JP2006188016A - Reflection preventing film - Google Patents
Reflection preventing film Download PDFInfo
- Publication number
- JP2006188016A JP2006188016A JP2005002822A JP2005002822A JP2006188016A JP 2006188016 A JP2006188016 A JP 2006188016A JP 2005002822 A JP2005002822 A JP 2005002822A JP 2005002822 A JP2005002822 A JP 2005002822A JP 2006188016 A JP2006188016 A JP 2006188016A
- Authority
- JP
- Japan
- Prior art keywords
- film
- layer
- refractive index
- hard coat
- active energy
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 230000003405 preventing effect Effects 0.000 title abstract description 6
- 239000002216 antistatic agent Substances 0.000 claims abstract description 36
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- 229920005989 resin Polymers 0.000 claims abstract description 19
- 239000011347 resin Substances 0.000 claims abstract description 19
- 125000002091 cationic group Chemical group 0.000 claims description 17
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 7
- 230000005484 gravity Effects 0.000 claims description 4
- 239000002904 solvent Substances 0.000 abstract description 16
- 239000000428 dust Substances 0.000 abstract description 13
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- 150000001875 compounds Chemical class 0.000 description 16
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 125000000217 alkyl group Chemical group 0.000 description 10
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
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- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
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- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 239000000654 additive Substances 0.000 description 2
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- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
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- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 2
- 238000007756 gravure coating Methods 0.000 description 2
- 229910001412 inorganic anion Inorganic materials 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
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- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
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- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 2
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Classifications
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/11—Anti-reflection coatings
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/14—Protective coatings, e.g. hard coatings
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/11—Anti-reflection coatings
- G02B1/111—Anti-reflection coatings using layers comprising organic materials
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/11—Anti-reflection coatings
- G02B1/113—Anti-reflection coatings using inorganic layer materials only
- G02B1/115—Multilayers
- G02B1/116—Multilayers including electrically conducting layers
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/18—Coatings for keeping optical surfaces clean, e.g. hydrophobic or photo-catalytic films
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Surface Treatment Of Optical Elements (AREA)
- Laminated Bodies (AREA)
- Paints Or Removers (AREA)
Abstract
Description
本発明は反射防止フィルム、さらに詳しくは、プラズマディスプレイ（ＰＤＰ）、ブラウン管（ＣＲＴ）、液晶ディスプレイ（ＬＣＤ）などの画像表示素子の表面の光の反射を効果的に防止すると共に、埃や塵などの付着を抑制する帯電防止効果の持続性及び耐擦傷性に優れ、かつ耐溶剤性にも優れる反射防止層が１層タイプの反射防止フィルムに関するものである。 The present invention is an antireflection film, and more specifically, it effectively prevents reflection of light on the surface of an image display element such as a plasma display (PDP), a cathode ray tube (CRT), a liquid crystal display (LCD), and dust, dust, etc. The antireflection layer which is excellent in the durability of the antistatic effect which suppresses adhesion of ink and scratches, and also has excellent solvent resistance relates to a single-layer type antireflection film.
ＰＤＰ、ＣＲＴ、ＬＣＤなどのディスプレイにおいては、画面に外部から光が入射し、この光が反射して表示画像を見ずらくすることがあり、特に近年、ディスプレイの大型化に伴い、上記問題を解決することが、ますます重要な課題となってきている。
このような問題を解決するために、これまで種々のディスプレイに対して、様々な反射防止処置や防眩処置がとられている。その一つとして反射防止フィルムを各種のディスプレイに使用することが行われている。
この反射防止フィルムは、従来、蒸着やスパッタリングなどのドライプロセス法により、基材フィルム上に、低屈折率の物質（ＭｇＦ2）を薄膜化する方法や、屈折率の高い物質［ＩＴＯ（錫ドープ酸化インジウム）、ＴｉＯ2など］と屈折率の低い物質（ＭｇＦ2、ＳｉＯ2など）を交互に積層する方法などで作製されている。しかしながら、このようなドライプロセス法で作製された反射防止フィルムは、製造コストが高くつくのを免れないという問題があった。
そこで、近年、ウエットプロセス法、すなわちコーティングにより反射防止フィルムを作製することが試みられている。しかしながら、このウエットプロセス法により作製された反射防止フィルムにおいては、前記のドライプロセス法による反射防止フィルムに比べて、表面の耐擦傷性に劣るという問題が生じる。
そこで、ウエットプロセス法における前記問題を解決するために、電離放射線硬化型樹脂組成物を用いて硬化層（ハードコート層）を形成することが行われている。例えば基材フィルム上に、（１）（Ａ）電離放射線による硬化樹脂を含む厚さ２〜２０μｍのハードコート層、（Ｂ）電離放射線による硬化樹脂と、アンチモンドープ酸化錫を含む少なくとも２種の金属酸化物を含み、屈折率が１.６５〜１.８０の範囲にある厚さ６０〜１６０ｎｍの高屈折率層、及び（Ｃ）シロキサン系ポリマーを含み、屈折率が１.３７〜１.４７の範囲にある厚さ８０〜１８０ｎｍの低屈折率層を順次積層してなる光学用フィルム（例えば、特許文献１参照）、（２）（Ａ）金属酸化物と、熱又は電離放射線による硬化物とを含む厚さ２〜２０μｍのハードコート層、及び（Ｂ）多孔性シリカとポリシロキサン系ポリマーとを含み、屈折率が１.３０〜１.４５の範囲にある厚さ４０〜２００ｎｍの低屈折率層を順次積層してなる光学用フィルム（例えば、特許文献２参照）などが開示されている。
これらの光学用フィルムは、画像表示素子の表面の光の反射を効果的に防止すると共に、耐擦傷性に優れる反射防止フィルムである。
一方、反射防止フィルムにおいては、埃や塵などの付着を防止するために、持続性に優れる帯電防止性能が要求される。前記光学用フィルムに持続性に優れる帯電防止性能を付与するには、例えば（１）の光学用フィルムにおいては、（Ｂ）高屈折率層の金属酸化物として、帯電防止性を発現する金属酸化物を、また、（２）の光学用フィルムにおいては、（Ａ）高屈折率層の金属酸化物として、帯電防止性を発現する金属酸化物を用いればよい。
しかしながら、低屈折率層のみをハードコート層に積層する１層タイプにおいては、低屈折率層にシロキサン化合物を用いたもの以外での帯電防止性能付き反射防止フィルムは、これまで開発されていないのが実状である。
In order to solve such a problem, various antireflection treatments and antiglare treatments have been taken for various displays so far. As one of them, an antireflection film is used for various displays.
Conventionally, this antireflection film is formed by a method of thinning a low refractive index substance (MgF 2 ) on a base film by a dry process method such as vapor deposition or sputtering, or a high refractive index substance [ITO (tin-doped Indium oxide), TiO 2, etc.] and a material having a low refractive index (MgF 2 , SiO 2, etc.) are alternately stacked. However, the antireflection film produced by such a dry process method has a problem that the production cost is unavoidable.
Therefore, in recent years, an attempt has been made to produce an antireflection film by a wet process method, that is, coating. However, the antireflection film produced by the wet process method has a problem that the surface is inferior in scratch resistance as compared with the antireflection film by the dry process method.
Therefore, in order to solve the above problems in the wet process method, a cured layer (hard coat layer) is formed using an ionizing radiation curable resin composition. For example, on a base film, (1) (A) a hard coat layer having a thickness of 2 to 20 μm containing a cured resin by ionizing radiation, (B) a cured resin by ionizing radiation, and at least two kinds including antimony-doped tin oxide A high refractive index layer having a thickness of 60 to 160 nm containing a metal oxide and having a refractive index in the range of 1.65 to 1.80, and (C) a siloxane-based polymer, and having a refractive index of 1.37 to 1. An optical film formed by sequentially laminating low refractive index layers having a thickness of 80 to 180 nm in the range of 47 (see, for example, Patent Document 1), (2) (A) metal oxide, and curing by heat or ionizing radiation A hard coat layer having a thickness of 2 to 20 μm, and (B) a porous silica and a polysiloxane polymer, and having a refractive index in the range of 1.30 to 1.45 and a thickness of 40 to 200 nm Laminate low refractive index layers sequentially. An optical film (see, for example, Patent Document 2) is disclosed.
These optical films are antireflection films that effectively prevent reflection of light on the surface of the image display element and are excellent in scratch resistance.
On the other hand, the antireflection film is required to have antistatic performance with excellent sustainability in order to prevent adhesion of dust and the like. In order to impart antistatic performance with excellent sustainability to the optical film, for example, in the optical film of (1), (B) a metal oxide that exhibits antistatic properties as a metal oxide of a high refractive index layer In the optical film (2), a metal oxide that exhibits antistatic properties may be used as the metal oxide of the (A) high refractive index layer.
However, in the one-layer type in which only the low refractive index layer is laminated on the hard coat layer, an antireflection film with antistatic performance other than those using a siloxane compound in the low refractive index layer has not been developed so far. Is real.
