JP2004309898A - Antireflection film - Google Patents
Antireflection film Download PDFInfo
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- JP2004309898A JP2004309898A JP2003105280A JP2003105280A JP2004309898A JP 2004309898 A JP2004309898 A JP 2004309898A JP 2003105280 A JP2003105280 A JP 2003105280A JP 2003105280 A JP2003105280 A JP 2003105280A JP 2004309898 A JP2004309898 A JP 2004309898A
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- refractive index
- index layer
- layer
- antireflection film
- antireflection
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- 229920005989 resin Polymers 0.000 claims abstract description 14
- 239000011347 resin Substances 0.000 claims abstract description 14
- 239000000758 substrate Substances 0.000 claims abstract description 9
- 238000004544 sputter deposition Methods 0.000 claims abstract description 7
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052738 indium Inorganic materials 0.000 claims description 4
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- 239000010419 fine particle Substances 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 1
- 238000010186 staining Methods 0.000 claims 1
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- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 description 3
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- 239000000203 mixture Substances 0.000 description 2
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- MRIKSZXJKCQQFT-UHFFFAOYSA-N (3-hydroxy-2,2-dimethylpropyl) prop-2-enoate Chemical compound OCC(C)(C)COC(=O)C=C MRIKSZXJKCQQFT-UHFFFAOYSA-N 0.000 description 1
- OYKPJMYWPYIXGG-UHFFFAOYSA-N 2,2-dimethylbutane;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCC(C)(C)C OYKPJMYWPYIXGG-UHFFFAOYSA-N 0.000 description 1
- BTJPUDCSZVCXFQ-UHFFFAOYSA-N 2,4-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC(CC)=C3SC2=C1 BTJPUDCSZVCXFQ-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- FDSUVTROAWLVJA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)COCC(CO)(CO)CO FDSUVTROAWLVJA-UHFFFAOYSA-N 0.000 description 1
- PTJDGKYFJYEAOK-UHFFFAOYSA-N 2-butoxyethyl prop-2-enoate Chemical compound CCCCOCCOC(=O)C=C PTJDGKYFJYEAOK-UHFFFAOYSA-N 0.000 description 1
- NLGDWWCZQDIASO-UHFFFAOYSA-N 2-hydroxy-1-(7-oxabicyclo[4.1.0]hepta-1,3,5-trien-2-yl)-2-phenylethanone Chemical compound OC(C(=O)c1cccc2Oc12)c1ccccc1 NLGDWWCZQDIASO-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
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- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
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- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 description 1
