from the results shown in Tables 1 to 3.
The anti-glare antireflection film of the present invention has very few bump-like failures, the visual field characteristics of a display device using a polarizing plate using the anti-glare antireflection film, and the difficulty of reflecting outside light (anti-glare property). ) Was confirmed to be very good. On the other hand, the antiglare antireflection film of Comparative Example 101 had white powder stains even though there was no lumpy failure, and was found to be unsuitable for use as an antiglare antireflection film. In addition, the visual field characteristics of the display device using the polarizing plate using the antiglare and antireflection film shown in Comparative Example 111 and the difficulty of reflection of external light (antiglare) are inferior to those of the present invention. Was confirmed.
[0148]
Example 2
<Preparation of coating solution for antiglare layer>
An antiglare layer coating solution (BG-2) was prepared according to the following formulation and stirred to prepare.
[0149]
{Anti-glare layer coating solution (BG-2) formulation}
Desolite KZ-7114A (manufactured by JSR Corporation, including zirconium oxide dispersion)
Hard coat coating liquid (translucent resin)) 100 parts by mass
DPHA (manufactured by Nippon Kayaku Co., Ltd., dipentaerythritol hexaacrylate
(Translucent resin) 57 parts by mass
MX150 (manufactured by Soken Chemical Co., Ltd., particle size 1.5 μm, refractive index 1.49, polymethylmethacrylate)
Relate beads (translucent fine particles)) 17 parts by mass
MX300 (manufactured by Soken Chemical Co., Ltd., particle size: 3.0 μm, refractive index: 1.49, polymethyl methacrylate)
Relate beads (translucent fine particles)) 7 parts by mass
KBM-5103 (manufactured by Shin-Etsu Chemical Co., Ltd., refractive index 1.42, γ-acryloxypro)
Pyrtrimethoxysilane) 1 part by mass
36 parts by mass of methyl ethyl ketone
146 parts by mass of methyl isobutyl ketone
[0150]
<Coating of anti-glare layer, production of light diffusion film>
The coating amount of 1.5 μm polymethyl methacrylate-based beads on a triacetyl cellulose film (TD-80U, manufactured by Fuji Photo Film Co., Ltd.) is 0.4 g / m.²After coating the antiglare coating solution (BG-2) and drying the solvent, an illuminance of 500 mW / cm using a 180 W / cm air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.)², Irradiation amount 500mJ / cm²The light diffusing film (B-01) was prepared by curing the coating layer by irradiating UV light. The dry film thickness of the antiglare layer of this film was 3.0 μm. The refractive index of the coating film obtained by applying a liquid containing no translucent fine particles and curing with ultraviolet rays was 1.61.
[0151]
On the anti-glare layer of the light diffusion film (B-01), the above-mentioned coating solution for low refractive index layer (TK-1) is applied using a bar coater, dried at 80 ° C., and further 10 ° C. at 120 ° C. The film was thermally crosslinked for minutes to form a low refractive index layer having a thickness of 0.098 μm, and an antiglare and antireflection film (B-01) was produced.
[0152]
The particle size and coating amount of the polymethylmethacrylate beads were changed, the dry film thickness of the antiglare layer was changed to 4.2 μm, and the light diffusion film (B− 02), (B-06) to (B-08) were prepared, and antiglare and antireflection films (B-02) and (B-06) to (B-08) were further prepared. The coating amount is shown in Table 4.
[0153]
The surface shown in Table 5 was changed from 1.5 μm polymethylmethacrylate beads to 3 μm silica beads (made by Nippon Shokubai Co., Ltd., refractive index 1.44), and changed the particle size and coating amount of 3.0 μm polymethylmethacrylate beads. Light diffusing films (B-03) to (B-05) were prepared so as to be uneven, and antiglare antireflection films (B-03) to (B-05) were further prepared. The coating amount is shown in Table 4.
[0154]
Without adding 1.5 μm polymethylmethacrylate beads, change 3.5 μm polymethylmethacrylate beads to crosslinked polystyrene beads, make the antiglare layer dry film thickness 3.0 μm, and make the surface irregularities shown in Table 5 Light diffusion films (B-09) to (B-10) were prepared, and antiglare and antireflection films (B-09) to (B-10) were further prepared. The coating amount is shown in Table 4.
[0155]
[Table 4]

[0156]
Using the anti-glare antireflection films (B-01) to (B-10) and the optical compensation film (KH-01) in the same manner as the anti-glare antireflection polarizing plate (BHHA-01) was produced. Antiglare and antireflection polarizing plates (BHHB-01) to (BHHB-10) were produced.
The same items as in Example 1 were evaluated for the obtained antiglare antireflection film and the produced liquid crystal display device. The results are shown in Tables 5 and 6.
[0157]
[Table 5]

[0158]
[Table 6]