本発明は、このような事情のもとで、ＰＤＰ、ＣＲＴ、ＬＣＤなどの画像表示素子の表面の光の反射を効果的に防止すると共に、埃や塵などの付着を抑制する帯電防止効果の持続性及び耐擦傷性に優れ、しかも耐溶剤性にも優れる反射防止層が１層タイプの反射防止フィルムを提供することを目的としてなされたものである。 Under such circumstances, the present invention effectively prevents reflection of light on the surface of image display elements such as PDPs, CRTs, and LCDs, and has an antistatic effect that suppresses adhesion of dust and dirt. An antireflection layer that is excellent in durability and scratch resistance and also has excellent solvent resistance is provided for the purpose of providing a one-layer type antireflection film.
本発明者らは、前記の優れた機能を有する反射防止フィルムを開発すべく鋭意研究を重ねた結果、基材フィルム上に、活性エネルギー線照射による硬化樹脂と特定量の帯電防止剤を含むハードコート層、及び活性エネルギー線照射による硬化樹脂と特定量の多孔性シリカ粒子を含む低屈折率層を順に積層することにより、その目的を達成し得ることを見出し、この知見に基づいて本発明を完成するに至った。
すなわち、本発明は、
（１）基材フィルムの少なくとも一方の面に、（Ａ）活性エネルギー線照射による硬化樹脂と、帯電防止剤２〜２５重量％を含む厚さ１〜２０μｍのハードコート層、及び（Ｂ）活性エネルギー線照射による硬化樹脂と、多孔性シリカ粒子３０〜８０重量％を含む厚さ０.０５〜０.３μｍの低屈折率層を順に有し、かつ表面抵抗率が５×１０12Ω／□以下であることを特徴とする反射防止フィルム、
（２）（Ａ）層における帯電防止剤が、分子内に１個以上の四級アンモニウム塩基を有するカチオン系帯電防止剤である上記(１)項に記載の反射防止フィルム、及び
（３）（Ｂ）層における多孔性シリカ粒子が、比重１.７〜１.９、屈折率１.２５〜１.３６及び平均粒径２０〜１００ｎｍのものである上記(１)又は(２)項に記載の反射防止フィルム、
を提供するものである。
As a result of intensive studies to develop the antireflection film having the above-described excellent functions, the present inventors have found that a hard film containing a cured resin and a specific amount of antistatic agent by irradiation with active energy rays is formed on the base film. It has been found that the purpose can be achieved by sequentially laminating a coating layer and a low refractive index layer containing a cured resin by irradiation with active energy rays and a specific amount of porous silica particles. It came to be completed.
That is, the present invention
(1) On at least one surface of the substrate film, (A) a hard resin layer having a thickness of 1 to 20 μm containing a cured resin by irradiation with active energy rays and 2 to 25% by weight of an antistatic agent, and (B) activity A cured resin by energy ray irradiation and a low refractive index layer having a thickness of 0.05 to 0.3 μm containing 30 to 80% by weight of porous silica particles are sequentially provided, and the surface resistivity is 5 × 10 12 Ω / □. An antireflective film characterized by:
(2) The antistatic film according to (1) above, wherein the antistatic agent in the layer (A) is a cationic antistatic agent having one or more quaternary ammonium bases in the molecule, and (3) ( B) The porous silica particles in the layer are those having a specific gravity of 1.7 to 1.9, a refractive index of 1.25 to 1.36, and an average particle size of 20 to 100 nm, as described in (1) or (2) above. Anti-reflection film,
Is to provide.
本発明によれば、ＰＤＰ、ＣＲＴ、ＬＣＤなどの画像表示素子の表面の光の反射を効果的に防止すると共に、埃や塵などの付着を抑制する帯電防止効果の持続性及び耐擦傷性に優れ、しかも耐溶剤性にも優れる反射防止層が１層タイプの反射防止フィルムを提供することができる。 According to the present invention, it is possible to effectively prevent reflection of light on the surface of an image display element such as a PDP, CRT, or LCD, and to maintain the antistatic effect that suppresses adhesion of dust, dust, etc., and scratch resistance. An antireflection layer which is excellent and also has excellent solvent resistance can provide an antireflection film of a single layer type.
本発明の反射防止フィルムは、ウエットプロセス法により、基材フィルムの少なくとも一方の面に、（Ａ）ハードコート層及び（Ｂ）低屈折率層が順次積層された構造を有している。
本発明の反射防止フィルムにおける基材フィルムについては特に制限はなく、従来反射防止フィルムの基材として公知のプラスチックフィルムの中から適宜選択して用いることができる。このようなプラスチックフィルムとしては、例えば、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンナフタレートなどのポリエステルフィルム、ポリエチレンフィルム、ポリプロピレンフィルム、セロファン、ジアセチルセルロースフィルム、トリアセチルセルロースフィルム、アセチルセルロースブチレートフィルム、ポリ塩化ビニルフィルム、ポリ塩化ビニリデンフィルム、ポリビニルアルコールフィルム、エチレン−酢酸ビニル共重合体フィルム、ポリスチレンフィルム、ポリカーボネートフィルム、ポリメチルペンテンフィルム、ポリスルホンフィルム、ポリエーテルエーテルケトンフィルム、ポリエーテルスルホンフィルム、ポリエーテルイミドフィルム、ポリイミドフィルム、フッ素樹脂フィルム、ポリアミドフィルム、アクリル樹脂フィルム、ノルボルネン系樹脂フィルム、シクロオレフィン樹脂フィルム等を挙げることができる。
これらの基材フィルムは、透明、半透明のいずれであってもよく、また、着色されていてもよいし、無着色のものでもよく、用途に応じて適宜選択すればよい。例えば液晶表示体の保護用として用いる場合には、無色透明のフィルムが好適である。
これらの基材フィルムの厚さは特に制限はなく、適宜選定されるが、通常１５〜２５０μｍ、好ましくは３０〜２００μｍの範囲である。また、この基材フィルムは、その表面に設けられる層との密着性を向上させる目的で、所望により片面又は両面に、酸化法や凹凸化法などにより表面処理を施すことができる。上記酸化法としては、例えばコロナ放電処理、クロム酸処理（湿式）、火炎処理、熱風処理、オゾン・紫外線照射処理などが挙げられ、また、凹凸化法としては、例えばサンドブラスト法、溶剤処理法などが挙げられる。これらの表面処理法は基材フィルムの種類に応じて適宜選ばれるが、一般にはコロナ放電処理法が効果及び操作性などの面から、好ましく用いられる。また、片面又は両面にプライマー処理を施したものも用いることができる。
The antireflection film of the present invention has a structure in which (A) a hard coat layer and (B) a low refractive index layer are sequentially laminated on at least one surface of a base film by a wet process method.
There is no restriction | limiting in particular about the base film in the antireflection film of this invention, It can select suitably from well-known plastic films as a base material of a conventional antireflection film, and can use it. Examples of such plastic films include polyester films such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate, polyethylene films, polypropylene films, cellophane, diacetyl cellulose films, triacetyl cellulose films, acetyl cellulose butyrate films, and polychlorinated salts. Vinyl film, polyvinylidene chloride film, polyvinyl alcohol film, ethylene-vinyl acetate copolymer film, polystyrene film, polycarbonate film, polymethylpentene film, polysulfone film, polyether ether ketone film, polyether sulfone film, polyetherimide film , Polyimide film, fluororesin film, Li amide film, acrylic resin film, norbornene resin film, a cycloolefin resin film.
These base films may be either transparent or translucent, may be colored, or may be uncolored, and may be appropriately selected depending on the application. For example, when used for protecting a liquid crystal display, a colorless and transparent film is suitable.
The thickness of these substrate films is not particularly limited and is appropriately selected, but is usually 15 to 250 μm, preferably 30 to 200 μm. Moreover, this base film can be surface-treated by an oxidation method, a concavo-convex method, or the like on one side or both sides as desired for the purpose of improving adhesion to a layer provided on the surface. Examples of the oxidation method include corona discharge treatment, chromic acid treatment (wet), flame treatment, hot air treatment, ozone / ultraviolet irradiation treatment and the like, and examples of the unevenness method include sand blast method and solvent treatment method. Is mentioned. These surface treatment methods are appropriately selected according to the type of the base film, but generally, the corona discharge treatment method is preferably used from the viewpoints of effects and operability. Moreover, what gave the primer process to the single side | surface or both surfaces can also be used.
