JPWO2006051784A1 - 反射防止フィルム、偏光板およびディスプレイ - Google Patents
反射防止フィルム、偏光板およびディスプレイ Download PDFInfo
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- JPWO2006051784A1 JPWO2006051784A1 JP2006544896A JP2006544896A JPWO2006051784A1 JP WO2006051784 A1 JPWO2006051784 A1 JP WO2006051784A1 JP 2006544896 A JP2006544896 A JP 2006544896A JP 2006544896 A JP2006544896 A JP 2006544896A JP WO2006051784 A1 JPWO2006051784 A1 JP WO2006051784A1
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Abstract
Description
例えば、特開平6−255053号公報には、少なくとも2層以上を有する熱可塑性樹脂シートにおいて、その少なくとも1層が、非晶質ポリオレフィンであることを特徴とする成形用熱可塑性樹脂シート及びその成形体が記載されている。この熱可塑性樹脂シートは、水蒸気バリア性、透明性に優れるとともに、金型との融着性が無く、広い温度範囲で成形が可能であると記載されている。
(1)反射防止層及び基材樹脂層を少なくとも有し、前記基材樹脂層が熱可塑性樹脂を主たる成分とする、a層及びb層を少なくとも含んでなり、前記a層の曲げ弾性率がb層の曲げ弾性率より大きく、かつ前記a層が反射防止層側に存在することを特徴とする反射防止フィルム。
(2)前記a層の熱可塑性樹脂が、ビニル芳香族重合体、ポリアクリレート重合体、ポリメタクリレート重合体、ビニル脂環式炭化水素重合体及びその水素化物のいずれかである(1)の反射防止フィルム。
(3)前記b層の熱可塑性樹脂が、脂環式構造含有重合体、セルロース重合体、ポリエステル重合体のいずれかである(1)又は(2)の反射防止フィルム。
(5)前記a層とb層の組み合わせが、a層/b層で表したとき、ビニル芳香族重合体/脂環式構造含有重合体、ポリアクリレート重合体/脂環式構造含有重合体、ポリメタクリレート重合体/脂環式構造含有重合体のいずれかである(1)〜(4)のいずれかの反射防止フィルム。
(6)前記反射防止層が、屈折率1.40以下の低屈折率層を含む層であることを特徴とする(1)〜(5)のいずれかの反射防止フィルム。
(7)前記基材樹脂層が、共押出法により得られたものであることを特徴とする(1)〜(6)のいずれかの反射防止フィルム。
(8)本発明の反射防止フィルムを偏光子に貼り合わせてなることを特徴とする偏光板。
また本発明の第3によれば、下記(9)のディスプレイが提供される。
(9)本発明の偏光板を備えることを特徴とするディスプレイ。
1)反射防止フィルム
本発明の反射防止フィルムは、反射防止層及び基材樹脂層を少なくとも有し、前記基材樹脂層が熱可塑性樹脂を主たる成分とする、a層及びb層を少なくとも含んでなり、前記a層の曲げ弾性率がb層の曲げ弾性率より大きく、かつ前記a層が反射防止層側に存在することを特徴とする。
本発明の反射防止フィルムの基材樹脂層は、熱可塑性樹脂を主たる成分とする、a層及びb層を少なくとも含むものである。ここで、「熱可塑性樹脂を主たる成分とする」とは、a層及びb層を構成する樹脂成分が熱可塑性樹脂であって、所望により配合剤等が含まれていてもよいという意味である。
a層に含まれる熱可塑性樹脂としては、透明性の高い熱可塑性樹脂であれば、特に制限されない。なかでも、光線透過率が80%以上、ヘイズが0.5%以下であるものが好ましい。
b層を構成する熱可塑性樹脂としては、透明性の高い熱可塑性樹脂であれば、特に制限されない。なかでも、光線透過率が80%以上、ヘイズが0.5%以下であるものが好ましい。
開環重合触媒としては、通常使用される公知のものを使用できる。
また、環状共役ジエン重合体としては、例えば、シクロペンタジエン、シクロヘキサジエン等の環状共役ジエン単量体を1,2−付加重合又は1,4−付加重合した重合体を挙げることができる。
本発明の反射防止フィルムの基材樹脂層は、熱可塑性樹脂を主たる成分とする、a層及びb層を少なくとも含み、前記a層の曲げ弾性率がb層の曲げ弾性率より大きいことを特徴とする。
