JP4262404B2 - Antiglare antireflection film, polarizing plate and liquid crystal display device - Google Patents

Description

【００５７】
（反射防止膜の評価）
得られたフィルムについて、以下の項目の評価を行った。
（１）平均反射率
分光光度計（日本分光（株）製）を用いて、３８０〜７８０ｎｍの波長領域において、入射角５°における分光反射率を測定した。結果には４５０〜６５０ｎｍの平均反射率を用いた。
（２）ヘイズ
得られたフィルムのヘイズをヘイズメーターＭＯＤＥＬ １００１ＤＰ（日本電色工業（株）製）を用いて測定した。
（３）鉛筆硬度評価
耐傷性の指標としてＪＩＳ Ｋ ５４００に記載の鉛筆硬度評価を行った。反射防止膜を温度２５℃、湿度６０％ＲＨで２時間調湿した後、ＪＩＳ Ｓ ６００６に規定する３Ｈの試験用鉛筆を用いて、１ｋｇの荷重で行い、下記のように評価した。
○：ｎ＝５の評価において傷が全く認められない
△：ｎ＝５の評価において傷が１または２つ
×：ｎ＝５の評価において傷が３つ以上
【００５８】
（４）接触角、指紋付着性評価
表面の耐汚染性の指標として、光学材料を温度２５℃、湿度６０％ＲＨで２時間調湿した後、水に対する接触角を測定した。またこのサンプル表面に指紋を付着させてから、それをクリーニングクロスで拭き取ったときの状態を観察して、以下のように指紋付着性を評価した。
○：指紋が完全に拭き取れる
△：指紋がやや見える
×：指紋がほとんど拭き取れない
【００５９】
（５）動摩擦係数測定
表面滑り性の指標として動摩擦係数にて評価した。動摩擦係数は試料を２５℃、相対湿度６０％で２時間調湿した後、ＨＥＩＤＯＮ−１４動摩擦測定機により５ｍｍφステンレス鋼球、荷重１００ｇ、速度６０ｃｍ／ｍｉｎにて測定した値を用いた。
（６）防眩性評価
作成した防眩性フィルムにルーバーなしのむき出し蛍光灯（８０００ｃｄ／ｍ²）を映し、その反射像のボケの程度を以下の基準で評価した。
◎:蛍光灯の輪郭が全くわからない
○:蛍光灯の輪郭がわずかにわかる
△:蛍光灯はぼけているが、輪郭は識別できる
×:蛍光灯がほとんどぼけない
（７）ギラツキ評価
作成した防眩性フィルムにルーバーありの蛍光灯拡散光を映し、表面のギラツキを以下の基準で評価した。
○:ほとんどギラツキが見られない
△:わずかにギラツキがある
×:目で識別できるサイズのギラツキがある
【００６０】
表２に実施例および比較例の結果を示す。実施例１〜７はいずれも反射防止性能に優れ、鉛筆硬度、指紋付着性、防眩性、ギラツキのような防眩性反射防止フィルムに必要とする全ての性能は良好であった。
比較例１は低屈折率層に無機フィラーが存在しないため、鉛筆硬度が悪く、耐傷性が不足していた。
比較例２および３は防眩性ハードコート層に無機フィラーが存在しないため、鉛筆硬度が悪く、耐傷性が不足していた。
比較例４はハードコート層に無機フィラーが存在しないため、鉛筆硬度が悪く、耐傷性が不足していた。
【００６１】
【表２】

