JP2011126279A - 光学積層フィルム、偏光板および光学製品 - Google Patents
光学積層フィルム、偏光板および光学製品 Download PDFInfo
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- JP2011126279A JP2011126279A JP2011003020A JP2011003020A JP2011126279A JP 2011126279 A JP2011126279 A JP 2011126279A JP 2011003020 A JP2011003020 A JP 2011003020A JP 2011003020 A JP2011003020 A JP 2011003020A JP 2011126279 A JP2011126279 A JP 2011126279A
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- 125000000725 trifluoropropyl group Chemical group [H]C([H])(*)C([H])([H])C(F)(F)F 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
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Abstract
【解決手段】透明樹脂基材フィルムの片面に、ハードコート層およびエアロゲル製の低屈折率層を順次積層してなり、該エアロゲルが、加水分解性有機珪素化合物またはその加水分解物で形成されたマトリックス中に微小な気泡が分散した透明性多孔質体からなり、基材フィルムが、ダイラインの深さまたは高さが0.1μm以下、揮発性成分含有量が0.1重量%以下、飽和吸水率が0.01重量%以下、膜厚変動3%以内の溶融押出フィルムであり、低屈折率層の膜厚が30〜500nmであり、ハードコート層の屈折率をnH、低屈折率層の屈折率をnLとしたとき、以下の式[1]、[2]および[3]を満たす光学積層フィルム。
式[1]:nL≦1.37
式[2]:nH≧1.53
式[3]:√nH−0.2<nL<√nH+0.2
【選択図】図1
Description
多層膜の低屈折率層としては、相対的に高屈折率を有する膜と相対的に低屈折率を有する膜とをこの順に積層したもの(例えば、特許文献1を参照)がある。
(1)透明樹脂を含んでなる基材フィルムの片面に、直接または他の層を介してハードコート層およびエアロゲルからなる低屈折率層をこの順に積層してなり、該エアロゲルが、加水分解性有機珪素化合物またはその加水分解物で形成されたマトリックス中に微小な気泡が分散した透明性多孔質体からなり、基材フィルムが溶融押出成形法で得られるものであり、そのダイラインの深さまたは高さが0.1μm以下、揮発性成分含有量が0.1重量%以下、飽和吸水率が0.01重量%以下、且つ膜厚変動が3%以内であり、低屈折率層の膜厚が30〜500nmであり、ハードコート層の屈折率をnH、低屈折率層の屈折率をnLとしたとき、以下の式[1]、[2]および[3]を満たし、且つ波長550nmにおける反射率が0.7%以下で、波長430〜700nmにおける反射率が1.4%以下である光学積層フィルム;
式[1]:nL≦1.37
式[2]:nH≧1.53
式[3]:√nH−0.2<nL<√nH+0.2
(2)ハードコート層の屈折率nHおよび低屈折率層の屈折率nLが、以下の式[4]、[5]および式[6]の関係を満たす前記(1)に記載の光学積層フィルム;
式[4]:1.25≦nL≦1.35
式[5]:nH≧1.55
式[6]:√nH−0.15<nL<√nH+0.15
(3)エアロゲルが、中空粒子がマトリックス中に分散されたものである前記(1)または(2)に記載の光学積層フィルム;
(4)ハードコート層が、ハードコート層形成用塗工液を基材フィルム上に塗工して、加熱または紫外線照射により硬化させたものである前記(1)〜(3)のいずれかに記載の光学積層フィルム;
(5)光学部材の反射防止保護フィルムである前記(1)〜(4)のいずれかに記載の光学積層フィルム;
(6)偏光板保護フィルムである前記(1)〜(4)のいずれかに記載の光学積層フィルム;
(7)前記(6)記載の偏光板保護フィルムの低屈折率層が設けられている面の反対側の面に偏光膜を積層してなる反射防止機能付偏光板;および