共押出法により積層体を得る方法は、具体的には、複数の押出機を用い、a層を構成する樹脂材料とb層を構成する樹脂材料とを多層ダイから押出すことにより成膜するものである。
その一方、厚みが100μmより厚くなると、フィルムが脆くなるため好ましくない。
透湿度は、JIS K 7209に準拠した方法で測定することができる。
(図1−a)に示すものは、a層−b層の2層構造からなる基材樹脂層(10A)、(図1−b)に示すものは、a層−b層−a層の3層構造からなる基材樹脂層(10B)、(図1−c)に示すものは、a層−b層−c層の3層構造からなる基材樹脂層(10C)、(図1−d)に示すものは、a層−x層−b層の3層構造からなる基材樹脂層(10D)、(図1−e)に示すものは、a層−x層−b層−x層−a層の5層構造からなる基材樹脂層(10E)、また、(図1−f)に示すものは、a層−x層−b層−x層−c層の5層構造からなる基材樹脂層(10F)である。本発明の反射防止フィルムを構成する基材樹脂層は、(図1−a)〜(図1−f)に示すものに限定されず、少なくともa層とb層を有するものであればよい。
本発明の反射防止フィルムは、前記基材樹脂層のa層上に反射防止層が形成されてなる。反射防止層は界面における反射を抑え、光線透過率を向上させる機能を有する層である。反射防止層としては、公知の層構成のものが採用でき、例えば、屈折率が相対的に低い低屈折率層からなるもの、屈折率が相対的に高い高屈折率層と、屈折率が相対的に低い低屈折率層が積層された層からなるもの等が挙げられる。
(b)前記式(1)で表される化合物の少なくとも1種の部分加水分解生成物。
(c)前記式(1)で表される化合物の少なくとも1種の完全加水分解生成物。
また、nは前記M(金属原子又は半金属原子)の原子価を表す。nが2以上のとき、Xは同一であっても相異なっていてもよい。
加水分解は、5〜100℃の温度で、2〜100時間、全容を撹拌することにより行うことができる。
得られる低屈折率層の厚みは、通常10〜1000nm、好ましくは50〜500nmである。
また、反射防止層が高屈折率層と低屈折率層からなる場合、基材樹脂層と高屈折率層との間、若しくは高屈折率層と低屈折率層との間にその他の層を介在させることができる。
ハードコート層は、基材樹脂層又は高屈折率層(以下、これらを「支持体」ということがある)の表面硬度、耐繰り返し疲労性及び耐擦傷性を補強する目的で形成される。ハードコート層の形成材料としては、JIS K 5400に規定される鉛筆硬度試験で、「HB」以上の硬度を示すものであれば特に制限されない。例えば、有機シリコーン系、メラミン系、エポキシ系、アクリル系、ウレタンアクリレート系等の有機系ハードコート材料;二酸化ケイ素等の無機系ハードコート材料;等が挙げられる。なかでも、接着力が良好であり、生産性に優れる観点から、ウレタンアクリレート系、多官能アクリレート系ハードコート材料の使用が好ましい。また、ハードコート層には、無機フィラーが含まれていてもよい。
具体的な例としてはパーフルオロアルキルシラン化合物、パーフルオロポリエーテルシラン化合物、フッ素含有シリコーン化合物を使用することができる。防汚層の形成方法は、形成する材料に応じて、例えば、蒸着、スパッタリング等の物理的気相成長法;化学的気相成長法;湿式低屈折率層形成法;等を用いることができる。 防汚層の厚みは特に制限はないが、通常20nm以下が好ましく、1〜10nmであるのがより好ましい。
本発明の偏光板は、本発明の反射防止フィルムを、偏光子に貼り合わせてなることを特徴とする。
また、ポリエン系の偏光子を製造する方法としては、PVA系フィルムを一軸に延伸した後に脱水触媒存在下で加熱・脱水する方法、ポリ塩化ビニル系フィルムを一軸に延伸した後に脱塩酸触媒存在下で加熱・脱水する方法等の公知の方法が挙げられる。
保護層の総厚みは、通常20〜300μm、好ましくは40〜200μmである。
本発明の偏光板は、本発明の反射防止フィルムを用いているので、反射防止性能、靭性及び表面硬度のすべての面に優れている。
本発明のディスプレイは、本発明の偏光板を備えることを特徴とする。本発明のディスプレイの好ましい具体例としては、液晶表示装置等が挙げられる。
(1)樹脂材料
樹脂a:
ポリメチルメタクリレート(以下、「PMMA」と略記する。商品名:アクリペットVH001,三菱レーヨン社製)
ポリスチレン(以下、「PS」と略記する。商品名:トーヨースチロールGP.G320C,東洋スチレン社製)
ノルボルネン樹脂(以下、「NB」と略記する。商品名:ゼオノア1060、日本ゼオン社製)
ポリカーボネート樹脂(以下、「PC」と略記する。商品名:パンライトK−1300Y,帝人化成社製)