【００６２】
[実施例８]
実施例１から７のフィルムを用いて防眩性反射防止偏光板を作成した。この偏光板を用いて反射防止層を最表層に配置した液晶表示装置を作成したところ、外光の映り込みがないために優れたコントラストが得られ、防眩性により反射像が目立たず優れた視認性を有していた。
【００６３】
[透明支持体の作成]
【００６４】
（１）３層共流延トリアセチルセルロースフィルムＡの作成
【００６５】
（トリアセチルセルロースドープＡ１の調製）
トリアセチルセルロース１７．４重量部、トリフェニルフォスフェート２．６重量部、ジクロロメタン６６重量部、メタノール５．８重量部、ノルマルブタノール８．２重量部からなる原料を攪拌しながら混合して溶解し、トリアセチルセルロースドープＡ１を調製した。
【００６６】
（トリアセチルセルロースドープＡ２の調製）
トリアセチルセルロース２４重量部、トリフェニルフォスフェート４重量部、ジクロロメタン６６重量部、メタノール６重量部からなる原料を攪拌しながら混合して溶解し、トリアセチルセルロースドープＡ２を調製した。
【００６７】
（３層共流延トリアセチルセルロースフィルムＡの作成）
特開平１１−２５４５９４等に従って、３層共流延ダイを用い、ドープＡ２の両側にドープＡ１を共流延するように配置して金属ドラム上に同時に吐出させて重層流延した後、流延膜をドラムから剥ぎ取り、乾燥して、ドラム面側から１０μｍ、６０μｍ、１０μｍの３層共流延トリアセチルセルロースフィルムを作成した。このフィルムには、各層間に明確な界面は形成されていなかった。
【００６８】
（２）低温溶解法によるトリアセチルセルロースフィルムＢの作成
【００６９】
（トリアセチルセルロースドープＢの調製）
トリアセチルセルロース２０重量部、酢酸メチル４８重量部、シクロヘキサノン２０重量部、メタノール５重量部、エタノール５重量部、トリフェニルフォスフェート／ビフェニルジフェニルフォスフェート（１／２）２重量部、シリカ（粒径２０ｎｍ）０．１重量部、２、４−ビス−（ｎ−オクチルチオ）−６−（４−ヒドロキシ−３，５−ジ−ｔｅｒｔ−ブチルアニリノ）−１、３、５−トリアジン０．２重量部を添加、攪拌して得られた不均一なゲル状溶液を、−７０℃にて６時間冷却した後、５０℃に加温し攪拌してドープＢを調製した。
【００７０】
（低温溶解法によるトリアセチルセルロースフィルムＢの作成）
特開平７−１１０５５に従い、上記トリアセチルセルロースドープＢを単層ドラム流延し、厚み８０μｍのトリアセチルセルロースフィルムＢを作成した。
【００７１】
（３）高温溶解法によるトリアセチルセルロースフィルムＣの作成
【００７２】
（トリアセチルセルロースドープＣの調製）
上記トリアセチルセルロースドープＢと同様にして得られた不均一なゲル状溶液を、ステンレス製密閉容器にて１ＭＰａ、１８０℃で５分間加熱した後、５０℃の水浴中に容器ごと投入し冷却し、トリアセチルセルロースドープＣを調製した。
【００７３】
（高温溶解法によるトリアセチルセルロースフィルムＣの作成）
特開平７−１１０５５に従い、上記トリアセチルセルロースドープＣを単層ドラム流延し、厚み８０μｍのトリアセチルセルロースフィルムＣを作成した。
【００７４】
[実施例９〜１７、比較例５〜９]
実施例１〜７、比較例１〜４における８０μｍの厚さのトリアセチルセルロースフィルムを表３記載のトリアセチルセルロースフィルムＡ〜Ｃ、ハードコート層塗布液Ａ〜Ｄ、防眩性ハードコート層用塗布液Ａ〜Ｄ、低屈折率層用塗布液Ａ〜Ｃに変更した以外は同様にして防眩性反射防止フィルムを作製した。
【００７５】
【表３】

