JP7325855B2 - 耐赤化層 - Google Patents
耐赤化層 Download PDFInfo
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- JP7325855B2 JP7325855B2 JP2021557866A JP2021557866A JP7325855B2 JP 7325855 B2 JP7325855 B2 JP 7325855B2 JP 2021557866 A JP2021557866 A JP 2021557866A JP 2021557866 A JP2021557866 A JP 2021557866A JP 7325855 B2 JP7325855 B2 JP 7325855B2
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Landscapes
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Description
△a*=a* a-a* i
△Ts=Ta-Ti
0.70~1=1/(1+0.025d/R)
HL≦0.9×HP
q=4πsin(θ/λ)
偏光層および耐赤化層等の厚みは、TEM(Transmission Electron Microscopy)機器を適用して測定することができる。前記TEM機器で偏光層や耐赤化層の断面を撮影した後に、撮影されたイメージから当該層の厚みを確認することができる。本実施例では、TEM機器としてHitachi社のH-7650製品を使用した。
中空粒子の粒度分布は、Otsuka Electronics社のELSZ-2000装備を用いて測定した。また、中空粒子の粒子直径および気孔サイズは、TEM(Transmission Electron Microscopy)機器を適用して測定した。本実施例では、TEM機器としてHitachi社のH-7650製品を使用した。前記粒子直径および気孔サイズは、前記TEM機器を使用して実施例等で製造された光学積層体(偏光板)における耐赤化層の断面を撮影(10000倍の倍率)した後に任意に50個の中空粒子を選択してそれぞれの粒子直径と気孔サイズを求め、その算術平均を粒子直径および気孔サイズの代表値とした。
色座標は、JASCO V-7100スペクトロフォトメーター(Spectrophotometer)を使用して測定した。前記JASCO V-7100スペクトロフォトメーターは、当該機器に内蔵された偏光子の吸収軸に対して測定対象偏光板の吸収軸を0度から360度まで回転させて透過率が最小となる地点で色座標(TD色座標)を測定し、前記透過率が最小となる地点でさらに測定対象偏光板の吸収軸を時計方向に90度回転させて色座標(MD色座標)を測定した後に、各測定値を基準として色座標の代表値を導き出す機器である。本明細書の実施例に記載された色座標は、前記JASCO V-7100スペクトロフォトメーターで確認される色座標である。
偏光板の単体透過率等は、JASCO V-7100スペクトロフォトメーター(Spectrophotometer)を使用して測定した。前記JASCO V-7100スペクトロフォトメーター(Spectrophotometer)は、偏光板の透過率等を380~780nmの範囲内で測定して前記波長範囲に対する代表値を導き出す機器であり、本実施例では、このようなJASCO V-7100スペクトロフォトメーター(Spectrophotometer)で確認される透過率を記載した。
偏光層に存在するカリウムKと亜鉛Znの重量比は、次の方式で測定した。まず、常温(約25℃)で約65重量%濃度の硝酸水溶液(2mL)に偏光層0.1g程度を溶かした後に、水(Deionized water)で40mLまで希釈した後に、ICP-OES(Optima 5300)を使用して偏光層に含まれているカリウムKと亜鉛Znの重量をそれぞれ測定した。