[0159]
The following was found from the results shown in Tables 4-6.
The anti-glare antireflection film of the present invention has very few bump-like failures, the visual field characteristics of a display device using a polarizing plate using the anti-glare antireflection film, and the difficulty of reflecting external light (anti-glare properties). ) Was confirmed to be very good. On the other hand, the antiglare antireflection film of Comparative Example 201 has Ra and Rz / Ra values that are outside the scope of the present invention, and a large number of bump-like failures occur, making it unsuitable for use as an antiglare antireflection film. Met. Moreover, although the antiglare antireflection film of Comparative Example 202 did not have a fluffy failure, white dust was generated, and it was found that the antiglare antireflection film was unsuitable for use as an antiglare antireflection film. The visual field characteristics of the display device using the polarizing plate using the antiglare and antireflection film shown in Comparative Examples 211 and 212, and the difficulty in reflecting outside light (antiglare) are inferior to those of the present invention. Was confirmed.
[0160]
Example 3
<Preparation of coating solution for antiglare layer>
An antiglare layer coating solution (BG-3) was prepared according to the following formulation and stirred to prepare.
[0161]
{Anti-glare layer coating solution (BG-3) formulation}
Trimethylolpropane triacrylate (translucent resin)) 100 parts by mass
SX350H (manufactured by Soken Chemical Co., Ltd., particle size 3.0 μm, refractive index 1.61, cross-linked polystyrene)
Beads (translucent fine particles)) 10 parts by mass
SX500H (manufactured by Soken Chemical Co., Ltd., particle size 5.0 μm, refractive index 1.61, cross-linked polystyrene)
Beads (translucent fine particles)) 10 parts by mass
KBM-5103 (manufactured by Shin-Etsu Chemical Co., Ltd., refractive index 1.42, γ-acryloxypro)
Pyrtrimethoxysilane) 1 part by mass
24 parts by mass of methyl ethyl ketone
96 parts by mass of methyl isobutyl ketone
[0162]
<Coating of anti-glare layer, production of light diffusion film>
On a triacetylcellulose film (manufactured by Fuji Photo Film Co., Ltd., TD-80U), the coating amount of 3.5 μm crosslinked polystyrene beads is 0.4 g / m.²After coating the antiglare layer coating solution (BG-3) and drying the solvent, an illuminance of 500 mW / cm using a 180 W / cm air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.)², Irradiation amount 500mJ / cm²The coating layer was cured by irradiating the ultraviolet rays, and a light diffusion film (C-01) was produced. The dry film thickness of the antiglare layer of this film was 4.2 μm. The refractive index of the translucent binder matrix was 1.52.
[0163]
On the anti-glare layer of the light diffusing film (C-01), the above coating solution for low refractive index layer (TK-1) is applied using a bar coater, dried at 80 ° C., and further 10 ° C. at 120 ° C. The film was heat-crosslinked for a minute to form a low refractive index layer having a thickness of 0.098 μm, and an antiglare and antireflection film (C-01) was produced.
[0164]
The light-diffusing films (C-02) to (C-03) were prepared so that the surface irregularities shown in Table 8 were obtained by changing the coating amount of the cross-linked polystyrene beads, and antiglare antireflection film (C-02). ) To (C-03). The coating amount is shown in Table 7.
[0165]
The 3.5 μm crosslinked polystyrene beads were changed to 3 μm silica beads (refractive index 1.44), the coating amount was changed, and a light diffusion film (C-04) was prepared so as to have surface irregularities shown in Table 8. Further, an antiglare antireflection film (C-04) was produced. The coating amount is shown in Table 7.
[0166]
Without adding 3.5 μm cross-linked polystyrene beads, 5 μm cross-linked polystyrene beads were changed to PMMA beads (refractive index 1.49), and a light diffusion film (C-05) was prepared so as to have surface irregularities shown in Table 8. Further, an antiglare antireflection film (C-05) was produced. The coating amount is shown in Table 7.
[0167]
[Table 7]

[0168]
Using the anti-glare antireflection films (C-01) to (C-05) and the optical compensation film (KH-01) in the same manner as the antiglare antireflection polarizing plate (BHHA-01) was produced. Antiglare and antireflection polarizing plates (BHHC-01) to (BHHC-05) were produced.
The same items as in Example 1 were evaluated for the obtained antiglare antireflection film and the produced liquid crystal display device. The results are shown in Tables 8 and 9.
[0169]
[Table 8]

[0170]
[Table 9]