トリアセチルセルロース(以下、「TAC」と略記する。厚さ40μm、商品名:KC40X2M,コニカミノルタ社製)
エチレン−酢酸ビニル共重合体(以下、「EVA1」と略記する。商品名:EVAFLEX、三井デュポンケミカル社製)
変性エチレン−酢酸ビニル共重合体(以下、「EVA2」と略記する。商品名:三菱モディックAP543)
基材樹脂層のa層とb層の曲げ弾性率は、JIS K 7171に準じて、引っ張り試験機(オートグラフAG−100kNIS、島津製作所社製)を使用して測定した。
(3)透湿度の測定
透湿度は、JIS K 7209に準拠して測定した。
(1−1)基材樹脂層を構成する透明フィルム(1A)の製造
PMMAを、目開き10μmのリーフディスク形状のポリマーフィルターを設置したダブルフライト型50mmの一軸押出機(スクリュー有効長さLとスクリュー径Dとの比L/D=28)に装填されたホッパーへ投入し、押出機出口温度260℃、押出機のギヤポンプの回転数12rpmで溶融樹脂をダイスリップの表面粗さRaが0.1μmであるマルチマニホールドダイに供給した。
無水マレイン酸変性スチレン・ブタジェン・スチレンブロック共重合体の水素添加物(商品名:タフテックM1913、旭化成社製、メルトインデックス値は200℃、5kg荷重で1.0g/10分、スチレンブロック含量30重量%、水素添加率80%以上、無水マレイン酸付加量2%)2部を、キシレン8部とメチルイソブチルケトン40部の混合溶媒に溶解し、孔径1μmのポリテトラフルオロエチレン製のフィルターをろ過して、ろ過した溶液のみをプライマー溶液として調製した。
6官能ウレタンアクリレートオリゴマー(商品名:NK オリゴ U−6HA、新中村化学社製)30部、ブチルアクリレート40部、イソボロニルメタクリレート(商品名:NK エステル 1B、新中村化学社製)30部、2,2−ジメトキシ−1,2−ジフェニルエタン−1−オン10部をホモジナイザーで混合して紫外線硬化性樹脂組成物からなるハードコート剤を調製した。
テトラメトキシシランのオリゴマー(商品名:メチルシリケート51、コルコート社製)と、メタノール、水、0.01Nの塩酸水溶液を質量比21:36:2:2で混合し、これを25℃の高温槽中で2時間撹拌して、重量平均分子量を850に調製し、シリコーンレジンを得た。次に、中空シリカ微粒子として中空シリカイソプロパノール分散ゾル(触媒化成工業社製、固形分20重量%、平均一次粒子径約35nm、外殻厚み約8nm)を前記シリコーンレジンに加え、中空シリカ微粒子/シリコーンレジン(縮合化合物換算)が固形分基準で重量比が8:2となるように配合し、その後、全固形分が1%になるようにメタノールで希釈し、低屈折率層形成用塗布液を調製した。
(1−1)で得た透明フィルム(1A)の両面に、高周波発信機(コロナジェネレータHV05−2、Tamtec社製)を用いて、出力電圧100%、出力250Wで、直径1.2mmのワイヤー電極で、電極長240mm、ワーク電極間1.5mmの条件で3秒間コロナ放電処理を行い、表面張力が0.072N/mになるように表面改質して表面改質済み基材樹脂フィルムを得た。
実施例1において、樹脂aとしてPMMAの代わりにPSを使用した以外は実施例1と同様にして、a層(20μm)−x層(4μm)−b層(52μm)−x層(4μm)−a層(20μm)の3種5層からなる幅600mm、厚さ100μmの透明フィルム(1B)を共押出成形により得た。その後は実施例1と同様にして、反射防止フィルム(2B)を作製した。
実施例1の共押出成形において、3種5層からなる透明フィルムに代えて、a層(30μm)−x層(4μm)−b層(66μm)の3種3層からなる透明フィルムを得る以外は実施例1と同様にして、幅600mm、厚さ100μmの透明フィルム(1C)を得た。その後は実施例1と同様にして、反射防止フィルム(2C)を得た。
実施例1において、樹脂bとしてNBの代わりにPCを使用した以外は実施例1と同様にして、a層(20μm)−x層(4μm)−b層(32μm)−x層(4μm)−a層(20μm)の3種5層からなる幅600mm、厚さ80μmの透明フィルム(1D)を共押出成形により得た。その後は実施例1と同様にして、反射防止フィルム(2D)を得た。
実施例1において、樹脂bとしてNBの代わりにTACを使用した。このTACフィルムの両面にEVA2の10重量%トルエン溶液を、乾燥後の厚さが3μmになるように塗布した。次に、厚さ20μmのPMMAフィルムをTACフィルムの両面に圧着ラミネートし、a層(20μm)−x層(3μm)−b層(40μm)−x層(3μm)−a層(20μm)の3種5層からなる幅600mm、厚さ86μmの透明フィルム(1E)を得た。その後は実施例1と同様にして、反射防止フィルム(2E)を得た。