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- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 1
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 1
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- 229910052799 carbon Inorganic materials 0.000 description 1
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- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
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- 238000007865 diluting Methods 0.000 description 1
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- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 1
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- 229910052739 hydrogen Inorganic materials 0.000 description 1
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- 229910001507 metal halide Inorganic materials 0.000 description 1
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- YDKNBNOOCSNPNS-UHFFFAOYSA-N methyl 1,3-benzoxazole-2-carboxylate Chemical compound C1=CC=C2OC(C(=O)OC)=NC2=C1 YDKNBNOOCSNPNS-UHFFFAOYSA-N 0.000 description 1
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- QCTJRYGLPAFRMS-UHFFFAOYSA-N prop-2-enoic acid;1,3,5-triazine-2,4,6-triamine Chemical compound OC(=O)C=C.NC1=NC(N)=NC(N)=N1 QCTJRYGLPAFRMS-UHFFFAOYSA-N 0.000 description 1
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Surface Treatment Of Optical Elements (AREA)
- Laminated Bodies (AREA)
- Transforming Electric Information Into Light Information (AREA)
- Devices For Indicating Variable Information By Combining Individual Elements (AREA)
Abstract
Description
【０００１】
【発明の属する技術分野】
本発明は、反射防止フィルムに関し、ＣＲＴ画面、ＬＣＤ画面、ＰＤＰ画面などのディスプレー、ガラスやプラステックからなるウインドウの表面で外光の反射を防止する反射防止フィルムに関する。
【０００２】
【従来の技術】
従来から、ディスプレーを使用する場所の多くは蛍光灯や太陽光等の外光がディスプレイ表面で反射する場所にあり、ディスプレイが本来表示している画面が見にくくなる。近年、このような環境下でのディスプレー表示画質の向上が要求され、この要求に対して、可視光の広範囲において反射防止の効果をもつ薄膜を積層した反射防止フィルムをディスプレーの表面に貼り付けることが行われている。反射防止フィルムとして、例えば特願２００１−２０４４７２号が出願されている。
【０００３】
【発明が解決しようとする課題】
反射防止層の薄膜を積層する際に各層の密着性が必要である。本発明は、反射防止の薄膜を積層することができる高い密着性を備える反射防止フィルムを提供することを課題とする。
【０００４】
【課題を解決するための手段】
すなわち本発明は、透明基材の少なくとも片面にハードコート層を備え、かつ透明基材側から中屈折率層、高屈折率層、低屈折率層の順に配置された反射防止層を備え、中屈折率層が電離放射線硬化型樹脂からなり、高屈折率層がスパッタリング法により形成されていることを特徴とする反射防止フィルムである。
【０００５】
以下、本発明を詳細に説明する。
【０００６】
［透明基材］
透明基材としてはプラスチックフィルムが用いられる。プラスチックはいかなるものであっても良い。例えば、ポリエチレンテレフタレート、トリアセチルセルロースのフィルム、ポリカーボネートが挙げられる。透明基材の厚みは、加工性やフレキシビリティの点から１０μｍ〜５００μｍが好ましい。
【０００７】
［ハードコート層］
ハードコート層は、その硬さは好ましくは２Ｈ以上、さらに好ましくは３Ｈ以上であり、さらに光学特性も考慮されていることが望ましい。このハードコート層を施すことによって、画面上に使用される場合であってもキズがつき難くなるなどの効果を付与することができる。
【０００８】
なお、ハードコート層は透明基材の反射防止層が設けられる側の面に設けられてもよく、その反対側の面に設けられてもよい。
【０００９】