耐赤化層の熱拡散度は、次のような方式で測定した。下記実施例で記述した方式で厚みが略60μm程度のTAC(Triacetyl cellulose)フィルム(ヒョースン社製、PG601F)上に耐赤化層を形成した状態で前記熱拡散度を評価した。この際、耐赤化層の厚みは、各実施例に記載されている。前記TACフィルム/耐赤化層の積層体の上面および下面にグラファイトコーティング(graphite coating)を行った。前記グラファイトコーティングは、CRAMLIN社のGRAPHITE製品を使用して形成した。前記製品は、スプレー方式でグラファイトコーティングができる製品であり、当該製品を前記積層体の上面(耐赤化層の面)と下面(TACフィルム)に1回程度噴射後に乾燥してグラファイト層を形成した。その後、NETZSCH社のLFA 457 MicroFlash製品を使用して熱拡散度を測定した。熱拡散度は、95℃の温度を基準として測定し、前記一つのグラファイト面から他のグラファイト面への温度伝達の可否を通じて確認した。このような方式で積層体(耐赤化層/TACフィルム)の熱拡散度を評価し、実施例では、TACフィルムに対する前記積層体の熱拡散度の相対比率を記載した。
耐赤化層の赤外線反射率は、次の方式で確認した。下記実施例で記述した方式で厚みが略60μm程度のTAC(Triacetyl cellulose)フィルム上に耐赤化層を形成した状態で前記赤外線反射率を評価した。この際、耐赤化層の厚みは、各実施例に記載されている。前記耐赤化層/TACフィルムの積層体のTACフィルムの下面(耐赤化層が形成されていないフィルムの面)にブラックテープ(TOMOEGAWA社、PETフィルム)を付着して暗色化処理を行い、SHIMADZU社のSolidspec 3700装備を使用して、反射率(Reflectance)モードで800~1300nmの波長領域における平均反射率を測定した。前記機器を使用すると、800nm~1300nmの範囲内で1nm間隔の波長範囲に対する反射率を確認することができ、本実施例では、各波長に対する反射率の算術平均値を赤外線反射率の代表値とした。
耐赤化層の小角X線散乱の評価は、次の方式で行った。下記実施例で記述した方式で厚みが略60μm程度のTAC(Triacetyl cellulose)フィルム上に耐赤化層を形成した状態で前記評価を進行した。この際、耐赤化層の厚みは、各実施例に記載されている。前記TACフィルム/耐赤化層の積層体を横および縦がそれぞれ1cm程度になるようにカットして試験片を製作する。前記試験片の耐赤化層に0.0733nmの波長のX線を4m離れた距離で照射して散乱ベクトルによる散乱強度を求めた。前記測定は、浦項加速器4Cビームラインで行い、垂直のサイズが0.023mm程度であり、水平のサイズが0.3mm程度であるX線を利用した。検出器としては、2D mar CCDを利用した。散乱された2D回折パターンのイメージを得た後に、これをstandard試料(polyethylene-block-polybutadiene-block-polystyrene,SEBS)を通じて得られたsample-to-detector距離を用いてcalibrationし、circular averageを通じて散乱ベクトル(q)による散乱強度を換算した。この際、散乱ベクトルは、下記数式Aにより求めた。
q=4πsinθ/λ
耐赤化層の屈折率およびCauchy Parameterは、次の方式で行った。下記実施例で記述した方式で厚みが略60μm程度のTAC(Triacetyl cellulose)フィルム上に耐赤化層を形成した状態で前記評価を進行した。この際、耐赤化層の厚みは、各実施例に記載されている。前記積層体(耐赤化層/TACフィルム)の耐赤化層に対して装備(J.A.Woollam Co.M-2000)を使用して前記特性を評価した。前記耐赤化層に対して前記装備を適用して70度の入射角の条件で380nm~1,000nmの波長範囲で線偏光を測定した。測定された線偏光データ(Ellipsometry data (Psi(Ψ)、delta(Δ)))をComplete EASE softwareを用いて下記一般式1のCauchy modelのMSEが25以下になるように最適化(fitting)して、下記数式6のn(λ)、A、BおよびCを求めた。最適化過程でRoughness機能をon(範囲-20~50nm)として適用した。