[0171]
The following was found from the results shown in Tables 7-9.
The anti-glare antireflection film of the present invention has very few bump-like failures, the visual field characteristics of a display device using a polarizing plate using the anti-glare antireflection film, and the difficulty of reflecting external light (anti-glare properties). ) Was confirmed to be very good.
[0172]
From the examples shown above, the liquid crystal display device provided with an antiglare antireflection film having an Ra of 0.02 to 1.0 μm and an Rz / Ra of 30 or less has excellent viewing angle characteristics and antiglare properties. It was confirmed to have
[0173]
【The invention's effect】
According to the present invention, the anti-glare antireflection film of the present invention is further provided with an optically anisotropic layer comprising a polarizer and a liquid crystalline compound, thereby widening the viewing angle (particularly the downward viewing angle), It is possible to provide a liquid crystal display device that hardly causes a decrease in contrast due to a change in viewing angle, gradation or black-and-white reversal, hue change, and the like, is inexpensive, and does not have uneven surface defects. That is, it is possible to obtain an antiglare antireflection film and further a polarizing plate, which can give excellent performance to the quality of the liquid crystal display device and also to the surface uniformity.
Furthermore, a liquid crystal display device and an image display device provided with a polarizing plate having excellent performance can be provided.
[Brief description of the drawings]
FIG. 1 is a schematic cross-sectional view showing the basic configuration of an antiglare and antireflection film.
[Explanation of symbols]
1 Anti-glare anti-reflection film
2 Transparent support
3 Antiglare layer
4 Low refractive index layer
5 Translucent fine particles (anti-glare particles)
6 Translucent fine particles (scattering particles)

Claims (6)

An antiglare antireflection film having at least one antiglare layer in which translucent fine particles are dispersed in a translucent binder matrix and a low refractive index layer having a lower refractive index than the lower layer on a transparent support. The refractive index of the translucent binder matrix in the antiglare layer is in the range of 1.48 to 2.00, and the difference in refractive index Δn between the translucent binder matrix and the translucent fine particles is 0. The internal haze value due to internal scattering of the antiglare layer is 30 to 80%, the surface haze value due to surface irregularities of the antiglare layer is 7 to 25%, Translucent fine particles for imparting antiglare properties having a haze value of 40 to 90%, using two or more kinds of translucent fine particles having different particle diameters, and at least one kind having a particle diameter of 1.6 to 12 μm And a particle size of 0.8 to 2.0 times the thickness of the antiglare layer , And the a in particulate least one confers internal scattering property, and the particle size of particles of particle size smaller than the thickness of the antiglare layer is 1.0～6.0Myuemu, translucent binder The difference in refractive index between the matrix and the translucent fine particles imparting the internal scattering property is 0.05 to 0.50, the surface roughness Ra is 0.02 to 1.00 μm, and Rz / Ra Is an antiglare antireflection film, wherein the antiglare film is 30 or less.   A polarizing plate having both surfaces of a polarizer sandwiched between protective films, wherein at least one of the protective films is the antiglare antireflection film according to claim 1.   2. An antiglare antireflection film according to claim 1, wherein the polarizing plate has both sides of the polarizer sandwiched between protective films, the protective film has an optically anisotropic layer made of a liquid crystalline compound on one side, and the other protective film is provided. A polarizing plate characterized by being a film.   The polarizing plate according to claim 3, wherein the liquid crystal compound is a discotic compound.   5. A liquid crystal display device, wherein the optically anisotropic layer side of the polarizing plate according to claim 2 is disposed on a liquid crystal cell surface. An antiglare antireflection film having at least one antiglare layer in which translucent fine particles are dispersed in a translucent binder matrix and a low refractive index layer having a lower refractive index than the lower layer on a transparent support. The antiglare antireflection film has a refractive index of the translucent binder matrix in the antiglare layer in the range of 1.48 to 2.00, and the translucent binder matrix and the translucent binder The difference Δn in refractive index with the light-sensitive fine particles is 0.00 to 0.50, the internal haze value due to internal scattering of the antiglare layer is 30 to 80%, and the surface unevenness of the antiglare layer is The surface haze value is 7 to 25%, the total haze value is 40 to 90%, two or more kinds of translucent fine particles having different particle diameters are used, and at least one kind has a particle diameter of 1.6 to 12 μm. Translucent fine particles for imparting antiglare properties, and The particle size is 0.8 to 2.0 times the thickness of the antiglare layer, at least one kind is a particle imparting internal scattering properties, and the particle size is smaller than the thickness of the antiglare layer. The particle size is 1.0 to 6.0 μm, the difference in refractive index between the translucent binder matrix and the translucent fine particles imparting the internal scattering property is 0.05 to 0.50, and the surface The roughness Ra is 0.02 to 1.00 μm and Rz / Ra is 30 or less, and the coating solution for forming an antiglare layer contains two or more kinds of translucent fine particles having different particle diameters. and a boiling point of 100 ° C. or more solvents viewed from 1 to 95% free of all solvents antiglare layer forming coating solution, the antiglare layer coating solution was coated on a transparent support, and heated and dried Thereafter, the antiglare layer is formed by light irradiation or heating, and a low refractive index layer coating solution is further applied on the antiglare layer, and light irradiation or heating is applied. A method for producing an antiglare antireflection film, which comprises heating to form a low refractive index layer .

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