JP2009262533A - 光学フィルムの製造方法、光学フィルム、偏光板、及び表示装置 - Google Patents
光学フィルムの製造方法、光学フィルム、偏光板、及び表示装置 Download PDFInfo
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- JP2009262533A JP2009262533A JP2008297748A JP2008297748A JP2009262533A JP 2009262533 A JP2009262533 A JP 2009262533A JP 2008297748 A JP2008297748 A JP 2008297748A JP 2008297748 A JP2008297748 A JP 2008297748A JP 2009262533 A JP2009262533 A JP 2009262533A
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Images
Landscapes
- Liquid Crystal (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polarising Elements (AREA)
Abstract
【解決手段】セルロースエステルと下記ポリマー(I)を含む組成物を溶融流延製膜してウェブを形成し、該ウェブを少なくとも1方向に1.1倍以上5.0倍以下で延伸処理することを特徴とする光学フィルムの製造方法。ポリマー(I):一般式(1)で表される部分構造を有するエチレン性不飽和モノマーと、置換基を有していてもよい芳香族基、置換基を有していてもよい複素環基、または置換基を有していてもよいシクロアルキル基を含有するエチレン性不飽和モノマーの少なくとも1種とを共重合させて得られるポリマー。
【選択図】なし
Description
ポリマー(I):一般式(1)で表される部分構造を有するエチレン性不飽和モノマーの少なくとも1種と、置換基を有していてもよい芳香族基、置換基を有していてもよい複素環基、または置換基を有していてもよいシクロアルキル基を含有するエチレン性不飽和モノマーの少なくとも1種とを共重合させて得られるポリマー。
2.前記ポリマー(I)が、前記一般式(1)で表される部分構造を有するエチレン性不飽和モノマーと、下記一般式(2)で表されるモノマーの少なくとも1種とを共重合させて得られるポリマーであることを特徴とする前記1に記載の光学フィルムの製造方法。
3.前記ポリマー(I)が、前記一般式(1)で表される部分構造を有するエチレン性不飽和モノマーと、下記一般式(3)で表されるモノマーの少なくとも1種とを共重合させて得られるポリマーであることを特徴とする前記1に記載の光学フィルムの製造方法。
4.前記ポリマー(I)が、前記一般式(1)で表される部分構造を有するエチレン性不飽和モノマーと、下記一般式(4)で表されるモノマーの少なくとも1種とを共重合させて得られるポリマーであることを特徴とする前記1に記載の光学フィルムの製造方法。
5.前記ポリマー(I)が、前記一般式(1)で表される部分構造を有するエチレン性不飽和モノマーと、下記一般式(5)で表されるモノマーの少なくとも1種とを共重合させて得られるポリマーであることを特徴とする前記1に記載の光学フィルムの製造方法。
6.前記一般式(1)で表される部分構造を有するエチレン性不飽和モノマーが、N−ビニルピロリドン、N−アクリロイルモルホリン、N−ビニルピペリドン、N−ビニルカプロラクタムまたは、これらの混合物であることを特徴とする前記1〜5のいずれか1項に記載の光学フィルムの製造方法。
0≦X≦2.40 … 式(2)
0.10≦Y≦3.00 … 式(3)
(式中、Xはアセチル基の置換度を示す。Yは炭素数3〜5のアシル基の置換度の総和を示す。)
9.前記1〜8のいずれか1項に記載の光学フィルムの製造方法で製造されたことを特徴とする光学フィルム。
まず、本発明の光学フィルムの詳細について説明する。