耐赤化層(空隙含有層(多孔性層))の表面積比(Surface Area Ratio)は、AFM機器(Atomic Force Microscope,Park Systems,XE7)を使用して測定した。実施例の記載のようにTACフィルムの一面に形成された耐赤化層(空隙含有層(多孔性層))を有する積層体を横および縦長さが1cmになるようにカットして製作したサンプルをカーボンテープを使用して機器のステージに固定させ、測定を行った。測定のための探針(tip)としては、PPP-NCHR 10(Force Constant:42N/m、Resonance Frequency 330kHz)を使用した。測定条件は、下記の通りである。
x-scan size:1μm
y-scan size:1μm
Scan rate:0.7~1Hz
Z Servo Gain:1
Set Point:10~15nm
Scope:Line
Orientation:X and Y axis
Regression Order:1
厚みが約30μmのPVA(poly(vinyl alcohol))フィルム(日本合成社、M3004L)をヨウ素I2 0.2重量%およびヨウ化カリウムKI 2.5重量%を含む28℃の染色液に60秒間浸漬させて染色処理した。次に、染色されたPVAフィルムをホウ素1重量%およびヨウ化カリウムKI 3重量%を含む35℃の水溶液(架橋液)に60秒間浸漬させて架橋処理した。この後、架橋されたPVAフィルムをロール間延伸方法を用いて5.4倍の延伸倍率で延伸させた。延伸されたPVAフィルムを25℃のイオン交換水に60秒間浸漬させて洗浄し、硝酸亜鉛2重量%およびヨウ化カリウムKI 5重量%を含む25℃の水溶液に30秒間浸漬させた。この後、PVAフィルムを80℃の温度で60秒間乾燥させてPVA偏光層を製造した。前記製造された偏光層の最終厚みは、約12μm程度であり、カリウム含量は、約0.9重量%であり、亜鉛含量は、約0.3重量%であった。また、1/(1+0.025d/R)は、約0.9であった。前記でdは、偏光層の厚み(12μm)であり、Rは、偏光層に含まれているカリウム成分の重量比K(単位:weight)と亜鉛成分の重量比Zn(単位:weight)の比率K/Znである。
厚みが約45μmのPVA(poly(vinyl alcohol))フィルム(日本合成社、M4504L)を円盤フィルムとして使用して偏光層を製造した。まず、前記円盤フィルムに対して膨潤処理を行った。膨潤処理は、円盤フィルムを25℃の温度の純水に30秒間浸漬して行った。膨潤処理過程で最終延伸倍率の約28%程度までが延伸されるように延伸を進行した。次に、純水にヨウ素I2およびヨウ化カリウムKIがそれぞれ0.2重量%および2.5重量%程度の濃度で溶解した染色液を使用して染色処理を行った。染色処理は、28℃の前記染色液内に円盤フィルムを約2分間浸漬して行った。この過程で最終延伸倍率の約40%程度までが延伸されるように延伸を進行した。この後、染色されたPVAフィルムをホウ素1重量%およびヨウ化カリウム3重量%を含む35℃の水溶液(架橋液)に60秒間浸漬させて架橋処理した。次に、前記円盤フィルムを延伸した。延伸は、ホウ酸とヨウ化カリウムをそれぞれ3重量%程度で含む水溶液(処理液)内で行った。前記処理液の温度は、50℃程度であった。次に、水溶液で前記延伸されたフィルムを洗浄した。この際、水溶液の温度は、約25℃程度であり、洗浄処理は、1分以内で行った。その後、フィルムを乾燥してPVA偏光層を製造した(厚み:27μm、総延伸倍率:5.4倍)。