(8)前記(7)記載の反射防止機能付偏光板を備える光学製品
がそれぞれ提供される。
式[2]:nH≧1.53
式[3]:√nH−0.2<nL<√nH+0.2、
式[5]:nH≧1.55
式[6]:√nH−0.15<nL<√nH+0.15
式[1]:nL≦1.37
式[3]:n√H−0.2<nL<√nH+0.2
ここで、nHは、ハードコート層の屈折率である。
特に、下記関係式[4]および[6]が満たされることが好ましい。
式[4]:1.25≦nL≦1.35
式[6]:√nH−0.15<nL<√nH+0.15
(a)式(i):SiX4表される化合物(以下、化合物(i)という)。
(b)前記化合物(i)の少なくとも1種の部分加水分解生成物(以下、化合物(ii)という)。
(c)前記化合物(i)の少なくとも1種の完全加水分解生成物(以下、化合物(iii)という)。
偏光膜の製造方法は特に限定されない。PVA系の偏光膜を製造する方法としては、PVA系フィルムにヨウ素イオンを吸着させた後に一軸に延伸する方法、PVA系フィルムを一軸に延伸した後にヨウ素イオンを吸着させる方法、PVA系フィルムへのヨウ素イオン吸着と一軸延伸とを同時に行う方法、PVA系フィルムを二色性染料で染色した後に一軸に延伸する方法、PVA系フィルムを一軸に延伸した後に二色性染料で吸着する方法、PVA系フィルムへの二色性染料での染色と一軸延伸とを同時に行う方法が挙げられる。また、ポリエン系の偏光膜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・脱水する方法などの公知の方法が挙げられる。
液晶96の液晶モードは特に限定されない。液晶モードとしては、例えば、TN(Twisted Nematic)型、STN(Super Twisted Nematic)型、HAN(Hybrid Alignment Nematic)型、MVA(Multiple Vertical Alignment)型、IPS(In Plane Switching)型、OCB(Optical Compensated Bend)型、などが挙げられる。
(1)基材フィルムの膜厚(基準膜厚、膜厚変動値)
フィルムを長さ方向に100mm毎に切り出し、その切り出したフィルムについて、接触式ウェブ厚さ計(明産社製、RC−101)を用いて、フィルムの幅方向に0.48mm毎に測定し、その測定値の算術平均値を基準膜厚T(μm)とする。膜厚変動は、前記測定した膜厚の内最大値をTMAX(μm)、最小値をTMIN(μm)として以下の式から算出する。
膜厚変動(%)=(TMAX−TMIN)/T×100
基材フィルム200mgを、表面に吸着していた水分や有機物を完全に除去した内径4mmのガラスチューブの試料容器に入れる。次に、その容器を温度100℃で60分間加熱し、容器から出てきた気体を連続的に捕集する。そして、捕集した気体を熱脱着ガスクロマトグラフィー質量分析計(TDS−GC−MS)で分析し、その中で分子量200以下の成分の合計量を残留揮発性成分として測定する。
ASTM D530に従い、23℃で1週間浸漬して増加重量を測定することにより求める。
非接触3次元表面形状・粗さ測定機(ザイゴ社製)を用いて、横5.6mm×縦4.4mmの視野で、縦を480分割、横を640分割して640×480升目で観察する。
高速分光エリプソメーター(J.A.Woollam社製、M−2000U)を用いて、測定波長245〜1000nm、入射角55°、60°および65°で測定し、その測定値を元に算出した値を屈折率とする。
2枚の偏光膜を偏光軸が平行になるように重ね合わせた場合の透過率(H0)と、直交に重ね合わせた場合の透過率(H90)それぞれを、JIS Z8701の2度視野(C光源)により、分光光度計を用いて測定し、以下の式から偏光度を求める。なお、前記H0及びH90は、視感度補正したY値である。
偏光度(%)=[(H0−H90)/(H0+H90)]1/2×100
光学積層フィルムの任意の3箇所について、分光光度計(日本分光社製:「紫外可視近赤外分光光度計V−570」)を用い、入射角5°で反射スペクトルを測定し、波長430〜700nmにおける光反射率を求め、波長550nmにおける光反射率と、波長430〜700nmにおける光反射率の最大値を波長430〜700nmにおける光反射率とする。