本発明の光学フィルムのレターデーションは特に限定されるものではないが、IPSモード型の液晶表示装置に用いられる場合、面内のレターデーション(Ro)が0≦Ro≦10nm、厚み方向のレターデーション(Rth)が−20≦Rth≦20nmの範囲を同時に満たすことが好ましい。より好ましくは(Ro)が0≦Ro≦5nm、(Rth)が−10≦Rth≦10nmの範囲であり、特に好ましくは(Ro)が0≦Ro≦5nm、(Rth)が−5≦Rth≦5nmの範囲である。レターデーションがこれらの範囲にある光学フィルムを用いると、ブレ・ぼやけが少なく、視野角安定性が高いIPSモード型液晶表示装置を提供することができる。
Ro=(nx−ny)×d
Rth={(nx+ny)/2−nz}×d
として表される。
セルロ−スには、1グルコ−ス単位の2位、3位、6位に1個ずつ、計3個の水酸基があり、置換度とは、1グルコ−ス単位に平均してアシル基がどのような位置にどれだけ結合しているかを示す数値である。従って、最大の置換度は3.00であり、上記アシル基で置換されていない部分は通常水酸基として存在しているものである。このようなセルロ−スの水酸基の一部またはすべてがアシル基で置換されたものをセルロースエステルと称している。なお、アシル基の置換度は、ASTM−D817に規定の方法により求めることができる。
0≦X≦2.40 … 式(2)
0.10≦Y<3.00 … 式(3)
(式中、Xはアセチル基の置換度を示す。Yは炭素数3〜5のアシル基の置換度の総和を示す。)
この内、特にセルロースアセテートプロピオネートが好ましく用いられ、中でも1.00≦A≦2.20であり、0.50≦B≦2.00が好ましい。より好ましくは1.20≦A≦2.00であり、0.70≦B≦1.70である。
装置:HLC−8220(東ソー(株)製)
カラム:TSKgel SuperHM−M(東ソー(株)製)
カラム温度:40℃
試料濃度:0.1質量%
注入量:10μl
流量:0.6ml/min
校正曲線:標準ポリスチレン:PS−1(Polymer Laboratories社製)Mw=2,560,000〜580までの9サンプルによる校正曲線を使用した。
まず、前記一般式(1)で表される部分構造を有するエチレン性不飽和モノマーついて説明する。
複素環基(例えば、ピリジル基、チアゾリル基、オキサゾリル基、イミダゾリル基等)が挙げられる。
重量平均分子量Mw、数平均分子量Mnは、ゲルパーミエーションクロマトグラフィー(GPC)を用いて測定した。
カラム: Shodex K806、K805、K803G(昭和電工(株)製を3本接続して使用した)
カラム温度:25℃
試料濃度: 0.1質量%
検出器: RI Model 504(GLサイエンス社製)
ポンプ: L6000(日立製作所(株)製)
流量: 1.0ml/min
校正曲線: 標準ポリスチレンSTK standard ポリスチレン(東ソー(株)製)Mw=1000000〜500の13サンプルによる校正曲線を使用した。13サンプルは、ほぼ等間隔に用いる。
本発明の光学フィルムは、セルロースエステル及び前記ポリマー(I)以外に、その他の添加剤として、可塑剤、酸化防止剤、紫外線吸収剤、粒子(マット剤)、等を含むことが好ましい。
本発明の光学フィルムには、可塑剤を添加することが好ましい。一般的に、可塑剤として知られる化合物を添加することは機械的性質向上、柔軟性を付与、耐吸水性付与、水分透過率の低減等のフィルムの改質の観点において好ましい。また、溶融流延法においては、用いるセルロースエステル単独のガラス転移温度よりも、可塑剤の添加によりフィルム構成材料の溶融温度を低下させる目的、または同じ加熱温度においてセルロースエステルよりも可塑剤を含むフィルム構成材料の粘度が低下できる目的を含んでいる。ここで、本発明において、フィルム構成材料の溶融温度とは、該材料が加熱され流動性が発現された状態において材料が加熱された温度を意味する。
本発明の光学フィルムにおいて、溶融製膜時の高温環境下では、光学フィルム成形材料の熱、及び酸素による分解が促進されるため、酸化防止剤を含有することが好ましい。