本発明の反射防止フィルムにおいては、前記基材フィルムの少なくとも一方の面に、まず（Ａ）活性エネルギー線照射による硬化樹脂と帯電防止剤とを含むハードコート層が設けられる。
この活性エネルギー線照射による硬化樹脂と帯電防止剤とを含むハードコート層は、例えば活性エネルギー線硬化性化合物と、前記の帯電防止剤と、所望により光重合開始剤などを含むハードコート層形成用塗工液を、基材フィルムの少なくとも一方の面にコーティングして塗膜を形成させ、活性エネルギー線を照射して、該塗膜を硬化させることにより、形成することができる。
ここで、活性エネルギー線硬化性化合物とは、電磁波又は荷電粒子線の中でエネルギー量子を有するもの、すなわち、紫外線又は電子線などを照射することにより、架橋、硬化する化合物を指す。
このような活性エネルギー線硬化性化合物としては、例えば光重合性プレポリマー及び／又は光重合性モノマーを挙げることができる。上記光重合性プレポリマーには、ラジカル重合型とカチオン重合型があり、ラジカル重合型の光重合性プレポリマーとしては、例えばポリエステルアクリレート系、エポキシアクリレート系、ウレタンアクリレート系、ポリオールアクリレート系などが挙げられる。ここで、ポリエステルアクリレート系プレポリマーとしては、例えば多価カルボン酸と多価アルコールの縮合によって得られる両末端に水酸基を有するポリエステルオリゴマーの水酸基を(メタ)アクリル酸でエステル化することにより、あるいは、多価カルボン酸にアルキレンオキシドを付加して得られるオリゴマーの末端の水酸基を(メタ)アクリル酸でエステル化することにより得ることができる。
In the antireflection film of the present invention, at least one surface of the substrate film is first provided with a hard coat layer containing (A) a cured resin by irradiation with active energy rays and an antistatic agent.
The hard coat layer containing a cured resin and an antistatic agent by this active energy ray irradiation is, for example, for forming a hard coat layer containing an active energy ray curable compound, the antistatic agent, and a photopolymerization initiator as required. The coating liquid can be formed by coating at least one surface of the substrate film to form a coating film, irradiating active energy rays, and curing the coating film.
Here, the active energy ray-curable compound refers to a compound having energy quanta in an electromagnetic wave or a charged particle beam, that is, a compound that is crosslinked and cured by irradiation with ultraviolet rays or electron beams.
Examples of such an active energy ray-curable compound include a photopolymerizable prepolymer and / or a photopolymerizable monomer. The photopolymerizable prepolymer includes a radical polymerization type and a cationic polymerization type, and examples of the radical polymerization type photopolymerizable prepolymer include polyester acrylate, epoxy acrylate, urethane acrylate, polyol acrylate, and the like. It is done. Here, as the polyester acrylate-based prepolymer, for example, by esterifying the hydroxyl group of a polyester oligomer having a hydroxyl group at both ends obtained by condensation of a polyvalent carboxylic acid and a polyhydric alcohol with (meth) acrylic acid, or It can be obtained by esterifying the terminal hydroxyl group of an oligomer obtained by adding an alkylene oxide to a polyvalent carboxylic acid with (meth) acrylic acid.
エポキシアクリレート系プレポリマーは、例えば、比較的低分子量のビスフェノール型エポキシ樹脂やノボラック型エポキシ樹脂のオキシラン環に、(メタ)アクリル酸を反応しエステル化することにより得ることができる。ウレタンアクリレート系プレポリマーは、例えば、ポリエーテルポリオールやポリエステルポリオールとポリイソシアネートの反応によって得られるポリウレタンオリゴマーを、(メタ)アクリル酸でエステル化することにより得ることができる。さらに、ポリオールアクリレート系プレポリマーは、ポリエーテルポリオールの水酸基を(メタ)アクリル酸でエステル化することにより得ることができる。これらの光重合性プレポリマーは１種用いてもよいし、２種以上を組み合わせて用いてもよい。
一方、カチオン重合型の光重合性プレポリマーとしては、エポキシ系樹脂が通常使用される。このエポキシ系樹脂としては、例えばビスフェノール樹脂やノボラック樹脂などの多価フェノール類にエピクロルヒドリンなどでエポキシ化した化合物、直鎖状オレフィン化合物や環状オレフィン化合物を過酸化物などで酸化して得られた化合物などが挙げられる。
光重合性モノマーとしては、例えば１,４−ブタンジオールジ(メタ)アクリレート、１,６−ヘキサンジオールジ(メタ)アクリレート、ネオペンチルグリコールジ(メタ)アクリレート、ポリエチレングリコールジ(メタ)アクリレート、ネオペンチルグリコールアジペートジ(メタ)アクリレート、ヒドロキシピバリン酸ネオペンチルグリコールジ(メタ)アクリレート、ジシクロペンタニルジ(メタ)アクリレート、カプロラクトン変性ジシクロペンテニルジ(メタ)アクリレート、エチレンオキシド変性リン酸ジ(メタ)アクリレート、アリル化シクロヘキシルジ(メタ)アクリレート、イソシアヌレートジ(メタ)アクリレート、トリメチロールプロパントリ(メタ)アクリレート、ジペンタエリスリトールトリ(メタ)アクリレート、プロピオン酸変性ジペンタエリスリトールトリ(メタ)アクリレート、ペンタエリスリトールトリ(メタ)アクリレート、プロピレンオキシド変性トリメチロールプロパントリ(メタ)アクリレート、トリス(アクリロキシエチル)イソシアヌレート、プロピオン酸変性ジペンタエリスリトールペンタ(メタ)アクリレート、ジペンタエリスリトールヘキサ(メタ)アクリレート、カプロラクトン変性ジペンタエリスリトールヘキサ(メタ)アクリレートなどの多官能アクリレートが挙げられる。これらの光重合性モノマーは１種用いてもよいし、２種以上を組み合わせて用いてもよく、また、前記光重合性プレポリマーと併用してもよい。
The epoxy acrylate prepolymer can be obtained, for example, by reacting (meth) acrylic acid with an oxirane ring of a relatively low molecular weight bisphenol type epoxy resin or novolak type epoxy resin and esterifying it. The urethane acrylate-based prepolymer can be obtained, for example, by esterifying a polyurethane oligomer obtained by reaction of polyether polyol or polyester polyol and polyisocyanate with (meth) acrylic acid. Furthermore, the polyol acrylate-based prepolymer can be obtained by esterifying the hydroxyl group of the polyether polyol with (meth) acrylic acid. These photopolymerizable prepolymers may be used alone or in combination of two or more.
On the other hand, as a cationic polymerization type photopolymerizable prepolymer, an epoxy resin is usually used. Examples of the epoxy resins include compounds obtained by epoxidizing polyphenols such as bisphenol resins and novolak resins with epichlorohydrin, etc., and compounds obtained by oxidizing a linear olefin compound or a cyclic olefin compound with a peroxide or the like. Etc.
Examples of the photopolymerizable monomer include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, neo Pentyl glycol adipate di (meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, caprolactone modified dicyclopentenyl di (meth) acrylate, ethylene oxide modified di (meth) phosphate Acrylate, allylated cyclohexyl di (meth) acrylate, isocyanurate di (meth) acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, propionic acid modified dipentaeryth Litol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, tris (acryloxyethyl) isocyanurate, propionic acid modified dipentaerythritol penta (meth) acrylate, dipentaerythritol Examples thereof include polyfunctional acrylates such as hexa (meth) acrylate and caprolactone-modified dipentaerythritol hexa (meth) acrylate. These photopolymerizable monomers may be used alone or in combination of two or more thereof, or may be used in combination with the photopolymerizable prepolymer.
所望により用いられる光重合開始剤としては、ラジカル重合型の光重合性プレポリマーや光重合性モノマーに対しては、例えばベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル、ベンゾイン−ｎ−ブチルエーテル、ベンゾインイソブチルエーテル、アセトフェノン、ジメチルアミノアセトフェノン、２,２−ジメトキシ−２−フェニルアセトフェノン、２,２−ジエトキシ−２−フェニルアセトフェノン、２−ヒドロキシ−２−メチル−１−フェニルプロパン−１−オン、１−ヒドロキシシクロヘキシルフェニルケトン、２−メチル−１−[４−(メチルチオ)フェニル]−２−モルフォリノ−プロパン−１−オン、４−(２−ヒドロキシエトキシ)フェニル−２(ヒドロキシ−２−プロプル)ケトン、ベンゾフェノン、ｐ−フェニルベンゾフェノン、４,４'−ジエチルアミノベンゾフェノン、ジクロロベンゾフェノン、２−メチルアントラキノン、２−エチルアントラキノン、２−ターシャリ−ブチルアントラキノン、２−アミノアントラキノン、２−メチルチオキサントン、２−エチルチオキサントン、２−クロロチオキサントン、２,４−ジメチルチオキサントン、２,４−ジエチルチオキサントン、ベンジルジメチルケタール、アセトフェノンジメチルケタール、ｐ−ジメチルアミン安息香酸エステルなどが挙げられる。また、カチオン重合型の光重合性プレポリマーに対する光重合開始剤としては、例えば芳香族スルホニウムイオン、芳香族オキソスルホニウムイオン、芳香族ヨードニウムイオンなどのオニウムと、テトラフルオロボレート、ヘキサフルオロホスフェート、ヘキサフルオロアンチモネート、ヘキサフルオロアルセネートなどの陰イオンとからなる化合物が挙げられる。これらは１種用いてもよいし、２種以上を組み合わせて用いてもよく、また、その配合量は、前記光重合性プレポリマー及び／又は光重合性モノマー１００重量部に対して、通常０.２〜１０重量部の範囲で選ばれる。 Examples of the photopolymerization initiator used as desired include radical polymerization type photopolymerizable prepolymers and photopolymerizable monomers such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin-n-butyl ether. Benzoin isobutyl ether, acetophenone, dimethylaminoacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, 4- (2-hydroxyethoxy) phenyl-2 (hydroxy-2-propyl) Ketone Benzophenone, p-phenylbenzophenone, 4,4′-diethylaminobenzophenone, dichlorobenzophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-aminoanthraquinone, 2-methylthioxanthone, 2-ethylthioxanthone 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, benzyldimethyl ketal, acetophenone dimethyl ketal, p-dimethylamine benzoate, and the like. Examples of the photopolymerization initiator for the cationic polymerization type photopolymerizable prepolymer include oniums such as aromatic sulfonium ions, aromatic oxosulfonium ions, aromatic iodonium ions, tetrafluoroborate, hexafluorophosphate, hexafluoro The compound which consists of anions, such as antimonate and hexafluoroarsenate, is mentioned. These may be used singly or in combination of two or more, and the blending amount is usually 0 with respect to 100 parts by weight of the photopolymerizable prepolymer and / or photopolymerizable monomer. It is selected in the range of 2 to 10 parts by weight.