ハードコード層は、通常、電離放射線硬化型樹脂または光重合性ポリマーからなる。電離放射線硬化型樹脂は、少なくとも電子線あるいは紫外線照射により硬化される樹脂を含有する塗料から形成される。具体的には、光重合性プレポリマー、光重合性モノマー、光重合開始剤を含有し、更に必要に応じて増感剤、非反応性樹脂、レベリング剤等の添加剤、溶剤を含有する。電離放射線硬化型塗料を硬化させるには、電子線あるいは紫外線を照射する。電子線を照射する場合、走査型あるいはカーテン型の電子線加速器を用い、加速電圧１０００ｋｅＶ以下、好ましくは１００〜３００ｋｅＶのエネルギーを有し、１００ｎｍ以下の波長領域の電子線を照射して行うことができる。紫外線を照射する場合、超高圧水銀灯、高圧水銀灯、低圧水銀灯、カーボンアーク、メタルハライドランプ等を用い、１００〜４００ｎｍ、好ましくは２００〜４００ｎｍの波長領域で、５０〜３００ｋｃａｌ／ｍｏｌのエネルギーを有する紫外線を照射する。
【００１０】
光重合性プレポリマーは、その構造、分子量が電離放射線硬化型塗料の硬化に関係し、電離放射線硬化型樹脂の接着性、硬度、耐クラック性等の特性を定めるものである。光重合性プレポリマーは骨格中に導入されたアクリロイル基が電離放射線照射されることにより、ラジカル重合する。ラジカル重合により硬化するものは硬化速度が速く、樹脂設計の自由度も大きいため、特に好ましい。
【００１１】
光重合性プレポリマーとしては、アクリロイル基を有するアクリル系プレポリマーが特に好ましく、１分子中に２個以上のアクリロイル基を有し、３次元網目構造となるものである。アクリル系プレポリマーとしては、ウレタンアクリレート、エポキシアクリレート、メラミンアクリレート、ポリエステルアクリレート等が使用できる。
【００１２】
光重合性モノマーは、高粘度の光重合性プレポリマーを希釈し、粘度を低下させ、作業性を向上させるために、また、架橋剤として塗膜強度を付与するために使用される。光重合性モノマーとしては、２−エチルヘキシルアクリレート、２−ヒドロキシエチルアクリレート、２−ヒドロキシプロピルアクリレート、ブトキシエチルアクリレート等の単官能アクリルモノマー、１、６−ヘキサジオールアクリレート、ネオペンチルグリコールジアクリレート、ヒドロキシパビリン酸エステルネオペンチルグリコールアクリレート等の２官能アクリルモノマー、ジペンタエリスリトールヘキサアクリレート、トリメチルプロパントリアクリレート、ペンタエリスリトールトリアクリレート等の多官能アクリルモノマー等の１種若しくは２種以上が使用される。
【００１３】
また、光重合性モノマーの混合量が多くなると塗膜は必要以上に硬くなるため、所望の硬度、あるいは所望の可撓性が得られるよう、混合割合は適宜選択するとよい。例えば、本発明の透明ハードコートフィルムを曲げる用途に使用する場合は、可撓性に優れた熱硬化性、熱可塑性アクリル樹脂、エポキシ樹脂等の非反応性樹脂を混合することにより、硬度を調節することができる。
【００１４】
光重合開始剤は、電離放射線の照射によりアクリロイル基の反応を短時間で開始させ、反応を促進させるために添加され、触媒的な作用を有するものである。光重合開始剤は、特に紫外線照射により硬化を行なう場合に必要とされ、高いエネルギーの電子線を照射する時には必要としない場合もある。光重合開始剤の種類としては、開裂することによりラジカル重合させるもの、水素を引き抜くことによりラジカル重合させるもの、あるいはイオンを発生させることによりカチオン重合させるものがある。
【００１５】
光重合開始剤としては、適宜選択できる。例えば、ベンゾインエーテル系、ケタール系、アセトフェノン系、チオキサントン系等のラジカル型光重合開始剤、ジアゾニウム塩、ジアリールヨードニウム塩、トリアリールスルホニウム塩等や複合系のカチオン型光重合開始剤が挙げられる。これらは１種で用いてもよく、あるいは２種以上を併せて使用してもよい。光重合開始剤は樹脂固型分に対して２〜１０重量％、好ましくは３〜６重量％混合して使用する。
【００１６】
［反射防止層］
本発明において反射防止層を構成する中屈折率層、高屈折率、低屈折率は、相対的な屈折率の高低による分類である。、中屈折率層は屈折率１．５〜１．９、高屈折率層は屈折率１．８〜２．５、低屈折率は屈折率１．３５〜１．５の範囲である。各層の厚みは通常１５〜１５０ｎｍであり、反射スペクトルの調整のために適宜調整される。
【００１７】
［中屈折率層］
中屈折率層は、電離放射線硬化型樹脂からなり、この中屈折率層は、好ましくは、チタン、ジルコニウム、インジウム、錫、セリウムおよびイットリウムからなる群から選ばれる少なくとも１種の金属の酸化物の微粒子を含有する。この酸化物の微粒子は、光の散乱を起こさないようにする観点から、好ましくは粒径が５〜５００ｎｍ、さらに好ましくは粒径が１０〜１００ｎｍのものを用いるとよい。
【００１８】
［高屈折率層］
高屈折率層はスパッタリング法を用いて形成する。高屈折率層は、好ましくは、チタン、ジルコニウム、インジウムおよび錫からなる群から選ばれる少なくとも１種の金属の酸化物からなる。金属酸化物層を形成するスパッタリングの方法としては、金属酸化物をターゲットとした方法の他、金属ターゲットを用い、酸素を導入しながら行う反応性スパッタリングの方法を用いることもできる。
【００１９】
［低屈折率層］
低屈折率層には、たとえば、含フッ素化合物または酸化ケイ素等の無機化合物を用いる。含フッ素化合物の架橋物は、好ましくは架橋性の含フッ素高分子化合物を加熱または電離放射線照射により形成される架橋物である。酸化ケイ素等の無機化合物も用いる場合、最表層にフッ素ポリマーを非常に薄く形成し、防汚染性を付与することが好ましい。
【００２０】
【実施例】
本発明を詳細に説明するために、以下に実施例を挙げて説明する。
評価は次の方法による。
【００２１】
［密着性］
密着性は、ＪＩＳ５４００に定められる方法で評価した。８点以上が◎、４〜７点が△、３点以下が×である。
【００２２】
［反射率］
反射率は、裏面に黒色のビニールテープを貼り、裏面反射の影響を除いてから、絶対反射率を測定し、その反射スペクトルから、３刺激値のＹを求めた。