バインダーとしてTMPTA(trimethylolpropane triacrylate)を適用し、中空シリカ粒子(Hollow Silica Particle)を適用して、耐赤化層を製造した。前記中空シリカ粒子としては、D10、D50およびD90粒径がそれぞれ32.1nm、62.6nmおよび123.4nmである粒子を使用した。この場合、耐赤化層を形成した後に、TEMで測定した気孔サイズの平均は、略38.3nm程度であり、粒子直径は、略53nm程度であった。前記バインダー、前記中空シリカ粒子、含フッ素化合物(RS-90、DIC社)および開始剤(Irgacure 127、Ciba社)を、固形分を基準として31:65:0.1:3.9の重量比(バインダー:中空シリカ粒子:含フッ素化合物:開始剤)で溶媒MIBK(methyl isobutyl ketone)に希釈してコーティング液を製造した。
バインダーとしてTMPTA(trimethylolpropane triacrylate)を適用し、中空シリカ粒子(Hollow Silica Particle)を適用して、耐赤化層を製造した。前記中空シリカ粒子としては、D10、D50およびD90粒径は、それぞれ39.9nm、70.6nmおよび126.0nmである粒子を使用した。この場合、耐赤化層を形成した後に、TEMで測定した気孔サイズの平均は、略44.1nm程度であり、粒子直径は、略61nm程度であった。前記バインダー、前記中空シリカ粒子、含フッ素化合物(RS-90、DIC社)および開始剤(Irgacure 127、Ciba社)を55.1:40:1.1:3.8の重量比(バインダー:中空シリカ粒子:含フッ素化合物:開始剤)で溶媒MIBK(methyl isobutyl ketone)に希釈してコーティング液を製造した。
バインダーとしてPETA(Pentaerythritol triacrylate)を適用し、中空シリカ粒子(Hollow Silica Particle)を適用して耐赤化層を製造した。前記中空シリカ粒子としては、D10、D50およびD90粒径がそれぞれ39.9nm、70.6nmおよび126.0nmである粒子を使用した。この場合、耐赤化層を形成した後にTEMで測定した気孔サイズの平均は、略44.1nm程度であり、粒子直径は、略61nm程度であった。前記バインダー、前記中空シリカ粒子、含フッ素化合物(RS-90,DIC社)および開始剤(Irgacure 127,Ciba社)を76.5:20:0.5:3.0の重量比(バインダー:中空シリカ粒子:含フッ素化合物:開始剤)で溶媒MIBK(methyl isobutyl ketone)に希釈してコーティング液を製造した。
バインダーとしてPETA(Pentaerythritol triacrylate)を適用し、中空シリカ粒子(Hollow Silica Particle)を適用して、耐赤化層を製造した。前記中空シリカ粒子としては、D10、D50およびD90粒径がそれぞれ39.9nm、70.6nmおよび126.0nmである粒子を使用した。この場合、耐赤化層を形成した後にTEMで測定した気孔サイズの平均は、略44.1nm程度であり、粒子直径は、略61nm程度であった。前記バインダー、前記中空シリカ粒子、含フッ素化合物(RS-90、DIC社)および開始剤(Irgacure 127、Ciba社)を86.5:10:0.5:3.0の重量比(バインダー:中空シリカ粒子:含フッ素化合物:開始剤)で溶媒MIBK(methyl isobutyl ketone)に希釈してコーティング液を製造した。
バインダーとしてPETA(Pentaerythritol triacrylate)を適用し、中空粒子でなく、ソリッドシリカ粒子(Solid Silica Particle)を適用して、樹脂層材料を製造した。前記ソリッドシリカ粒子としては、D10、D50およびD90粒径がそれぞれ43.1nm、69.9nmおよび125.8nmである粒子を使用した。この場合、樹脂層を形成した後にTEMで測定した粒子直径は、略60nm程度であった。前記バインダー、前記ソリッドシリカ粒子、含フッ素化合物(RS-90、DIC社)および開始剤(Irgacure 127、Ciba社)を31:65:0.1:3.9の重量比(バインダー:ソリッドシリカ粒子:含フッ素化合物:開始剤)で溶媒MIBK(methyl isobutyl ketone)に希釈してコーティング液を製造した。