PMMAを単層押出しし、厚みが100μmの透明フィルム(1F)を得、その他は実施例1と同様にして、反射防止フィルム(2F)を得た。
NBからなる単層フィルムで、厚みが100μmの透明フィルム(1G)を用い、その他は実施例1と同様にして、反射防止フィルム(2G)を得た。
(6−1)偏光子の製造
厚さ75μmのポリビニルアルコールフィルム(商品名:クラレビニロン#7500、クラレ社製)をチャック装着し、ヨウ素0.2g/L、ヨウ化カリウム30g/Lの組成の水溶液に浸漬するとともに、同時に6.0倍に一軸延伸しつつ、5分間に亘ってホウ酸処理を行った。最後に、室温で24時間乾燥し、偏光子を作製した。偏光度は99.995%であった。
ノルボルネン樹脂フィルム(商品名:ゼオノアフィルムZF−14−100、厚み100μm、日本ゼオン社製)を、同軸二軸延伸機を使用して、オーブン温度(予熱温度、延伸温度、熱固定温度とも)136℃、縦延伸倍率1.41倍、横延伸倍率1.41倍で同時二軸延伸を行い、厚さ89μmの延伸フィルムを得た。得られた延伸フィルムの面内のリターデーション(Re)は20nm、厚さ方向のリターデーション(Rth)は300nmであった。この延伸フィルム(透明フィルム(3))を保護層として用いた。
フィルム面内の主屈折率をnx、nyとし、フィルムの厚さをd(nm)とすると、Re=(nx−ny)×dで求めた。
また、フィルムの厚さ方向のリターデーション(Rth)は、フィルム面内の主屈折率をnx、nyとし、フィルムの厚さ方向の屈折率をnzとし、フィルムの厚さをd(nm)すると、Rth=〔(nx+ny)/2−nz〕×dで求めた。
測定した結果、Re、Rthのバラツキは、ともに2%以内であった。
反射防止フィルム(2A)及び透明フィルム(3)の表面に、高周波発信機(コロナジェネレーターHV05−2、Tamtec社製)を用いて、出力電圧100%、出力250Wで、直径1.2mmのワイヤー電極で、電極長240mm、ワーク電極間1.5mmの条件で3秒間コロナ放電処理を行った。
反射防止フィルム(2A)の表面処理を施した面にアクリル系接着剤(商品名:DP−8005クリア、住友スリーエム社製)を介して偏光子を貼り合わせ、また偏光子のもう一方の面にアクリル系接着剤(商品名:DP−8005クリア、住友スリーエム社製)を介して、透明フィルム(3)を透明フィルム(3)の表面改質処理を施した面側にして貼り合わせて、偏光板(4A)を作製した。
市販の液晶モニター(TNモード、OCBモード、VAモード、MVAモード、IPSモードの20V型液晶モニターを用いた)から、液晶セルを挟んでいる偏光板及び視野角補償フィルムを剥がし、その代わりに上記で得た偏光板(4A)を貼り合わせて評価用モニターを得た。
実施例6において、反射防止フィルム(2A)に代えて、反射防止フィルム(2B)〜(2G)をそれぞれ用いる以外は、実施例6と同様にして、偏光板(4B)〜(4G)をそれぞれ作製した。また、得られた偏光板(4B)〜(4G)をそれぞれ貼り合わせて評価用モニターを得た。
(A)傷つき視認性試験
実施例1〜5、比較例1,2で得られた反射防止フィルムの視認側の表面硬度を、JIS K 5600に従って、2Hの鉛筆を用いて500g荷重で測定した。測定後の偏光板を液晶パネルに配置した後にディスプレイを白表示にして、斜め45度の角度で画面を観察した。鉛筆による傷が認められない場合は○、傷が認められる場合には×として評価した。
実施例1〜5、比較例1,2で得られた反射防止フィルム(2A)〜(2G)のそれぞれを1cm×5cmに打ち抜いて、試験フィルムを得た。得られた試験フィルム(10)を、図6に示すように3mmφのスチール製の棒(2)に巻きつけ、巻きつけたフィルム(10)が棒(2)のところで折れるか否かをテストした。合計10回テストを行い、折れなかった回数を可とう性を表す指標とした。
実施例1〜5、比較例1,2で得られた反射防止フィルム(2A)〜(2G)のそれぞれにつき、分光光度計を用い、所定の入射角における反射スペクトルを測定し、波長550nmにおける反射率として求めた。
市販の液晶モニター(TNモード、OCBモード、VAモード、MVAモード、IPSモードの20V型液晶モニターを用いた)から、液晶セルを挟んでいる偏光板及び視野角補償フィルムのうち、視認側に設置されている、偏光板及び視野角補償フィルムを剥がし取り、それに代えて、実施例6〜10及び比較例3、4で得た偏光板(3A)〜(3G)を該液晶セルに設置した。次いで、背景を黒表示で白文字を表示させて、正面から視線を上下左右に移動させ、その際に白文字が読み取れなくなる角度を測定した。