フェノール系化合物は既知の化合物であり、例えば、米国特許第4,839,405号明細書の第12〜14欄に記載されており、2,6−ジアルキルフェノール誘導体化合物が含まれる。このような化合物のうち好ましい化合物として、下記一般式(a)で表される化合物が好ましい。
本発明において有用な酸化防止剤の一つとして、下記一般式(b)で表されるヒンダードアミン系化合物が好ましい。
本発明において有用な酸化防止剤の一つとして、下記一般式(c−1)、(c−2)、(c−3)、(c−4)、(c−5)で表される部分構造を分子内に有する化合物が好ましい。
本発明において有用な酸化防止剤の一つとして、下記一般式(d)で表されるイオウ系化合物が好ましい。
紫外線吸収剤は、偏光子や表示装置の紫外線に対する劣化防止の観点から、波長370nm以下の紫外線の吸収能に優れており、かつ液晶表示性の観点から、波長400nm以上の可視光の吸収が少ないものが好ましい。
また、本発明の光学フィルムには、マット剤として微粒子を加えることが好ましい。本発明に使用される微粒子としては無機化合物として、例えば、二酸化珪素、二酸化チタン、酸化アルミニウム、酸化ジルコニウム、炭酸カルシウム、炭酸カルシウム、タルク、クレイ、焼成カオリン、焼成珪酸カルシウム、水和ケイ酸カルシウム、ケイ酸アルミニウム、ケイ酸マグネシウム及びリン酸カルシウムを挙げることができる。
本発明の光学フィルムは、液晶表示品質の向上のために、フィルム中にレターデーション制御剤を添加したり、配向膜を形成して液晶層を設け、偏光板保護フィルムと液晶層由来のレターデーションを複合化したりすることにより光学補償能を付与することができる。レターデーションを調節するために添加する化合物は、欧州特許911,656A2号明細書に記載されているような、二つ以上の芳香族環を有する芳香族化合物をレターデーション制御剤として使用することもできる。或いは、特開2006−2025号公報に記載の棒状化合物が挙げられる。また二種類以上の芳香族化合物を併用してもよい。該芳香族化合物の芳香族環には、芳香族炭化水素環に加えて、芳香族性ヘテロ環を含む芳香族性ヘテロ環であることが特に好ましく、芳香族性ヘテロ環は一般に、不飽和ヘテロ環である。中でも、特開2006−2026号公報に記載の1,3,5−トリアジン環が特に好ましい。
酸掃去剤とは製造時から持ち込まれるセルロースエステル中に残留する酸(プロトン酸)をトラップする役割を担う剤である。また、セルロースエステルを溶融するとポリマー中の水分と熱により側鎖の加水分解が促進し、セルロースアセテートプロピオネートならば酢酸やプロピオン酸が生成する。酸と化学的に結合できればよく、エポキシ、3級アミン、エーテル構造等を有する化合物が挙げられるが、これに限定されるものでない。
本発明の光学フィルムは、溶融流延法により製造される。
本発明の光学フィルムの寸法変化率は80℃、90%RHの高温高湿下、50時間の処理において、±1.0%以内であることが好ましく、より好ましくは±0.5%以内、さらに好ましくは±0.4%以内であり、特に好ましくは±0.3%以内であることが特に好ましい。
本発明の偏光板について述べる。
本発明の光学フィルムが用いられる表示装置の内、好適に使用される液晶表示装置について説明する。
(光学フィルムF−1の作製)
下記の添加剤、セルロースエステルを用いて、溶融流延法により光学フィルムF−1を作製した。
本発明のポリマー AMP−1 10質量部
IRGANOX−1010(チバ・ジャパン社製) 0.5質量部
GSY−P101(堺化学工業株式会社製) 0.3質量部
Sumilizer−GS(住友化学社製) 0.3質量部
Tinuvin−928(チバ・ジャパン社製) 2.0質量部
アエロジルNAX50(日本アエロジル社製) 0.2質量部
KE−P100 (日本触媒社製) 0.02質量部
上記の添加剤、セルロースエステルを混合し、60℃ 5時間減圧乾燥した。このセルロースエステル組成物を、2軸式押出し機を用いて235℃で溶融混合しペレット化した。