一方、ハードコート層に含有させる帯電防止剤に特に制限はなく、従来公知の非イオン系、アニオン系、カチオン系、両性系帯電防止剤の中から選ばれる少なくとも１種が用いられる。これらの中で、効果及びハードコート層に対する均質分散性などの点から、分子内に１個以上の四級アンモニウム塩基を有するカチオン系帯電防止剤が好適である。
四級アンモニウム塩基を有するカチオン系帯電防止剤は、低分子型及び高分子型のいずれも使用することができるが、効果の持続性及びブリードアウトやガス発生の防止性などの点から、高分子型カチオン系帯電防止剤が好ましい。
上記高分子型カチオン系帯電防止剤としては、従来公知のものの中から、任意のものを適宜選択して用いることができる。具体的には、分子内に、一般式（Ｉ）
で表される四級アンモニウム塩基を有する高分子重合体を好ましく挙げることができる。
上記一般式（Ｉ）において、Ｒ1及びＲ2で示されるアルキル基並びにＲ3のうちのアルキル基としては、炭素数１〜６のアルキル基、特に炭素数１〜４のアルキル基が好ましく、また、Ｒ3のうちのアラルキル基としては、ベンジル基が好ましい。炭素数１〜４のアルキル基としては、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基が挙げられる。
On the other hand, the antistatic agent contained in the hard coat layer is not particularly limited, and at least one selected from conventionally known nonionic, anionic, cationic, and amphoteric antistatic agents is used. Among these, a cationic antistatic agent having one or more quaternary ammonium bases in the molecule is preferable from the viewpoints of effects and homogeneous dispersibility with respect to the hard coat layer.
As the cationic antistatic agent having a quaternary ammonium base, either a low molecular type or a high molecular type can be used. However, in terms of durability of the effect and prevention of bleeding out and gas generation, the polymer Type cationic antistatic agents are preferred.
As the polymer-type cationic antistatic agent, an arbitrary one can be appropriately selected from conventionally known ones. Specifically, in the molecule, the general formula (I)
Preferred examples include a polymer having a quaternary ammonium base represented by the formula:
In the general formula (I), the alkyl group represented by R 1 and R 2 and the alkyl group in R 3 are preferably an alkyl group having 1 to 6 carbon atoms, particularly an alkyl group having 1 to 4 carbon atoms, The aralkyl group in R 3 is preferably a benzyl group. Examples of the alkyl group having 1 to 4 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, and tert-butyl group.
一方、Ｘn-は無機陰イオン、有機陰イオンのいずれであってもよく、その例としてはＦ-、Ｃｌ-、Ｂｒ-、Ｉ-のハロゲンイオン、ＮＯ3 -、ＣｌＯ4 -、ＢＦ4 -、ＣＯ3 2-、ＳＯ4 2-などの無機陰イオン、ＣＨ3ＯＳＯ3 -、Ｃ2Ｈ5ＯＳＯ3 -、さらには酢酸、マロン酸、コハク酸、マレイン酸、フマル酸、ｐ−トルエンスルホン酸、トリフルオロ酢酸などの有機酸の残基からなる有機陰イオンが挙げられる。
このような高分子型四級アンモニウム塩系帯電防止剤としては、例えば以下に示す化合物、すなわち、ポリビニルベンジル型［（ａ）］、ポリ(メタ)アクリレート型［（ｂ）］、スチレン−(メタ)アクリレート共重合体型［（ｃ）］、スチレン−マレイミド共重合体型［（ｄ）］、メタクリレート−メタクリルイミド共重合体型［（ｅ）］などを挙げることができる。なお、（ｃ）、（ｄ）及び（ｅ）の共重合体型においては、ランダム共重合体型及びブロック共重合体型のいずれであってもよい。
一方、低分子型カチオン系帯電防止剤としては、例えば、一般式（II）
で表される四級アンモニウム塩基を有する化合物を好ましく挙げることができる。
上記一般式（II）におけるＡの例としては、ラウリル基などのドデシル基、ミリスチル基などのテトラデシル基、パルミチル基などのヘキサデシル基、ステアリル基などのオクタデシル基、エイコシル基、ベヘニル基などが挙げられる。
また、Ｒ4、Ｒ5、Ｒ6、Ｙm-及びｍは、それぞれ一般式（Ｉ）におけるＲ1、Ｒ2、Ｒ3、Ｘn-及びｎと同じである。
本発明においては、この低分子型カチオン系帯電防止剤は１種用いてもよいし、２種以上を組み合わせて用いてもよい。
On the other hand, X n− may be either an inorganic anion or an organic anion. Examples thereof include halogen ions of F − , Cl − , Br − and I − , NO 3 − , ClO 4 − and BF 4. -, CO 3 2-, SO 4 2- , etc. of the inorganic anion, CH 3 OSO 3 -, C 2 H 5 OSO 3 -, more acetic acid, malonic acid, succinic acid, maleic acid, fumaric acid, p- toluene Examples include organic anions composed of residues of organic acids such as sulfonic acid and trifluoroacetic acid.
Examples of such a polymer type quaternary ammonium salt antistatic agent include the following compounds, that is, polyvinylbenzyl type [(a)], poly (meth) acrylate type [(b)], styrene- (meta ) Acrylate copolymer type [(c)], styrene-maleimide copolymer type [(d)], and methacrylate-methacrylimide copolymer type [(e)]. The copolymer types (c), (d) and (e) may be either a random copolymer type or a block copolymer type.
On the other hand, as a low molecular type cationic antistatic agent, for example, the general formula (II)
The compound which has the quaternary ammonium base represented by these can be mentioned preferably.
Examples of A in the general formula (II) include dodecyl groups such as lauryl groups, tetradecyl groups such as myristyl groups, hexadecyl groups such as palmityl groups, octadecyl groups such as stearyl groups, eicosyl groups, and behenyl groups. .
R 4 , R 5 , R 6 , Y m− and m are the same as R 1 , R 2 , R 3 , X n− and n in the general formula (I), respectively.
In the present invention, the low molecular weight cationic antistatic agent may be used singly or in combination of two or more.
さらに、本発明においては、帯電防止剤として、分子内に１個以上の四級アンモニウム塩基及び１個以上の重合性不飽和基を有する反応性カチオン系帯電防止剤を用いてもよい。
このような反応性カチオン系帯電防止剤を用いることにより、活性エネルギー線を照射した際に、前述の活性エネルギー線硬化性化合物と共重合して、形成される高分子鎖内に取り込まれるため、得られる反射防止フィルムは、帯電防止性能の持続性が向上する。
この反応性カチオン系帯電防止剤としては、例えば一般式（III）
で表される反応性四級アンモニウム塩系化合物などを挙げることができる。
本発明においては、この反応性カチオン系帯電防止剤は１種用いてもよいし、２種以上を組み合わせて用いてもよい。また、前記高分子型カチオン系帯電防止剤、低分子型カチオン系帯電防止剤及び反応性カチオン系帯電防止剤を適当に組み合わせて用いることができる。
Furthermore, in the present invention, a reactive cationic antistatic agent having one or more quaternary ammonium bases and one or more polymerizable unsaturated groups in the molecule may be used as the antistatic agent.
By using such a reactive cationic antistatic agent, when active energy rays are irradiated, it is copolymerized with the aforementioned active energy ray-curable compound and incorporated into the formed polymer chain. The resulting antireflection film improves the sustainability of the antistatic performance.
Examples of the reactive cationic antistatic agent include, for example, the general formula (III)
The reactive quaternary ammonium salt type compound etc. which are represented by these can be mentioned.
In the present invention, this reactive cationic antistatic agent may be used alone or in combination of two or more. Further, the polymer cationic antistatic agent, the low molecular cationic antistatic agent and the reactive cationic antistatic agent can be used in appropriate combination.