得られた偏光板を適当な大きさ(10インチ四方)に切り出し、低屈折率層を形成させたほうの面を上面にして、図3に示す液晶表示素子に偏光板(図3の上側偏光板21)として組み込んで液晶表示素子を作製する。次いで、市販のライトボックス(商品名:ライトビュア−7000PRO、ハクバ写真産業社製)の上に、液晶表示素子をのせて簡易液晶パネルを作製し、液晶表示素子の表示を黒にして、正面よりパネルを目視にて観察し、以下の3段階で評価を行う。
○:グレア(視野内で過度に輝度が高い点や面が見えることによっておきる不快感や見にくさのことで、光源から直接または間接に受けるギラギラしたまぶしさなどのことをいう)や映りこみがまったくない。
△:グレアや映りこみが少し見られる。
×:グレアや映りこみが画面全面で見られる。
前記(8)で作成した液晶表示パネルを暗室に設置し、暗表示の時と明表示の時の正面から5°の位置における輝度を色彩輝度計(トプコン社製、色彩輝度計BM−7)を用いて測定する。そして、明表示の輝度と暗表示の輝度の比(=明表示の輝度/暗表示の輝度)を計算し、これをコントラストとする。コントラストが大きいほど、視認性に優れる。
ノルボルネン系重合体(製品名「ZEONOR 1420R」、日本ゼオン社製;ガラス転移温度136℃、飽和吸水率0.01重量%未満)のペレットを、空気を流通させた熱風乾燥機を用いて110℃で、4時間乾燥した。そしてこのペレットを、リーフディスク形状のポリマーフィルター(濾過精度30μm)を設置したダイリップ内面に表面粗さRa=0.05μmのクロムメッキを施したリップ幅650mmのコートハンガータイプのTダイを有する短軸押出機を用いて、260℃で溶融押出して600mm幅の基材フィルム1Aを得た。得られた基材フィルム1Aの揮発性成分の含有量は0.01重量%以下、飽和吸水率は0.01重量%以下であった。また、この基材フィルム1Aの基準膜厚は40μm、膜厚変動は2.3%、ダイラインの深さは0.01μmであった。
5酸化アンチモンの変性アルコールゾル(固形分濃度30%、触媒化成社製)100重量部に、紫外線硬化型ウレタンアクリレート(日本合成化学者製、商品名「紫光UV7000B」)10重量部、光重合開始剤(チバガイキー社製、商品名「イルガキュアー184」)0.4重量部を混合し、紫外線硬化型のハードコート層形成用組成物1を得た。
テトラメトキシシランのオリゴマー(コルコート社製「メチルシリケート51」)と、メタノールを質量比47:75で混合してA液を調製し、また水、アンモニア水(アンモニア28重量%)、メタノールを重量比で60:1.2:97.2で混合してB液を調製した。
そして、A液とB液を16:17の重量比で混合してシリコンアルコキシド溶液1を得た。
A液を調製する際、テトラメトキシシランのオリゴマーとメタノールを質量比47:78で混合する他は、製造例3と同様にしてシリコンアルコキシド溶液2を得た。
A液を調製する際、テトラメトキシシランのオリゴマー(コルコート社製「メチルシリケート51」)メタノールを質量比47:79で混合する他は、製造例3と同様にしてシリコンアルコキシド溶液3を得た。
テトラエトキシシラン300gとエタノール455gを混合し、これに1.0質量%クエン酸水溶液295gを添加した後に、室温にて1時間攪拌することでテトラエトキシシラン加水分解物Aを調製した。
そして、テトラエトキシシラン加水分解物Aを1020部、末端反応性ジメチルシリコーンオイル(日本ユニカー社製L−9000)を0.42部、プロピレングリコールモノメチルエーテルを2700部およびイソプロピルアルコール6300部を混合して低屈折率層形成用組成物を得た。
厚さ45μmのPVAフィルム(重合度2400、ケン化度99.9%)を純水中で膨潤させてから、ヨウ素1重量%とヨウ化カリウム3重量%の混合水溶液に浸漬し、前記PVAフィルムを染色した。次いで、このフィルムを4.5重量%ホウ酸水溶液に浸漬し、長手方向に5.3倍延伸し、続いて5重量%ホウ砂水溶液に浸漬し、長手方向における総延伸倍率が5.5倍となるように延伸した。延伸後、フィルム表面の水分を取り除き、50℃で乾燥して偏光膜を調製した。この偏光膜の厚さは18μm、偏光度は99.95%であった。
製造例1で得られた基材フィルム1Aの両面に、高周波発振機(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い、表面張力が0.072N/mになるように表面改質して基材フィルム1Bを得た。