同様に以下、本発明のポリマーAMP−1、セルロースエステルC−1、延伸倍率を下記表2、表3、表4、表5に記載の化合物、条件に変更する以外は同様にして、本発明の光学フィルムF−2〜F−39、比較の光学フィルムF−40〜F−47を作製した。なお化合物の添加量は、F−1の化合物と同量で置き換えた。
装置:HLC−8220(東ソー(株)製)
カラム:TSKgel SuperHM−M(東ソー(株)製)
カラム温度:40℃
試料濃度:0.1質量%
注入量:10μl
流量:0.6ml/min
校正曲線:標準ポリスチレン:PS−1(Polymer Laboratories社製)Mw=2,560,000〜580までの9サンプルによる校正曲線を使用した。
上記のようにして作製した試料について、以下に記載した評価を行なった。その結果を表4、表5に示す。
得られた光学フィルムを、自動複屈折計KOBRA−21−ADH(王子計測機器社製)を用いて温度23℃、湿度55%RHの環境下で、波長が590nmにおける屈折率nx、ny、nzを求め、下記の式に従って、フィルム面内方向のレターデーション(Ro)、及び厚み方向のレターデーション(Rth)を算出した。
Rth={(nx+ny)/2−nz}×d
(式中、フィルム面内の遅相軸方向の屈折率nx、進相軸方向の屈折率ny、厚み方向の屈折率nz、フィルムの膜厚をd(nm)とする)
(ヘイズ)
得られた光学フィルムから、JIS K−6714に従って、ヘイズメーター(1001DP型、日本電色工業(株)製)を使用して測定した。
巻芯に原反フィルムを巻き取る作業を行い、巻始めでシワが発生して不良となった場合は巻芯から原反フィルムを取り外して、再度巻き取る作業を行った。この時の不良回数をカウントした。この作業を10回行い平均値を求め、下記レベルにランク分けを行った。
B:1回以上3回未満
C:3回以上5回未満
D:5回以上
(馬の背故障、巻芯転写)
巻き取った光学フィルム原反試料をポリエチレンシートで2重に包み、図8に示すような保存方法で、28℃、55%の条件下で30日間保存した。その後、箱から取り出し、ポリエチレンシートを開け、フィルム原反試料表面に点灯している蛍光灯の管を反射させて映し、その歪みあるいは細かい乱れを観察し、馬の背故障を下記レベルにランク分けした。
B:蛍光灯が部分的に曲がって見える
C:蛍光灯がまだらに映って見える
また、保存後のフィルム原反試料を巻き返して、巻芯部分より何mまで、50μm以上の点状の変形、または幅手方向の帯状の変形がはっきり見える巻芯転写が発生している長さを測定し、下記レベルにランク分けを行った。
B:巻芯部分より15〜30m
C:巻芯部分より30〜50m
D:巻芯部分より50m以上
(偏光板の作製)
厚さ120μmの長尺ロールポリビニルアルコールフィルムを沃素1質量部、ホウ酸4質量部を含む水溶液100質量部に浸漬し、50℃で5倍に搬送方向に延伸して偏光膜を作った。次に、この偏光膜の片面に下記の条件でアルカリケン化処理した前記光学フィルムF−1を偏光板保護フィルムとして完全ケン化型ポリビニルアルコール5%水溶液を接着剤として貼り、更に偏光膜のもう一方の面に同様にアルカリケン化処理したコニカミノルタオプト社製KC4UXを貼り合わせ、乾燥して偏光板P−1を作製した。同様にして前記光学フィルムF−2〜F−45を用いて偏光板P−2〜P−45を作製した。
ケン化工程 2M−NaOH 50℃ 90秒
水洗工程 水 30℃ 45秒
中和工程 10質量%HCl 30℃ 45秒
水洗工程 水 30℃ 45秒
ケン化処理後、水洗、中和、水洗の順に行い、次いで80℃で乾燥を行った。
IPSモードの液晶セルを含む液晶表示装置[松下電器産業(株)製パナソニック液晶テレビVIERA TH−26LX60]から液晶パネルを取り出し、液晶セルの上下に配置されていた偏光板を取り除いて、上記作製した各々の偏光板を偏光子の遅相軸が液晶セルの長辺と平行(0±0.2度)となるように液晶セルの両面にアクリル粘着剤(厚み20μm)を用いて貼着した。その際前記光学フィルムF−1〜F−47が液晶セル側になるように貼合し、光学フィルムの偏光板としての特性を評価した。結果を表6に示す。
液晶表示パネル(液晶表示装置)に静止画像、動画像を表示させ、それらを目視観察し、視認性を下記のようにランク評価した。