本発明においては、（Ａ）層であるハードコート層中の前記帯電防止剤の含有量は、２〜２５重量％の範囲で選定される。該帯電防止剤の含有量が上記範囲にあれば、反射防止フィルムは、良好な帯電防止性能を発揮すると共に、他の性能に悪影響を及ぼすことがない。この含有量は、好ましくは３〜２５重量％、より好ましくは５〜２０重量％の範囲である。
本発明において用いられるこのハードコート層形成用塗工液は、必要に応じ、適当な溶剤中に、前記の活性エネルギー線硬化性化合物と、帯電防止剤と、所望により用いられる前記の光重合開始剤、さらには各種添加剤、例えば酸化防止剤、紫外線吸収剤、光安定剤、レベリング剤、消泡剤などを、それぞれ所定の割合で加え、溶解又は分散させることにより、調製することができる。
この際用いる溶剤としては、例えばヘキサン、ヘプタン、シクロヘキサンなどの脂肪族炭化水素、トルエン、キシレンなどの芳香族炭化水素、塩化メチレン、塩化エチレンなどのハロゲン化炭化水素、メタノール、エタノール、プロパノール、ブタノール、１−メトキシ−２−プロパノールなどのアルコール、アセトン、メチルエチルケトン、２−ペンタノン、メチルイソブチルケトン、イソホロンなどのケトン、酢酸エチル、酢酸ブチルなどのエステル、エチルセロソルブなどのセロソルブ系溶剤などが挙げられる。
このようにして調製された塗工液の濃度、粘度としては、コーティング可能な濃度、粘度であればよく、特に制限されず、状況に応じて適宜選定することができる。
次に、基材フィルムの少なくとも一方の面に、上記塗工液を、従来公知の方法、例えばバーコート法、ナイフコート法、ロールコート法、ブレードコート法、ダイコート法、グラビアコート法などを用いて、コーティングして塗膜を形成させ、乾燥後、これに活性エネルギー線を照射して該塗膜を硬化させることにより、ハードコート層が形成される。
活性エネルギー線としては、例えば紫外線や電子線などが挙げられる。上記紫外線は、高圧水銀ランプ、ヒュージョンＨランプ、キセノンランプなどで得られる。一方電子線は、電子線加速器などによって得られる。この活性エネルギー線の中では、特に紫外線が好適である。なお、電子線を使用する場合は、重合開始剤を添加することなく、硬化膜を得ることができる。
本発明においては、（Ａ）ハードコート層の厚さは１〜２０μｍの範囲である。この厚さが１μｍ未満では得られる反射防止フィルムの耐擦傷性が十分に発揮されないおそれがあるし、また２０μｍを超えるとハードコート層にクラックが発生することがある。このハードコート層の好ましい厚さは２〜１５μｍの範囲である。
本発明の光学用フィルムにおいては、この（Ａ）ハードコート層の屈折率は、通常１.４５〜１.６０、好ましくは１.４９〜１.５５の範囲である。
In the present invention, the content of the antistatic agent in the hard coat layer as the layer (A) is selected in the range of 2 to 25% by weight. When the content of the antistatic agent is within the above range, the antireflection film exhibits good antistatic performance and does not adversely affect other performances. This content is preferably in the range of 3 to 25% by weight, more preferably 5 to 20% by weight.
The hard coat layer-forming coating solution used in the present invention may be prepared by using the active energy ray-curable compound, the antistatic agent, and the photopolymerization start as required, in an appropriate solvent, if necessary. It can be prepared by adding an agent, and further various additives, for example, an antioxidant, an ultraviolet absorber, a light stabilizer, a leveling agent, an antifoaming agent, and the like at a predetermined ratio and dissolving or dispersing them.
Examples of the solvent used in this case include aliphatic hydrocarbons such as hexane, heptane, and cyclohexane, aromatic hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as methylene chloride and ethylene chloride, methanol, ethanol, propanol, butanol, Examples include alcohols such as 1-methoxy-2-propanol, ketones such as acetone, methyl ethyl ketone, 2-pentanone, methyl isobutyl ketone, and isophorone, esters such as ethyl acetate and butyl acetate, and cellosolv solvents such as ethyl cellosolve.
The concentration and viscosity of the coating solution thus prepared are not particularly limited as long as the concentration and viscosity can be coated, and can be appropriately selected depending on the situation.
Next, the coating liquid is applied to at least one surface of the base film using a conventionally known method such as a bar coating method, a knife coating method, a roll coating method, a blade coating method, a die coating method, or a gravure coating method. Then, coating is performed to form a coating film, and after drying, the coating film is cured by irradiating the active energy ray to form a hard coat layer.
Examples of the active energy rays include ultraviolet rays and electron beams. The ultraviolet rays can be obtained with a high-pressure mercury lamp, a fusion H lamp, a xenon lamp, or the like. On the other hand, the electron beam is obtained by an electron beam accelerator or the like. Among these active energy rays, ultraviolet rays are particularly preferable. In addition, when using an electron beam, a cured film can be obtained, without adding a polymerization initiator.
In the present invention, the thickness of the (A) hard coat layer is in the range of 1 to 20 μm. If the thickness is less than 1 μm, the resulting antireflection film may not exhibit sufficient scratch resistance, and if it exceeds 20 μm, cracks may occur in the hard coat layer. The preferred thickness of this hard coat layer is in the range of 2 to 15 μm.
In the optical film of the present invention, the refractive index of the (A) hard coat layer is usually from 1.45 to 1.60, preferably from 1.49 to 1.55.
本発明の反射防止フィルムにおいては、前記ハードコート層上に、（Ｂ）活性エネルギー線照射による硬化樹脂と多孔性シリカ粒子とを含む低屈折率層が設けられる。
この活性エネルギー線照射による硬化樹脂と多孔性シリカ粒子とを含む低屈折率層は、例えば活性エネルギー線硬化性化合物と、前記の多孔性シリカ粒子と、所望により光重合開始剤などを含む低屈折率層形成用塗工液を、（Ａ）ハードコート層上にコーティングして塗膜を形成させ、活性エネルギー線を照射して、該塗膜を硬化させることにより、形成することができる。
前記の活性エネルギー線硬化性化合物及び所望により用いられる光重合開始剤については、前述の（Ａ）ハードコート層の説明において示したとおりである。
この（Ｂ）層に含まれる多孔性シリカ粒子としては、比重が１.７〜１.９、屈折率が１.２５〜１.３６及び平均粒径が２０〜１００ｎｍの範囲にあるものが好ましく用いられる。このような性状を有する多孔性シリカ粒子を用いることにより、反射防止性能に優れる１層タイプの反射防止フィルムを得ることができる。
本発明においては、この（Ｂ）層中の多孔性シリカ粒子の含有量は、３０〜８０重量％の範囲で選定される。該多孔性シリカ粒子の含有量が上記範囲にあれば、当該（Ｂ）層は所望の低屈折率を有する層となり、得られる反射防止フィルムは、反射防止性に優れたものとなる。該多孔性シリカ粒子の好ましい含有量は、５０〜８０重量％であり、特に６０〜７５重量％の範囲が好ましい。
当該（Ｂ）層は、厚さが０.０５〜０.３μｍであって、屈折率が、通常１.３０〜１.４２の範囲にある。当該（Ｂ）層の厚さや屈折率が上記範囲にあれば、反射防止性能、帯電防止性能及び耐擦傷性に優れる反射防止フィルムを得ることができる。（Ｂ）層の厚さは、好ましくは０.０７〜０.１３μｍであり、屈折率は、好ましくは１.３５〜１.４０の範囲である。
In the antireflection film of the present invention, a low refractive index layer containing (B) a cured resin by irradiation with active energy rays and porous silica particles is provided on the hard coat layer.
The low refractive index layer containing a cured resin and porous silica particles by irradiation with active energy rays is, for example, a low refractive index containing an active energy ray curable compound, the porous silica particles, and a photopolymerization initiator as required. The coating liquid for forming the rate layer can be formed by coating the (A) hard coat layer to form a coating film, irradiating active energy rays and curing the coating film.
About the said active energy ray hardening compound and the photoinitiator used depending on necessity, it is as having shown in description of the above-mentioned (A) hard-coat layer.
The porous silica particles contained in the layer (B) are preferably those having a specific gravity of 1.7 to 1.9, a refractive index of 1.25 to 1.36, and an average particle size of 20 to 100 nm. Used. By using porous silica particles having such properties, a single-layer type antireflection film having excellent antireflection performance can be obtained.
In the present invention, the content of the porous silica particles in the layer (B) is selected in the range of 30 to 80% by weight. If content of this porous silica particle exists in the said range, the said (B) layer will become a layer which has a desired low refractive index, and the obtained antireflection film will be excellent in antireflection property. The preferable content of the porous silica particles is 50 to 80% by weight, and particularly preferably 60 to 75% by weight.