厚みが略60μm程度のTAC(Triacetyl cellulose)フィルム(ヒョースン社、PG601F)上に耐赤化層(空隙含有層)を形成した。耐赤化層は、製造例3の耐赤化層(A)材料をMayer barでコートし、60℃程度で1分程度乾燥した後に、紫外線を照射(252mJ/cm2)して、最終厚みが約450nm程度になるように形成した。前記形成された耐赤化層のTACフィルムと接する面と反対側の表面に対して測定した表面積比(Surface Area Ratio)は、約0.148水準であった。
製造例4のコーティング溶液をMayer barを用いて実施例1と同じTACフィルムにコートし、60℃で1分間乾燥した後に、紫外線を照射(252mJ/cm2)して、最終厚みが600nmになるように耐赤化層を形成した。前記形成された耐赤化層のTACフィルムと接する面と反対側の表面に対して測定した表面積比(Surface Area Ratio)は、約0.0359水準であった。
製造例5のコーティング材料を使用して実施例1と同じ方式で耐赤化層(空隙含有層) を形成するものの、前記耐赤化層の最終厚みは、略950nm程度になるように形成した。前記形成された耐赤化層のTACフィルムと接する面と反対側の表面に対して測定した表面積比(Surface Area Ratio)は、約0.109水準であった。
空隙含有層の厚みを300nm程度に変更したことを除いて、実施例1と同一に耐赤化層を製造した。前記形成された耐赤化層のTACフィルムと接する面と反対側の表面に対して測定した表面積比(Surface Area Ratio)は、約0.0715水準であった。
空隙含有層の厚みを400nm程度に変更したことを除いて、実施例1と同一に耐赤化層を製造した。前記形成された耐赤化層のTACフィルムと接する面と反対側の表面に対して測定した表面積比(Surface Area Ratio)は、約0.1643水準であった。
製造例5の耐赤化層のコーティング材料を適用して厚みが約500nmの空隙含有層を形成したことを除いて、実施例1と同一に耐赤化層を製造した。前記形成された耐赤化層のTACフィルムと接する面と反対側の表面に対して測定した表面積比(Surface Area Ratio)は、約0.2207水準であった。
製造例4の耐赤化層用コーティング材料を適用したことを除いて、実施例6と同一に耐赤化層を製造した。前記形成された耐赤化層のTACフィルムと接する面と反対側の表面に対して測定した表面積比(Surface Area Ratio)は、約0.0387水準であった。
製造例3の耐赤化層用コーティング材料を適用したことを除いて、実施例6と同一に耐赤化層を製造した。前記形成された耐赤化層のTACフィルムと接する面と反対側の表面に対して測定した表面積比(Surface Area Ratio)は、約0.0513水準であった。
製造例6の材料を適用して厚みが約3000nmの空隙含有層を形成したことを除いて、実施例6と同一に耐赤化層を製造した。前記形成された耐赤化層のTACフィルムと接する面と反対側の表面に対して測定した表面積比(Surface Area Ratio)は、約0.0611水準であった。
厚みが略60μm程度のTAC(Triacetyl cellulose)フィルム(ヒョースン社、PG601F)上に樹脂層を形成した。製造例7の樹脂層(A)材料をMayer barでコートし、60℃程度で1分程度乾燥した後に紫外線を照射(252mJ/cm2)して、最終厚みが約450nm程度になるように樹脂層を形成した。前記形成された樹脂層のTACフィルムと接する面と反対側の表面に対して測定した表面積比(Surface Area Ratio)は、約0.01水準であった。
製造例1で得られた偏光層(A)に一般的な光学用水系接着剤層(厚み:100nm)を適用して保護フィルムとして厚みが略30μm程度のCOP(Cycloolefin Polymer)フィルム(製造社:Zeon)を付着した。前記製造したCOPフィルムと偏光層(A)の積層体の偏光層(A)に実施例1の耐赤化層の空隙含有層を上記と同じ水系接着剤(厚み:100nm)で付着した。次に、偏光板の下部にアクリル系粘着剤層を形成して保護フィルム(COPフィルム)、接着剤層、偏光層、接着剤層、耐赤化層(空隙含有層)、保護フィルム(TACフィルム)および粘着剤層が順次積層された構造の偏光板(光学積層体)を製造した。