○:黒がしまって見え、鮮明であるが、わずかに動画像のブレが認められる
△:黒のしまりがなく、鮮明さがやや低く、動画像のブレが認められる
×:黒のしまりがなく、鮮明さが低く、動画像のブレが気になる
(視野角の評価)
23℃、55%RHの環境で、ELDIM社製EZ−Contrast160Dを用いて液晶表示装置の視野角測定を行った。視野角は、コントラスト(白表示と黒表示の比)が20以上の領域を有効視野角とした。
○:有効視野角がやや変動する
△:有効視野角が狭くなる
×:有効視野角が著しく狭くなる
2 フィルター
3 スタチックミキサー
4 流延ダイ
5 回転支持体(第1冷却ロール)
6 挟圧回転体(タッチロール)
7 回転支持体(第2冷却ロール)
8 回転支持体(第3冷却ロール)
9 剥離ロール
10 フィルム
11 ダンサーロール
12 延伸装置
13 スリッター
14 エンボスリング
15 バックロール
16 巻取り装置
21a、21b 保護フィルム
22a、22b 位相差フィルム
23a、23b フィルムの遅相軸方向
24a、24b 偏光子の透過軸方向
25a、25b 偏光子
26a、26b 偏光板
27 液晶セル
29 液晶表示装置
31 ダイ本体
32 スリット
41 金属スリーブ
42 弾性ローラ
43 金属製の内筒
44 ゴム
45 冷却水
51 外筒
52 内筒
53 空間
54 冷却液
55a、55b 回転軸
56a、56b 外筒支持フランジ
60 流体軸筒
61a、61b 内筒支持フランジ
62a、62b 中間通路
110 巻芯本体
117 支え板
118 架台
120 セルロースエステルフィルム原反
Claims (13)
- セルロースエステルと下記ポリマー(I)を含む組成物を溶融流延製膜してウェブを形成し、該ウェブを少なくとも1方向に1.1倍以上5.0倍以下で延伸処理することを特徴とする光学フィルムの製造方法。
ポリマー(I):一般式(1)で表される部分構造を有するエチレン性不飽和モノマーの少なくとも1種と、置換基を有していてもよい芳香族基、置換基を有していてもよい複素環基、または置換基を有していてもよいシクロアルキル基を含有するエチレン性不飽和モノマーの少なくとも1種とを共重合させて得られるポリマー。
- 前記一般式(1)で表される部分構造を有するエチレン性不飽和モノマーが、N−ビニルピロリドン、N−アクリロイルモルホリン、N−ビニルピペリドン、N−ビニルカプロラクタムまたは、これらの混合物であることを特徴とする請求項1〜5のいずれか1項に記載の光学フィルムの製造方法。
- 前記一般式(1)で表される部分構造を有するエチレン性不飽和モノマーがN−アクリロイルモルホリンであることを特徴とする請求項1〜5のいずれか1項に記載の光学フィルムの製造方法。
- 前記セルロースエステルが、下記式(1)〜(3)の置換度を同時に満たすセルロースエステルであることを特徴とする請求項1〜7のいずれか1項に記載の光学フィルムの製造方法。
2.40≦X+Y≦3.00 … 式(1)
0≦X≦2.40 … 式(2)
0.10≦Y≦3.00 … 式(3)
(式中、Xはアセチル基の置換度を示す。Yは炭素数3〜5のアシル基の置換度の総和を示す。) - 請求項1〜8のいずれか1項に記載の光学フィルムの製造方法で製造されたことを特徴とする光学フィルム。
- 請求項1〜8のいずれか1項に記載の光学フィルムの製造方法で製造された光学フィルムであって、面内のレターデーション(Ro)が0≦Ro≦10nm、厚み方向のレターデーション(Rth)が−20≦Rth≦20nmの範囲を同時に満たすことを特徴とする光学フィルム。
- 請求項9または10に記載の光学フィルムを少なくとも一方の面に用いたことを特徴とする偏光板。
- 請求項9または10に記載の光学フィルム、または請求項11に記載の偏光板を液晶セルの少なくとも一方の面に用いたことを特徴とする表示装置。
- 前記液晶セルが、IPSモード型であることを特徴とする請求項12に記載の表示装置。
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