The (B) layer has a thickness of 0.05 to 0.3 μm and a refractive index of usually 1.30 to 1.42. When the thickness and refractive index of the (B) layer are in the above ranges, an antireflection film having excellent antireflection performance, antistatic performance and scratch resistance can be obtained. The thickness of the layer (B) is preferably 0.07 to 0.13 μm, and the refractive index is preferably in the range of 1.35 to 1.40.
本発明において用いられるこの低屈折率層形成用塗工液は、必要に応じ、適当な溶剤中に、前記の活性エネルギー線硬化性化合物と、多孔性シリカ粒子と、所望により用いられる前記の光重合開始剤、さらには各種添加剤、例えば酸化防止剤、紫外線吸収剤、光安定剤、レベリング剤、消泡剤などを、それぞれ所定の割合で加え、溶解又は分散させることにより、調製することができる。
この際用いる溶剤については、前述のハードコート層形成用塗工液の説明において示したとおりである。
このようにして調製された塗工液の濃度、粘度としては、コーティング可能な濃度、粘度であればよく、特に制限されず、状況に応じて適宜選定することができる。
（Ａ）ハードコート層上に、この塗工液を、従来公知の方法、例えばバーコート法、ナイフコート法、ロールコート法、ブレードコート法、ダイコート法、グラビアコート法などを用いて、コーティングして塗膜を形成させ、乾燥後、これに活性エネルギー線を照射して該塗膜を硬化させることにより、（Ｂ）低屈折率層が形成される。
活性エネルギー線については、前述のハードコート層の説明において示したとおりである。
The coating solution for forming a low refractive index layer used in the present invention comprises the above-mentioned active energy ray-curable compound, porous silica particles, and the above-mentioned light used as required, in an appropriate solvent, if necessary. It can be prepared by adding a polymerization initiator and further various additives such as an antioxidant, an ultraviolet absorber, a light stabilizer, a leveling agent, an antifoaming agent, etc. in a predetermined ratio and dissolving or dispersing them. it can.
The solvent used in this case is as described in the description of the hard coat layer forming coating solution.
The concentration and viscosity of the coating solution thus prepared are not particularly limited as long as the concentration and viscosity can be coated, and can be appropriately selected depending on the situation.
(A) The coating liquid is coated on the hard coat layer using a conventionally known method such as a bar coating method, a knife coating method, a roll coating method, a blade coating method, a die coating method, or a gravure coating method. A coating film is formed, dried, and then irradiated with active energy rays to cure the coating film, thereby forming a (B) low refractive index layer.
The active energy ray is as described in the description of the hard coat layer.
本発明においては、前記（Ａ）ハードコート層及び（Ｂ）低屈折率層の形成は、以下に示す方法で行うのが有利である。
まず、基材フィルムの一方の面にハードコート層形成用塗工液をコーティングして塗膜を形成させ、活性エネルギー線を照射してハーフキュア状態に硬化させる。この際、紫外線を照射する場合には、光量は、通常５０〜１５０ｍＪ／ｃｍ2程度である。次いで、このようにして形成されたハーフキュア状態の硬化層上に、低屈折率層形成用塗工液をコーティングして塗膜を形成させ、活性エネルギー線を十分に照射し、前記ハーフキュア状態の硬化層と共に完全に硬化させる。この際、紫外線を照射する場合、光量は、通常２００〜１０００ｍＪ／ｃｍ2程度である。
このようにして、基材フィルム上に、（Ａ）層と（Ｂ）層間の密着性に優れる（Ａ）ハードコート層及び（Ｂ）低屈折率層が順次形成される。
このようにして作製された本発明の反射防止フィルムにおいては、表面抵抗率が５×１０12Ω／□以下である。この表面抵抗率が５×１０12Ω／□以下であれば、帯電防止性能が発揮され、該反射防止フィルムには、埃や塵などが付着しにくくなる。表面抵抗率の下限については特に制限はないが、通常１×１０8Ω／□程度である。また、本発明の反射防止フィルムの可視光線の平均反射率は３％以下である。
さらに、（Ａ）ハードコート層上に、（Ｂ）活性エネルギー線照射による硬化樹脂を含む低屈折率層が設けられているため、帯電防止性能の持続性に優れると共に、耐溶剤性を有し、溶剤による帯電防止性能の低下が抑制される。
なお、表面抵抗率の測定については後で説明する。
このようにして、各種画像表示素子の表面の光の反射を効果的に防止すると共に、埃や塵などの付着を抑制する帯電防止効果の持続性及び耐擦傷性に優れ、かつ耐溶剤性にも優れる反射防止層が１層タイプの反射防止フィルムを得ることができる。
本発明の反射防止フィルムにおいては、基材フィルムの一方の面にハードコート層が設けられている場合、該ハードコート層とは反対側の面に、液晶表示体などの被着体に貼着させるための粘着剤層を形成させることができる。この粘着剤層を構成する粘着剤としては、光学用途用のもの、例えばアクリル系粘着剤、ウレタン系粘着剤、シリコーン系粘着剤が好ましく用いられる。この粘着剤層の厚さは、通常５〜１００μｍ、好ましくは１０〜６０μｍの範囲である。
さらに、この粘着剤層の上に、剥離フィルムを設けることができる。この剥離フィルムとしては、例えばグラシン紙、コート紙、ラミネート紙などの紙及び各種プラスチックフィルムに、シリコーン樹脂などの剥離剤を塗付したものなどが挙げられる。この剥離フィルムの厚さについては特に制限はないが、通常２０〜１５０μｍ程度である。
In the present invention, the (A) hard coat layer and (B) low refractive index layer are advantageously formed by the following method.
First, a hard coat layer-forming coating solution is coated on one surface of the base film to form a coating film, which is irradiated with active energy rays and cured to a half-cured state. In this case, when irradiating with ultraviolet rays, the amount of light is usually about 50 to 150 mJ / cm 2 . Next, a coating film is formed by coating a coating solution for forming a low refractive index layer on the cured layer in the half-cured state thus formed, and the half-cured state is sufficiently irradiated with active energy rays. And completely cured together with the cured layer. Under the present circumstances, when irradiating an ultraviolet-ray, a light quantity is about 200-1000mJ / cm < 2 > normally.
In this way, (A) a hard coat layer and (B) a low refractive index layer excellent in adhesion between the (A) layer and the (B) layer are sequentially formed on the base film.
In the antireflection film of the present invention thus produced, the surface resistivity is 5 × 10 12 Ω / □ or less. When the surface resistivity is 5 × 10 12 Ω / □ or less, antistatic performance is exhibited, and dust and dust are less likely to adhere to the antireflection film. The lower limit of the surface resistivity is not particularly limited, but is usually about 1 × 10 8 Ω / □. Moreover, the average reflectance of visible light of the antireflection film of the present invention is 3% or less.
Furthermore, because (A) the hard coating layer is provided with a low refractive index layer containing (B) a cured resin by irradiation with active energy rays, it has excellent antistatic performance and solvent resistance. The decrease in antistatic performance due to the solvent is suppressed.
The measurement of the surface resistivity will be described later.
In this way, while effectively preventing the reflection of light on the surface of various image display elements, the antistatic effect for suppressing the adhesion of dust, dust, etc. is excellent in durability and scratch resistance, and in solvent resistance. An antireflection layer having an excellent antireflection film can be obtained.
In the antireflection film of the present invention, when a hard coat layer is provided on one surface of the base film, it is attached to an adherend such as a liquid crystal display on the surface opposite to the hard coat layer. A pressure-sensitive adhesive layer can be formed. As an adhesive which comprises this adhesive layer, the thing for optical uses, for example, an acrylic adhesive, a urethane type adhesive, and a silicone type adhesive, are used preferably. The thickness of this pressure-sensitive adhesive layer is usually 5 to 100 μm, preferably 10 to 60 μm.
Furthermore, a release film can be provided on this pressure-sensitive adhesive layer. Examples of the release film include paper such as glassine paper, coated paper, and laminate paper, and various plastic films coated with a release agent such as silicone resin. Although there is no restriction | limiting in particular about the thickness of this peeling film, Usually, it is about 20-150 micrometers.
次に、本発明を実施例により、さらに詳細に説明するが、本発明は、これらの例によってなんら限定されるものではない。
なお、各例で得られた反射防止フィルムの物性は、以下に示す方法に従って測定した。
（１）波長５００ｎｍ、６００ｎｍ及び７００ｎｍにおける反射率
分光光度計［(株)島津製作所製「ＵＶ−３１０１ＰＣ」］により、波長５００ｎｍ、６００ｎｍ及び７００ｎｍにおける反射率を測定した。
（２）表面抵抗率
ＪＩＳ Ｋ ６９１１に準拠し、(株)アドバンテスト社製デジタルエレクトロメーターに連結した平行電極を使用して測定した。なお、エタノール拭取り後の表面抵抗率は、以下のようにして測定した。
エタノールを染み込ませたガーゼで低屈折率層の表面を５往復拭き、さらに乾いたガーゼで５往復拭いたのち、２３℃、相対湿度５０％の環境下に３０分間放置後、前記表面抵抗率の測定と同様にして行った。
（３）耐擦傷性
スチールウール＃００００を使用し、荷重９.８×１０-3Ｎ／ｍｍ2で５往復擦った後に目視観察を行い、下記の判定基準で評価した。
○：傷が付かない。
×：傷が付く。
EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
In addition, the physical property of the antireflection film obtained in each example was measured according to the method shown below.