基材フィルム1Aの代わりに、厚さ40μmのトリアセチルセルロース(TAC)フィルム(コニカ社製、商品名「KC4UX2M」、Tg=120℃、飽和吸水率=4.5重量%、揮発性成分の含有量=6.0重量%、以下「基材フィルム2A」と記す。)を用いた他は、実施例1と同様な操作を行い、光学積層フィルム2E(偏光板保護フィルム)および反射機能付偏光板2Fを得た。このときのハードコート層の屈折率は1.62、低屈折率層の屈折率は1.33であった。この偏光板を用いて光学性能の評価を行った。評価結果を表1に示す。
基材フィルムとして、基材フィルム1Aの代わりに、厚さ50μmのポリエチレンテレフタレートフィルム(東洋紡社製、商品名「コスモシャイン A4300」、以下「基材フィルム3A」と記す。)を用いたほかは、実施例1と同様な操作を行い、光学積層フィルム3Eおよび反射機能付偏光板3Fを得た。このときのハードコート層の屈折率は1.62、低屈折率層の屈折率は1.33であった。この偏光板を用いて光学性能の評価を行った。評価結果を表1に示す。
基材フィルム1Aの代わりに、トリアセチルセルロースフィルムを用いた偏光板(ポラテクノ社製、商品名「スーパーハイコントラスト偏光板 SKN−18243T」、偏光度99.993%)を用いた他は、実施例1と同様にして、ハードコート層および低屈折率層を形成させて、光学積層フィルム4Eを得た。この光学積層フィルム4Eは偏光膜が積層されているので、このフィルムをそのまま反射機機能付偏光板として用いて光学性能の評価を行った。評価結果を表1に示す。
比較例1
低屈折率層を形成する際に、シリコンアルコキシド溶液1の代わりに、製造例4で得られたシリコンアルコキシド溶液2を使用した他は、実施例1と同様な操作を行い、偏光板保護フィルム5Eおよび反射防止機能付偏光板5Fを得た。このときのハードコート層の屈折率は1.62、低屈折率層の屈折率は1.39であった。この偏光板を用いて光学性能の評価を行った。評価結果を表1に示す。
低屈折率層を形成する際に、シリコンアルコキシド溶液1の代わりに、製造例5で得られたシリコンアルコキシド溶液3を使用した他は、実施例1と同様な操作を行い、光学積層フィルム6E(偏光板保護フィルム)および反射防止機能付偏光板6Fを得た。このときのハードコート層の屈折率は1.62.低屈折率層の屈折率は1.40であった。この偏光板を用いて光学性能の評価を行った。評価結果を表1に示す。
ハードコート層形成用組成物として、ハードコート層形成用組成物2(紫外線硬化型高屈折率剤;大日本インキ社製、ダイキュアクリアSD−715)を用い、さらに低屈折率層として製造例6で得た低屈折率層形成用組成物を用いた他は、実施例1と同様な操作を行い、光学積層フィルム7Eおよび反射防止機能付偏光板7Fを得た。このときのハードコート層の屈折率は1.52、低屈折率層の屈折率は1.45であった。この偏光板を用いて光学性能の評価を行った。評価結果を表1に示す。
式[1]:nL≦1.37、
式[2]:nH≧1.53
式[3]:√nH−0.2<nL<√nH+0.2
を満たす光学積層フィルム(実施例1〜3)は、波長550nmにおける光反射率および波長430〜700nmにおける光反射率が小さく、視認性および明暗表示のコントラストに優れる。
Claims (14)
- 透明樹脂を含んでなる基材フィルムの片面に、直接または他の層を介してハードコート層およびエアロゲルからなる低屈折率層をこの順に積層してなり、該エアロゲルが、加水分解性有機珪素化合物またはその加水分解物で形成されたマトリックス中に微小な気泡が分散した透明性多孔質体からなり、基材フィルムが溶融押出成形法で得られるものであり、そのダイラインの深さまたは高さが0.1μm以下、揮発性成分含有量が0.1重量%以下、飽和吸水率が0.01重量%以下、且つ膜厚変動が3%以内であり、低屈折率層の膜厚が30〜500nmであり、ハードコート層の屈折率をnH、低屈折率層の屈折率をnLとしたとき、以下の式[1]、[2]および[3]を満たし、且つ波長550nmにおける反射率が0.7%以下で、波長430〜700nmにおける反射率が1.4%以下である光学積層フィルム。
式[1]:nL≦1.37
式[2]:nH≧1.53
式[3]:√nH−0.2<nL<√nH+0.2 - ハードコート層の屈折率nHおよび低屈折率層の屈折率nLが、以下の式[4]、[5]および式[6]の関係を満たす請求項に1記載の光学積層フィルム。
式[4]:1.25≦nL≦1.35
式[5]:nH≧1.55
式[6]:√nH−0.15<nL<√nH+0.15 - エアロゲルが、中空粒子がマトリックス中に分散されたものである請求項1または2に記載の光学積層フィルム。