【００２３】
［実施例１］
１００μｍのポリエチレンテレフタレートフィルム（帝人（株）製、ＯＰＦＷ）に、紫外線硬化型ハードコート剤（大日本インキ化学（株）製、）をバーコーターで塗布、８０Ｗの高圧水銀灯を照射、硬化し厚さ５μｍのハードコート層を設け、この上にジペンタエリスリトールペンタアクリレートとジペンタエリスリトールヘキサアクリレートの混合物（ＤＰＨＡ、日本化薬（株）製）７５ｇ、ビス（４−メタクリロイルチオフェニル）スルフィド（ＭＰＳＭＡ、住友精化（株）製）７５ｇ、平均粒径５０ｎｍのＩＴＯ粒子（シーアイ化成（株）製）１００ｇを、４３９ｇのメチルエチルケトン／シクロヘキサノン（５０％／５０％）混合溶媒に溶解した。得られた溶液に、光重合開始剤（イルガキュア９０７、チバガイギー（株）製）５．０ｇおよび光増感剤（カヤキュアーＤＥＴＸ、日本化薬（株）製）３．０ｇを４９ｇのメチルエチルケトンに溶解した溶液を加えたものをバーコーターで塗工硬化し、中屈折率層を１００ｎｍとなるように形成した。更に、高屈折率層としてスパッタリングにより酸化チタンを２０ｎｍ形成した。この上に熱架橋性含フッ素ポリマー（オプスターＪＮ７２２８、ＪＳＲ（株）製）を塗布硬化し、１００ｎｍの低屈折率層を形成した。
評価結果を表１に示す。
【００２４】
【表１】
［比較例１］
高屈折率層を真空蒸着法で形成した以外は実施例１と同様に行った。電離放射線硬化型塗料を硬化させるためには紫外線を照射した。紫外線の照射は、８０Ｗの高圧水銀灯を用いて紫外線を照射した。
評価結果を表１に示す。
【００２６】
【発明の効果】
本発明によれば、電離放射線硬化型樹脂からなる中屈折率層の上に、高屈折率層をスパッタリング法により積層することにより、密着性の高い反射防止フィルムを提供することができる。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to an anti-reflection film, and more particularly to an anti-reflection film for preventing reflection of external light on the surface of a display such as a CRT screen, an LCD screen, a PDP screen, and a window made of glass or plastic.
[0002]
[Prior art]
2. Description of the Related Art Conventionally, many places where a display is used are located where external light such as a fluorescent lamp or sunlight is reflected on a display surface, and it is difficult to see a screen originally displayed by the display. In recent years, it has been required to improve display image quality in such an environment. In response to this demand, an anti-reflection film in which thin films having an anti-reflection effect are applied over a wide range of visible light is adhered to the surface of the display. Has been done. For example, Japanese Patent Application No. 2001-204472 has been applied as an antireflection film.
[0003]
[Problems to be solved by the invention]
When laminating a thin film of an antireflection layer, the adhesion of each layer is necessary. An object of the present invention is to provide an antireflection film having high adhesion on which an antireflection thin film can be laminated.
[0004]
[Means for Solving the Problems]
That is, the present invention comprises a hard coat layer on at least one side of the transparent substrate, and comprises an antireflection layer arranged in the order of a medium refractive index layer, a high refractive index layer, and a low refractive index layer from the transparent substrate side, An antireflection film, wherein the refractive index layer is made of an ionizing radiation curable resin, and the high refractive index layer is formed by a sputtering method.
[0005]
Hereinafter, the present invention will be described in detail.