(1) Reflectance at wavelengths of 500 nm, 600 nm, and 700 nm The reflectance at wavelengths of 500 nm, 600 nm, and 700 nm was measured with a spectrophotometer [manufactured by Shimadzu Corporation “UV-3101PC”].
(2) Surface resistivity Based on JISK6911, it measured using the parallel electrode connected with the digital electrometer by Corporation | KK ADVANTEST. In addition, the surface resistivity after wiping off ethanol was measured as follows.
Wipe the surface of the low refractive index layer 5 times with gauze soaked with ethanol, and then wipe 5 times with dry gauze. After leaving it in an environment of 23 ° C. and 50% relative humidity for 30 minutes, It carried out like the measurement.
(3) Scratch resistance A steel wool # 0000 was used and rubbed 5 times with a load of 9.8 × 10 −3 N / mm 2 , followed by visual observation, and evaluated according to the following criteria.
○: Not scratched.
×: Scratched.
実施例１
（１）Ａ液（ハードコート層形成用塗工液）の調製
３官能アクリレートモノマーであるペンタエリスリトールトリアクリレート［東亜合成(株)製、商品名「アロニックスＭ−３０５」、固形分濃度１００％］４５重量部、光重合開始剤として２−メチル−１−[４−(メチルチオ)フェニル]−２−モルホリノ−プロパン−１−オン［チバ・スペシャルティ・ケミカルズ社製、商品名「イルガキュア９０７」、固形分濃度１００％］０.９重量部、及び四級アンモニウム塩基を有する高分子型のカチオン系帯電防止剤［コルコート社製、商品名「コルコートＮＲ−１２１Ｘ−９ＩＰＡ」、固形分濃度９.５重量％］９０重量部からなる混合物を、１−メトキシ−２−プロパノールで希釈して固形分濃度３５重量％のＡ液（ハードコート層形成用塗工液）を調製した。
（２）Ｂ液（低屈折率層形成用塗工液）の調製
３官能アクリレートモノマーであるペンタエリスリトールトリアクリレート［東亜合成(株)製、商品名「アロニックスＭ−３０５」、固形分濃度１００％］１０重量部、多孔性シリカ粒子のメチルイソブチルケトン（ＭＩＢＫ）分散体［触媒化成工業(株)製、商品名「ＥＬＣＯＭ ＲＴ−１００２ＳＩＶ」、固形分濃度２１重量％、多孔性シリカ粒子：比重１.８、屈折率１.３０、平均粒径６０ｎｍ］１４２重量部、光重合開始剤として２−メチル−１−[４−(メチルチオ)フェニル]−２−モルホリノ−プロパン−１−オン［チバ・スペシャルティ・ケミカルズ社製、商品名「イルガキュア９０７」、固形分濃度１００％］０.５重量部及びレベリング剤として変性ポリジメチルシロキサン［東レ・ダウコーニングシリコーン(株)製、商品名「ＳＨ２８ＰＡ」、固形分濃度１００％］０.００５重量部からなる混合物を、ＭＩＢＫ／１−メトキシ−２−プロパノール混合溶剤（重量比１／１）で希釈して固形分濃度２.５重量％のＢ液（低屈折率層形成用塗工液）を調製した。
（３）反射防止フィルムの作製
基材フィルムとして厚さ８０μｍのトリアセチルセルロースフィルム［富士写真フィルム(株)製、商品名「Ｔ−８０ＵＺ」］表面に、前記（１）で得たＡ液を硬化後の厚さが３μｍになるように、マイヤーバーＮｏ．８で塗布した。次いで、９０℃で１分間乾燥したのち、紫外線を光量８０ｍＪ／ｃｍ2で照射して、ハーフキュア状態に硬化させた。
次に、このハーフキュア面に、前記（２）で得たＢ液を硬化後の厚さが０.１μｍになるようにマイヤーバーＮｏ．４で塗布した。次いで、８０℃で１分間乾燥したのち、紫外線を光量３５０ｍＪ／ｃｍ2で照射して、完全硬化させ、トリアセチルセルロースフィルム上に、屈折率１.５０のハードコート層及び屈折率１.３６の低屈折率層を順次形成させることにより、反射防止フィルムを作製した。
このようにして作製された反射防止フィルムの物性を第１表に示す。
なお、各コート層の厚さは、大塚電子(株)製「ＭＣＰＤ−２０００」により測定し、屈折率は(株)アタゴ製アッベ屈折計（Ｎａ光源、波長：約５９０ｎｍ）により測定した。（以下、同様）
実施例２
実施例１（１）において、帯電防止剤「コルコートＮＲ−１２１Ｘ−９ＩＰＡ」の使用量を６０重量部に変更した以外は、実施例１と同様に実施して、反射防止フィルムを作製した。ハードコート層の屈折率：１.４９
このようにして作製した反射防止フィルムの物性を第１表に示す。
実施例３
実施例１（２）において、多孔性シリカ粒子のＭＩＢＫ分散体「ＥＬＣＯＭ ＲＴ−１００２ＳＩＶ」の使用量を１２０重量部に変更した以外は、実施例１と同様に実施して、反射防止フィルムを作製した。低屈折率層の屈折率：１.４０
このようにして作製した反射防止フィルムの物性を第１表に示す。
Example 1
(1) Preparation of liquid A (hard coat layer forming coating liquid) pentaerythritol triacrylate which is a trifunctional acrylate monomer [manufactured by Toagosei Co., Ltd., trade name “Aronix M-305”, solid content concentration 100%] 45 parts by weight, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one [manufactured by Ciba Specialty Chemicals, trade name “Irgacure 907” as a photopolymerization initiator, solid Polymer concentration type antistatic agent having a partial concentration of 100%] and 0.9 part by weight and a quaternary ammonium base [manufactured by Colcoat Co., Ltd., trade name “Colcoat NR-121X-9IPA”, solid content concentration of 9.5 wt. %] A mixture of 90 parts by weight was diluted with 1-methoxy-2-propanol, and a liquid A (solid coating solution for forming a hard coat layer) having a solid concentration of 35% by weight. It was prepared.
(2) Preparation of liquid B (coating liquid for forming a low refractive index layer) Pentaerythritol triacrylate [manufactured by Toagosei Co., Ltd., trade name “Aronix M-305”, solid content concentration 100% ] 10 parts by weight, methyl isobutyl ketone (MIBK) dispersion of porous silica particles [manufactured by Catalyst Kasei Kogyo Co., Ltd., trade name "ELCOM RT-1002SIV", solid content concentration 21% by weight, porous silica particles: specific gravity 1 .8, refractive index 1.30, average particle size 60 nm] 142 parts by weight, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one [Ciba Made by Specialty Chemicals, trade name “Irgacure 907”, solid content concentration 100%] 0.5 part by weight and modified polydimethylsiloxane [Toray Da A mixture comprising 0.005 parts by weight of a product name “SH28PA”, solid concentration 100%] manufactured by Uconing Silicone Co., Ltd. is diluted with a MIBK / 1-methoxy-2-propanol mixed solvent (weight ratio 1/1). As a result, a liquid B (a coating liquid for forming a low refractive index layer) having a solid content concentration of 2.5% by weight was prepared.
(3) Production of antireflection film The liquid A obtained in (1) above was formed on the surface of a triacetyl cellulose film [Fuji Photo Film Co., Ltd., trade name “T-80UZ”] having a thickness of 80 μm as a base film. The Meyer bar No. was adjusted so that the thickness after curing was 3 μm. 8 was applied. Next, after drying at 90 ° C. for 1 minute, ultraviolet rays were irradiated at a light amount of 80 mJ / cm 2 to be cured in a half-cured state.
Next, on this half-cure surface, the Meyer bar No. 2 was adjusted so that the thickness after curing the liquid B obtained in (2) was 0.1 μm. 4 was applied. Next, after drying at 80 ° C. for 1 minute, ultraviolet rays are irradiated at a light amount of 350 mJ / cm 2 to completely cure, and on the triacetyl cellulose film, a hard coat layer having a refractive index of 1.50 and a refractive index of 1.36. An antireflection film was prepared by sequentially forming a low refractive index layer.
Table 1 shows the physical properties of the antireflection film thus prepared.
The thickness of each coat layer was measured by “MCPD-2000” manufactured by Otsuka Electronics Co., Ltd., and the refractive index was measured by an Abbe refractometer (Na light source, wavelength: about 590 nm) manufactured by Atago Co., Ltd. (Hereinafter the same)
Example 2
An antireflection film was produced in the same manner as in Example 1 except that the amount of the antistatic agent “Colcoat NR-121X-9IPA” was changed to 60 parts by weight in Example 1 (1). Refractive index of hard coat layer: 1.49
Table 1 shows the physical properties of the antireflection film thus prepared.