- 中空粒子が、シリカ微粒子である請求項3に記載の光学積層フィルム。
- 低屈折率層が、超臨界乾燥法により形成されたものである請求項1〜4のいずれかに記載の光学積層フィルム。
- 低屈折率層が、フッ素樹脂を含有するものである請求項1〜5のいずれかに記載の光学積層フィルム。
- ハードコート層が、ハードコート層形成用塗工液を基材フィルム上に塗工して、加熱または紫外線照射により硬化させたものである請求項1〜6のいずれかに記載の光学積層フィルム。
- ハードコート層形成用塗工液が、ウレタンアクリレート系材料または多官能アクリレート系ハードコート材料である請求項7に記載の光学積層フィルム。
- 透明樹脂が、脂環式構造を有する重合体樹脂およびポリエステル樹脂からなる群から選ばれる樹脂である請求項1〜8のいずれかに記載の光学積層フィルム。
- 請求項1〜9のいずれかに記載の光学積層フィルムから成る光学部材の反射防止保護フィルム。
- 請求項1〜10のいずれかに記載の光学積層フィルムから成る偏光板保護フィルム。
- 液晶表示素子に偏光板とともに組み込んだときの、正面から5°の位置における明表示と暗表示のコントラスト(明表示の輝度/暗表示の輝度)が280以上である請求項11に記載の偏光板保護フィルム。
- 請求項11または12に記載の偏光板保護フィルムの低屈折率層が設けられている面の反対側の面に偏光膜を積層してなる反射防止機能付偏光板。
- 請求項13に記載の反射防止機能付偏光板を備える光学製品。
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- 2004-06-28 KR KR1020057024810A patent/KR101078127B1/ko active IP Right Grant
- 2004-06-28 EP EP04746588.5A patent/EP1640748A4/en not_active Withdrawn
- 2004-06-28 JP JP2005511072A patent/JPWO2005001525A1/ja active Pending
- 2004-06-28 WO PCT/JP2004/009119 patent/WO2005001525A1/ja active Application Filing
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KR20180049603A (ko) * | 2016-11-03 | 2018-05-11 | 연세대학교 산학협력단 | 다공성 물질을 이용한 광학체 및 이를 제조하기 위한 광학 제조장치 |
KR101930138B1 (ko) * | 2016-11-03 | 2018-12-17 | 연세대학교 산학협력단 | 다공성 물질을 이용한 광학체 및 이를 제조하기 위한 광학 제조장치 |
KR20180134251A (ko) * | 2017-06-08 | 2018-12-18 | 삼성에스디아이 주식회사 | 반사방지 필름, 이를 포함하는 편광판 및 이를 포함하는 광학표시장치 |
KR102040301B1 (ko) | 2017-06-08 | 2019-11-04 | 삼성에스디아이 주식회사 | 반사방지 필름, 이를 포함하는 편광판 및 이를 포함하는 광학표시장치 |
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WO2005001525A1 (ja) | 2005-01-06 |
KR20060072099A (ko) | 2006-06-27 |
TW200508647A (en) | 2005-03-01 |
US7285323B2 (en) | 2007-10-23 |
JP5045823B2 (ja) | 2012-10-10 |
TWI339741B (en) | 2011-04-01 |
KR101078127B1 (ko) | 2011-10-28 |
JPWO2005001525A1 (ja) | 2007-09-20 |
EP1640748A4 (en) | 2015-11-11 |
EP1640748A1 (en) | 2006-03-29 |
US20060164740A1 (en) | 2006-07-27 |
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