[0006]
[Transparent substrate]
A plastic film is used as the transparent substrate. The plastic may be any. For example, polyethylene terephthalate, a film of triacetyl cellulose, and polycarbonate are mentioned. The thickness of the transparent substrate is preferably from 10 μm to 500 μm from the viewpoint of processability and flexibility.
[0007]
[Hard coat layer]
The hardness of the hard coat layer is preferably 2H or more, more preferably 3H or more, and it is desirable that optical characteristics are also taken into consideration. By applying the hard coat layer, it is possible to provide an effect such that a scratch is hardly formed even when the hard coat layer is used on a screen.
[0008]
The hard coat layer may be provided on the surface of the transparent substrate on which the antireflection layer is provided, or may be provided on the opposite surface.
[0009]
The hard code layer is usually made of an ionizing radiation curable resin or a photopolymerizable polymer. The ionizing radiation-curable resin is formed from a paint containing at least a resin that is cured by irradiation with an electron beam or ultraviolet rays. Specifically, it contains a photopolymerizable prepolymer, a photopolymerizable monomer, and a photopolymerization initiator, and further contains, if necessary, additives such as a sensitizer, a non-reactive resin, and a leveling agent, and a solvent. In order to cure the ionizing radiation-curable paint, it is irradiated with an electron beam or ultraviolet rays. Irradiation with an electron beam can be performed by using a scanning or curtain type electron beam accelerator and irradiating an electron beam having an acceleration voltage of 1000 keV or less, preferably energy of 100 to 300 keV, and a wavelength region of 100 nm or less. it can. When irradiating ultraviolet rays, an ultrahigh-pressure mercury lamp, a high-pressure mercury lamp, a low-pressure mercury lamp, a carbon arc, a metal halide lamp, or the like is used. Irradiate.
[0010]
The structure and molecular weight of the photopolymerizable prepolymer relate to the curing of the ionizing radiation-curable coating material, and determine the properties of the ionizing radiation-curable resin, such as adhesiveness, hardness, and crack resistance. The photopolymerizable prepolymer undergoes radical polymerization when the acryloyl group introduced into the skeleton is irradiated with ionizing radiation. Those cured by radical polymerization are particularly preferred because they have a high curing rate and a high degree of freedom in resin design.
[0011]
As the photopolymerizable prepolymer, an acrylic prepolymer having an acryloyl group is particularly preferable, and an acrylic prepolymer having two or more acryloyl groups in one molecule and having a three-dimensional network structure is preferable. As the acrylic prepolymer, urethane acrylate, epoxy acrylate, melamine acrylate, polyester acrylate and the like can be used.
[0012]
The photopolymerizable monomer is used for diluting a high-viscosity photopolymerizable prepolymer, lowering the viscosity and improving workability, and for imparting coating strength as a crosslinking agent. Examples of the photopolymerizable monomer include monofunctional acrylic monomers such as 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, and butoxyethyl acrylate, 1,6-hexadiol acrylate, neopentyl glycol diacrylate, and hydroxypropyl acrylate. One or two or more of bifunctional acrylic monomers such as biphosphate neopentyl glycol acrylate and the like and polyfunctional acrylic monomers such as dipentaerythritol hexaacrylate, trimethylpropane triacrylate and pentaerythritol triacrylate are used.
[0013]
In addition, when the mixing amount of the photopolymerizable monomer increases, the coating film becomes harder than necessary. Therefore, the mixing ratio may be appropriately selected so as to obtain a desired hardness or a desired flexibility. For example, when used for bending the transparent hard coat film of the present invention, the hardness is adjusted by mixing a non-reactive resin such as a thermosetting resin having excellent flexibility, a thermoplastic acrylic resin, or an epoxy resin. can do.
[0014]
The photopolymerization initiator is added to start the reaction of the acryloyl group in a short time by irradiation with ionizing radiation and promote the reaction, and has a catalytic action. The photopolymerization initiator is required particularly when curing is performed by ultraviolet irradiation, and may not be required when irradiating a high energy electron beam. Types of photopolymerization initiators include those that undergo radical polymerization by cleavage, those that undergo radical polymerization by extracting hydrogen, and those that undergo cationic polymerization by generating ions.