Example 3
An antireflection film was produced in the same manner as in Example 1, except that the amount of porous silica particle MIBK dispersion “ELCOM RT-1002SIV” was changed to 120 parts by weight. did. Refractive index of the low refractive index layer: 1.40
Table 1 shows the physical properties of the antireflection film thus prepared.
比較例１
実施例１（１）におけるＡ液の調製において、帯電防止剤を用いなかったこと以外は、実施例１と同様に実施して、反射防止フィルムを作製した。ハードコート層の屈折率：１.４９
このようにして作製した反射防止フィルムの物性を第１表に示す。
比較例２
実施例１（１）のＡ液の調製において、光重合開始剤「イルガキュア９０７」の使用量を１.８重量部に変更した以外は、実施例１（１）と同様にして、ハードコート層形成用塗工液を調製した。
次に、基材フィルムとして、厚さ８０μｍのトリアセチルセルロースフィルム「Ｔ８０ＵＺ」（前出）表面に、前記ハードコート層形成用塗工液を硬化後の厚さが３μｍになるように、マイヤーバーＮｏ．８で塗布した。次いで、９０℃で１分間乾燥したのち、紫外線を光量３５０ｍＪ／ｃｍ2で照射して完全硬化させ、ハードコートフィルムを作製した。
このようにして作製されたハードコートフィルムの物性を第１表に示す。
Comparative Example 1
In the preparation of the liquid A in Example 1 (1), an antireflection film was produced in the same manner as in Example 1 except that no antistatic agent was used. Refractive index of hard coat layer: 1.49
Table 1 shows the physical properties of the antireflection film thus prepared.
Comparative Example 2
A hard coat layer was prepared in the same manner as in Example 1 (1) except that the amount of the photopolymerization initiator “Irgacure 907” was changed to 1.8 parts by weight in the preparation of Liquid A in Example 1 (1). A forming coating solution was prepared.
Next, on the surface of the triacetylcellulose film “T80UZ” (described above) having a thickness of 80 μm as the base film, the Myer bar is set so that the thickness after curing the hard coat layer forming coating solution becomes 3 μm. No. 8 was applied. Next, after drying at 90 ° C. for 1 minute, ultraviolet rays were irradiated with a light amount of 350 mJ / cm 2 to be completely cured to produce a hard coat film.
The physical properties of the hard coat film thus prepared are shown in Table 1.
第１表から、本発明の反射防止フィルム（実施例１〜３）は、いずれも反射防止性に優れると共に、初期及びエタノール拭取り後の表面抵抗が低く、良好な帯電防止性及び耐溶剤性を有しており、耐擦傷性にも優れている。
これに対し、比較例１は、ハードコート層に帯電防止剤を含んでいないので、初期及びエタノール拭取り後の表面抵抗率が高く、帯電防止性に劣る。また、比較例２は、低屈折率層が設けられていないので、反射防止性に劣り、かつエタノール拭取り後の表面抵抗率が高く、耐溶剤性に劣る。
From Table 1, the antireflection films of the present invention (Examples 1 to 3) are all excellent in antireflection properties, have low surface resistance after initial and ethanol wiping, and have good antistatic properties and solvent resistance. And has excellent scratch resistance.
On the other hand, since the comparative example 1 does not contain the antistatic agent in the hard coat layer, the surface resistivity after initial and ethanol wiping is high and the antistatic property is inferior. Moreover, since the comparative example 2 is not provided with the low refractive index layer, it is inferior in antireflection property, has high surface resistivity after ethanol wiping, and inferior in solvent resistance.
本発明の反射防止フィルムは、画像表示素子の表面の光の反射を効果的に防止すると共に、埃や塵などの付着を抑制する帯電防止効果の持続性及び耐擦傷性に優れ、かつ耐溶剤性にも優れており、例えばＰＤＰ、ＣＲＴ、ＬＣＤなどのディスプレイに好適に用いられる。 The antireflection film of the present invention effectively prevents reflection of light on the surface of an image display element, has excellent antistatic effect for suppressing adhesion of dust, dust and the like, has excellent durability and scratch resistance, and is solvent resistant. For example, it is suitably used for displays such as PDP, CRT, and LCD.
Claims (3)
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005002822A JP4390717B2 (en) | 2005-01-07 | 2005-01-07 | Antireflection film |
| CNB2005800460983A CN100476458C (en) | 2005-01-07 | 2005-12-28 | Reflection preventive film |
| PCT/JP2005/024273 WO2006073139A1 (en) | 2005-01-07 | 2005-12-28 | Reflection preventive film |
| KR1020077017767A KR101314407B1 (en) | 2005-01-07 | 2005-12-28 | Reflection preventive film |
| TW095100409A TWI389798B (en) | 2005-01-07 | 2006-01-05 | An anti-reflectance film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005002822A JP4390717B2 (en) | 2005-01-07 | 2005-01-07 | Antireflection film |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| JP2006188016A true JP2006188016A (en) | 2006-07-20 |
| JP2006188016A5 JP2006188016A5 (en) | 2007-04-19 |
| JP4390717B2 JP4390717B2 (en) | 2009-12-24 |
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| Application Number | Title | Priority Date | Filing Date |
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| JP (1) | JP4390717B2 (en) |
| KR (1) | KR101314407B1 (en) |
| CN (1) | CN100476458C (en) |
| TW (1) | TWI389798B (en) |
| WO (1) | WO2006073139A1 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008242076A (en) * | 2007-03-27 | 2008-10-09 | Nippon Shokubai Co Ltd | Antistatic hard coat composition and optical article |
| JP2009086660A (en) * | 2007-09-12 | 2009-04-23 | Dainippon Printing Co Ltd | Optical layered body, method of producing the same, polarizer and image display device |
| JP2010170089A (en) * | 2008-12-22 | 2010-08-05 | Nof Corp | Reflection preventing film |
| JP2011008155A (en) * | 2009-06-29 | 2011-01-13 | Toppan Printing Co Ltd | Antistatic antireflection film, polarizing plate having the same, and display |
| JP2012072275A (en) * | 2010-09-28 | 2012-04-12 | Fujifilm Corp | Hard coat layer-forming composition, optical film, production method for optical film, polarizing plate and image display device |
| JP2013199568A (en) * | 2012-03-23 | 2013-10-03 | Riken Technos Corp | Active energy ray-curable resin composition |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101900985B1 (en) * | 2011-03-28 | 2018-09-20 | 도판 인사츠 가부시키가이샤 | Antireflection film and method for producing same |
| CN111057261B (en) * | 2019-12-20 | 2022-05-03 | 合肥乐凯科技产业有限公司 | Anti-dazzle hardened film and preparation method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4014133B2 (en) * | 2001-10-23 | 2007-11-28 | 日東電工株式会社 | Antireflection film, optical element and image display device |
| JP3980423B2 (en) * | 2002-07-01 | 2007-09-26 | 日東電工株式会社 | HARD COAT FILM, ITS MANUFACTURING METHOD, OPTICAL ELEMENT AND IMAGE DISPLAY DEVICE |
| JP4404337B2 (en) * | 2003-02-20 | 2010-01-27 | 大日本印刷株式会社 | Anti-reflection laminate |
-
2005
- 2005-01-07 JP JP2005002822A patent/JP4390717B2/en active Active
- 2005-12-28 WO PCT/JP2005/024273 patent/WO2006073139A1/en not_active Application Discontinuation
- 2005-12-28 CN CNB2005800460983A patent/CN100476458C/en active Active
- 2005-12-28 KR KR1020077017767A patent/KR101314407B1/en active IP Right Grant
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2006
- 2006-01-05 TW TW095100409A patent/TWI389798B/en active
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008242076A (en) * | 2007-03-27 | 2008-10-09 | Nippon Shokubai Co Ltd | Antistatic hard coat composition and optical article |
| JP2009086660A (en) * | 2007-09-12 | 2009-04-23 | Dainippon Printing Co Ltd | Optical layered body, method of producing the same, polarizer and image display device |
| JP2010170089A (en) * | 2008-12-22 | 2010-08-05 | Nof Corp | Reflection preventing film |
| JP2011008155A (en) * | 2009-06-29 | 2011-01-13 | Toppan Printing Co Ltd | Antistatic antireflection film, polarizing plate having the same, and display |
| JP2012072275A (en) * | 2010-09-28 | 2012-04-12 | Fujifilm Corp | Hard coat layer-forming composition, optical film, production method for optical film, polarizing plate and image display device |
| JP2013199568A (en) * | 2012-03-23 | 2013-10-03 | Riken Technos Corp | Active energy ray-curable resin composition |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100476458C (en) | 2009-04-08 |
| TW200631775A (en) | 2006-09-16 |
| KR101314407B1 (en) | 2013-10-04 |
| TWI389798B (en) | 2013-03-21 |
| JP4390717B2 (en) | 2009-12-24 |
| CN101099093A (en) | 2008-01-02 |
| WO2006073139A1 (en) | 2006-07-13 |
| KR20070095386A (en) | 2007-09-28 |
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