測定結果を第2表に示す。
上記液晶表示性能の評価試験で作製した液晶表示装置を暗表示し、温度60℃、湿度90%で300時間放置した。その後、暗室内で暗表示した表示画面全体を真正面から観察し、以下の指標で評価した。
○:全体的に均一な黒表示になっており、光漏れがない。
△:額縁の上下左右に暗表示の色むらが見られる。
×:額縁の上下左右に光漏れが見られる。
評価結果を第2表に示す。
上記液晶表示性能の評価試験で作製した液晶表示装置を暗表示し、温度60℃、湿度90%で300時間放置し、暗室内で、その表示画面全体を真正面から観察し、輝点の数を数えた。評価結果を第2表に示す。
Claims (9)
- 反射防止層及び基材樹脂層を少なくとも有し、前記基材樹脂層が熱可塑性樹脂を主たる成分とする、a層及びb層を少なくとも含んでなり、前記a層の曲げ弾性率がb層の曲げ弾性率より大きく、かつ前記a層が反射防止層側に存在することを特徴とする反射防止フィルム。
- 前記a層の熱可塑性樹脂が、ビニル芳香族重合体、ポリアクリレート重合体、ポリメタクリレート重合体、ビニル脂環式炭化水素重合体及びその水素化物のいずれかである請求項1に記載の反射防止フィルム。
- 前記b層の熱可塑性樹脂が、脂環式構造含有重合体、セルロース重合体、ポリエステル重合体のいずれかである請求項1または2に記載の反射防止フィルム。
- 前記a層とb層の曲げ弾性率の差が、0.2GPa〜2.5GPaである請求項1〜3のいずれかに記載の反射防止フィルム。
- 前記a層とb層の組み合わせが、a層/b層で表したとき、ビニル芳香族重合体/脂環式構造含有重合体、ポリアクリレート重合体/脂環式構造含有重合体、ポリメタクリレート重合体/脂環式構造含有重合体のいずれかである請求項1〜4のいずれかに記載の反射防止フィルム。
- 前記反射防止層が、屈折率1.40以下の低屈折率層を含む層であることを特徴とする請求項1〜5のいずれかに記載の反射防止フィルム。
- 前記基材樹脂層が、共押出法により得られたものであることを特徴とする請求項1〜6のいずれかに記載の反射防止フィルム。
- 請求項1〜7のいずれかに記載の反射防止フィルムを偏光子に貼り合わせてなることを特徴とする偏光板。
- 請求項8に記載の偏光板を備えることを特徴とするディスプレイ。
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2005
- 2005-11-02 TW TW094138399A patent/TW200630226A/zh unknown
- 2005-11-08 CN CN2005800462404A patent/CN101099094B/zh active Active
- 2005-11-08 JP JP2006544896A patent/JP4803036B2/ja active Active
- 2005-11-08 WO PCT/JP2005/020456 patent/WO2006051784A1/ja active Application Filing
- 2005-11-08 EP EP05802997A patent/EP1811319A4/en not_active Withdrawn
- 2005-11-08 US US11/667,274 patent/US7875341B2/en active Active
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EP1811319A1 (en) | 2007-07-25 |
US7875341B2 (en) | 2011-01-25 |
WO2006051784A1 (ja) | 2006-05-18 |
CN101099094A (zh) | 2008-01-02 |
KR101232516B1 (ko) | 2013-02-12 |
EP1811319A4 (en) | 2010-03-31 |
US20080032146A1 (en) | 2008-02-07 |
TW200630226A (en) | 2006-09-01 |
KR20070067245A (ko) | 2007-06-27 |
CN101099094B (zh) | 2011-07-13 |
JP4803036B2 (ja) | 2011-10-26 |
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