[0015]
The photopolymerization initiator can be appropriately selected. Examples thereof include radical type photopolymerization initiators such as benzoin ether type, ketal type, acetophenone type and thioxanthone type, diazonium salts, diaryliodonium salts, triarylsulfonium salts and the like, and composite type photopolymerization initiators. These may be used alone or in combination of two or more. The photopolymerization initiator is used in a mixture of 2 to 10% by weight, preferably 3 to 6% by weight, based on the solid resin component.
[0016]
[Anti-reflective layer]
In the present invention, the medium refractive index layer, the high refractive index, and the low refractive index constituting the antireflection layer are classified according to the relative refractive index. The middle refractive index layer has a refractive index of 1.5 to 1.9, the high refractive index layer has a refractive index of 1.8 to 2.5, and the low refractive index has a refractive index of 1.35 to 1.5. The thickness of each layer is usually 15 to 150 nm, and is appropriately adjusted for adjusting the reflection spectrum.
[0017]
[Medium refractive index layer]
The middle refractive index layer is made of an ionizing radiation-curable resin, and the middle refractive index layer is preferably made of at least one metal oxide selected from the group consisting of titanium, zirconium, indium, tin, cerium and yttrium. Contains fine particles. The oxide fine particles preferably have a particle size of 5 to 500 nm, more preferably 10 to 100 nm, from the viewpoint of preventing light scattering.
[0018]
[High refractive index layer]
The high refractive index layer is formed by a sputtering method. The high refractive index layer is preferably made of an oxide of at least one metal selected from the group consisting of titanium, zirconium, indium and tin. As a sputtering method for forming a metal oxide layer, a reactive sputtering method using a metal target while introducing oxygen, in addition to a method using a metal oxide as a target, can also be used.
[0019]
[Low refractive index layer]
For the low refractive index layer, for example, a fluorine-containing compound or an inorganic compound such as silicon oxide is used. The crosslinked product of the fluorine-containing compound is preferably a crosslinked product formed by heating or ionizing radiation irradiation of a crosslinkable fluorine-containing polymer compound. When an inorganic compound such as silicon oxide is also used, it is preferable to form a very thin fluoropolymer on the outermost layer to impart antifouling properties.
[0020]
【Example】
In order to explain the present invention in detail, examples will be described below.
Evaluation is based on the following method.
[0021]
[Adhesion]
The adhesion was evaluated by the method specified in JIS5400. 8 or more points are ◎, 4 to 7 points are Δ, and 3 or less points are X.
[0022]
[Reflectance]
The reflectivity was determined by applying a black vinyl tape to the back surface, removing the influence of back surface reflection, measuring the absolute reflectivity, and determining the tristimulus value Y from the reflection spectrum.
[0023]
[Example 1]
A 100 μm polyethylene terephthalate film (manufactured by Teijin Limited, OPFW) was coated with an ultraviolet-curable hard coat agent (manufactured by Dainippon Ink and Chemicals, Inc.) using a bar coater, irradiated with an 80 W high-pressure mercury lamp, cured and cured. A 5 μm hard coat layer was provided, on which 75 g of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.), bis (4-methacryloylthiophenyl) sulfide (MPSMA, Sumitomo) 100 g of ITO particles (manufactured by Seika Chemical Co., Ltd.) and 100 g of ITO particles having an average particle size of 50 nm (manufactured by CI Kasei Co., Ltd.) were dissolved in 439 g of a mixed solvent of methyl ethyl ketone / cyclohexanone (50% / 50%). 5.0 g of a photopolymerization initiator (Irgacure 907, manufactured by Ciba Geigy) and 3.0 g of a photosensitizer (Kayacure DETX, manufactured by Nippon Kayaku) were dissolved in 49 g of methyl ethyl ketone. The solution to which the solution was added was applied and cured with a bar coater to form a middle refractive index layer having a thickness of 100 nm. Further, titanium oxide was formed to a thickness of 20 nm as a high refractive index layer by sputtering. A heat-crosslinkable fluoropolymer (OPSTAR JN7228, manufactured by JSR Corporation) was applied thereon and cured to form a low refractive index layer having a thickness of 100 nm.