実施例2で製造した耐赤化層を適用したことを除いて、実施例10と同一に偏光板を製造した。
実施例3で製造した耐赤化層を適用したことを除いて、実施例10と同一に偏光板を製造した。
耐赤化層を適用しないことを除いて、実施例10と同一に偏光板を製造した。
実施例4で製造した耐赤化層を適用したことを除いて、実施例10と同一に偏光板を製造した。
実施例5で製造した耐赤化層を適用したことを除いて、実施例10と同一に偏光板を製造した。
耐赤化層を適用しないことを除いて、実施例13と同一に偏光板を製造した。
実施例6で製造した耐赤化層を適用したことを除いて、実施例10と同一に偏光板を製造した。
実施例7で製造した耐赤化層を適用したことを除いて、実施例15と同一に偏光板を製造した。
実施例8で製造した耐赤化層を適用したことを除いて、実施例15と同一に偏光板を製造した。
実施例9で製造した耐赤化層を適用したことを除いて、実施例15と同一に偏光板を製造した。
製造例1で得られた偏光層(A)に一般的な光学用水系接着剤層(厚み:100nm)を適用して保護フィルムとして厚みが略30μm程度のCOP(Cycloolefin Polymer)フィルム(製造社:Zeon)を付着した。前記製造したCOPフィルムと偏光層(A)の積層体の偏光層(A)に比較例1の樹脂層を上記と同じ水系接着剤(厚み:100nm)で付着した。次に、偏光板の下部にアクリル系粘着剤層を形成して保護フィルム(COPフィルム)、接着剤層、偏光層、接着剤層、樹脂層、保護フィルム(TACフィルム)および粘着剤層が順次積層された構造の偏光板(光学積層体)を製造した。
耐赤化層 20
更なる層 30
偏光層 100
保護フィルム 301
保護フィルム 302
Claims (12)
- 耐赤化層であって、
前記耐赤化層は、空隙含有層であるか、前記空隙含有層を含む積層体であり、
前記空隙含有層は、小角X線散乱の散乱強度のlog値グラフで0.1~0.184nm-1(0.0758~0.1256nm-1を除く)の散乱ベクトルの範囲内でピークを示し、下記数式4を満たす、耐赤化層:
[数式4]
HL≦0.9×HP
数式4で、HLは、高分子フィルムと前記高分子フィルムの一面に形成された前記耐赤化層の積層体の熱拡散度であり、HPは、前記高分子フィルムの熱拡散度である。 - 前記空隙含有層の空隙のサイズが0.5nm~100nmの範囲内である、請求項1に記載の耐赤化層。
- 前記空隙含有層の空隙の体積分率が0.1以上である、請求項1または2に記載の耐赤化層。
- 前記空隙含有層は、バインダーおよび中空粒子を含む、請求項1~3のいずれか一項に記載の耐赤化層。
- バインダーは、2個~10個の範囲内の重合性官能基を有する多官能性アクリレートの重合物を含む、請求項4に記載の耐赤化層。
- 中空粒子は、粒度分布の重量累積曲線でD10粒径、D50粒径およびD90粒径がそれぞれ25nm~50nm、50nm~95nmおよび100nm~200nmの範囲内にある、請求項4または5に記載の耐赤化層。
- 前記空隙含有層は、ソリッド粒子を含まない、請求項1~6のいずれか一項に記載の耐赤化層。
- 前記空隙含有層は、厚みが200nm以上である、請求項1~7のいずれか一項に記載の耐赤化層。
- 光学機能層と、前記光学機能層の少なくとも一面に形成されている請求項1~8のいずれか一項に記載の耐赤化層と、を含む、光学積層体。
- 前記耐赤化層は、光学機能層と隣接して存在し、前記耐赤化層と前記光学機能層との距離が90μm以内である、請求項9のいずれか一項に記載の光学積層体。
- 前記光学機能層がヨウ素系偏光層である、請求項10に記載の光学積層体。
- カバーガラスと前記カバーガラスに付着した光学積層体とを含み、前記光学積層体は、光学機能層と、前記光学機能層の少なくとも一面に形成されている請求項1~8のいずれか一項に記載の耐赤化層と、を含む、ディスプレイ装置。
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