Table 1 shows the evaluation results.
[0024]
[Table 1]
[Comparative Example 1]
The same operation as in Example 1 was performed except that the high refractive index layer was formed by a vacuum evaporation method. Ultraviolet rays were applied to cure the ionizing radiation-curable paint. Ultraviolet irradiation was performed using an 80 W high-pressure mercury lamp.
Table 1 shows the evaluation results.
[0026]
【The invention's effect】
According to the present invention, an antireflection film having high adhesion can be provided by laminating a high refractive index layer on a middle refractive index layer made of an ionizing radiation curable resin by a sputtering method.
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003105280A JP2004309898A (en) | 2003-04-09 | 2003-04-09 | Antireflection film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003105280A JP2004309898A (en) | 2003-04-09 | 2003-04-09 | Antireflection film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2004309898A true JP2004309898A (en) | 2004-11-04 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2003105280A Pending JP2004309898A (en) | 2003-04-09 | 2003-04-09 | Antireflection film |
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| Country | Link |
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| JP (1) | JP2004309898A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007316576A (en) * | 2006-04-26 | 2007-12-06 | Nitto Denko Corp | Hard-coated antiglare film, polarizing plate, image display, and method of manufacturing hard-coated antiglare film |
| JP2007334064A (en) * | 2006-06-15 | 2007-12-27 | Nitto Denko Corp | Antidazzle hard coat film, and polarizing plate and image display apparatus using the same |
| JP2008032763A (en) * | 2006-07-26 | 2008-02-14 | Nitto Denko Corp | Hard coat film, polarizing plate using the same and image display device |
| US8883935B2 (en) | 2010-04-29 | 2014-11-11 | Battelle Memorial Institute | High refractive index composition |
| WO2022181562A1 (en) * | 2021-02-24 | 2022-09-01 | 東京応化工業株式会社 | Photocurable liquid composition, cured object, and method for producing cured object |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10206603A (en) * | 1997-01-20 | 1998-08-07 | Dainippon Printing Co Ltd | Reflection preventive film and manufacture thereof |
| JP2000214302A (en) * | 1999-01-20 | 2000-08-04 | Dainippon Printing Co Ltd | Antireflection film and its production |
| JP2001281408A (en) * | 2000-03-29 | 2001-10-10 | Dainippon Printing Co Ltd | Antireflection film and method for manufacturing the same |
| JP2001337202A (en) * | 2000-05-29 | 2001-12-07 | Teijin Ltd | Antireflection film |
-
2003
- 2003-04-09 JP JP2003105280A patent/JP2004309898A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10206603A (en) * | 1997-01-20 | 1998-08-07 | Dainippon Printing Co Ltd | Reflection preventive film and manufacture thereof |
| JP2000214302A (en) * | 1999-01-20 | 2000-08-04 | Dainippon Printing Co Ltd | Antireflection film and its production |
| JP2001281408A (en) * | 2000-03-29 | 2001-10-10 | Dainippon Printing Co Ltd | Antireflection film and method for manufacturing the same |
| JP2001337202A (en) * | 2000-05-29 | 2001-12-07 | Teijin Ltd | Antireflection film |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007316576A (en) * | 2006-04-26 | 2007-12-06 | Nitto Denko Corp | Hard-coated antiglare film, polarizing plate, image display, and method of manufacturing hard-coated antiglare film |
| JP2007334064A (en) * | 2006-06-15 | 2007-12-27 | Nitto Denko Corp | Antidazzle hard coat film, and polarizing plate and image display apparatus using the same |
| JP2008032763A (en) * | 2006-07-26 | 2008-02-14 | Nitto Denko Corp | Hard coat film, polarizing plate using the same and image display device |
| US8883935B2 (en) | 2010-04-29 | 2014-11-11 | Battelle Memorial Institute | High refractive index composition |
| WO2022181562A1 (en) * | 2021-02-24 | 2022-09-01 | 東京応化工業株式会社 | Photocurable liquid composition, cured object, and method for producing cured object |
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