【００７６】
前述の評価を同様に行った結果を表４に示した。
【００７７】
【表４】

【００７８】
実施例９〜１７はいずれも反射防止性能に優れ、鉛筆硬度、指紋付着性、防眩性、ギラツキのような防眩性反射防止フィルムに必要とする全ての性能は良好であった。
比較例５および比較例９は低屈折率層に無機フィラーが存在しないため、鉛筆硬度が悪く、耐傷性が不足していた。
比較例６および７は防眩性ハードコート層に無機フィラーが存在しないため、鉛筆硬度が悪く、耐傷性が不足していた。
比較例８はハードコート層に無機フィラーが存在しないため、鉛筆硬度が悪く、耐傷性が不足していた。
【００７９】
[実施例１０]
実施例１から９のフィルムを用いて防眩性反射防止偏光板を作成した。この偏光板を用いて反射防止層を最表層に配置した液晶表示装置を作成したところ、外光の映り込みがないために優れたコントラストが得られ、防眩性により反射像が目立たず優れた視認性を有していた。
【００８０】
【発明の効果】
本発明の防眩性反射防止フィルムは、支持体上に防眩性ハードコート層と低屈折率層を形成するのみによって、簡便かつ安価に製造可能であり、しかも十分な反射防止性能と耐傷性、さらには防汚性を有する。
本発明のこのような優れた防眩性反射防止フィルムを用いた偏光板及び液晶表示装置を提供することにある。
【図面の簡単な説明】
【図１】防眩性反射防止フィルムの層構成を示す断面模式図である。
【符号の説明】
１ 防眩性反射防止フィルム
２ 透明支持体
３ ハードコート層
４ 防眩性ハードコート層
５ 低屈折率層
６ マット粒子[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an antireflection film having antiglare properties, a polarizing plate using the same, and a liquid crystal display device.
[0002]
[Prior art]
In general, an antireflection film prevents contrast reduction and image reflection due to reflection of external light in an image display device such as a cathode ray tube display (CRT), a plasma display (PDP), and a liquid crystal display (LCD). In order to reduce the reflectivity using the principle of optical interference, it is placed on the outermost surface of the display.
[0003]
However, in an antireflection film having only a hard coat layer and a low refractive index layer on a transparent support, the low refractive index layer must be sufficiently lowered in order to reduce the reflectance, and triacetyl In order to make the average reflectance from 450 nm to 650 nm 1.6% or less in an antireflection film using cellulose as a support and a UV-coated film of dipentaerythritol hexaacrylate as a hard coat layer, the refractive index is 1.40 or less. Must be.
Examples of materials having a refractive index of 1.40 or less include magnesium fluoride and calcium fluoride for inorganic materials, and fluorine-containing compounds with a high fluorine content for organic materials, but these fluorine compounds are arranged on the outermost surface of the display because they have no cohesive force. As a film, the scratch resistance was insufficient. Therefore, in order to have sufficient scratch resistance, a compound having a refractive index of 1.43 or more is required. Thus, it is difficult to achieve both reduction in reflectance and scratch resistance.
[0004]
Japanese Patent Application Laid-Open No. 7-287102 describes that the reflectance is reduced by increasing the refractive index of the hard coat layer. However, since such a high refractive index hard coat layer has a large difference in refractive index with the support, color unevenness of the film occurs, and the wavelength dependence of the reflectance also greatly fluctuates.
[0005]
Japanese Patent Application Laid-Open No. 7-333404 describes an antiglare antireflection film having excellent gas barrier properties, antiglare properties, and antireflection properties. However, since a silicon oxide film by CVD is essential, wet coating is required. Inferior in productivity.
[0006]
[Problems to be solved by the invention]
The object of the present invention is to produce an antiglare hard coat layer and a low refractive index layer on a support, which can be easily and inexpensively manufactured, and has sufficient antireflection performance and scratch resistance, and further is antifouling. It is providing the anti-glare antireflection film which has property.
Another object of the present invention is to provide a polarizing plate and a liquid crystal display device using such an excellent antiglare antireflection film.
[0007]
[Means for Solving the Problems]
  According to the present invention, an antiglare antireflection film, a polarizing plate and a liquid crystal display device having the following constitution are provided, and the above object is achieved.
  1. In an antiglare antireflection film having an antiglare hard coat layer and a low refractive index layer having a refractive index of 1.38 to 1.49 on a transparent support,
  All layers contain inorganic fillerAnd
The particle size of the inorganic filler contained in the antiglare hard coat layer is 1 to 100 nm,
The film thickness of the antiglare hard coat layer is 1 to 10 μm,
The antiglare hard coat layer contains matte particles having an average particle diameter of 1.0 to 10.0 μm,
The inorganic filler contained in the antiglare hard coat layer is an oxide of at least one metal selected from zirconium, titanium, aluminum, indium, zinc, tin, and antimony, and the content thereof is antiglare. 30 to 75% of the total mass of the hard coat layer
An antiglare antireflection film characterized by that.
  2The above-mentioned, characterized in that it has a hard coat layer containing an inorganic filler in the lower layer of the antiglare hard coat layer1The antiglare antireflection film described in 1.
  31. The antiglare hard coat layer contains a binder and an inorganic filler, and the refractive index of the mixture of the binder and the inorganic filler is 1.57 to 2.00.Or 2The antiglare antireflection film as described.
  4The low refractive index layer is composed of a fluorine-containing compound crosslinked with heat or ionizing radiation and an inorganic filler, and has a dynamic friction coefficient of 0.03 to 0.15 and a contact angle with water of 90 to 120 °. 1 to above3The anti-glare antireflection film according to any one of the above.
  5The inorganic filler contained in the low refractive index layer is silica or magnesium fluoride, and the content thereof is 15 to 40% of the total mass of the low refractive index layer.4The anti-glare antireflection film according to any one of the above.
  6The inorganic filler contained in the hard coat layer is silica or alumina, and the content thereof is 30 to 70% of the total mass of the hard coat layer.2-5The anti-glare antireflection film according to any one of the above.
  7The haze is 3.0 to 20.0%, and the average reflectance at 450 to 650 nm is 1.8% or less.6The anti-glare antireflection film according to any one of the above.
  8The material of the transparent support is triacetylcellulose, polyethylene terephthalate, or polyethylene naphthalate,7The anti-glare antireflection film according to any one of the above.
  9The transparent support is a triacetyl cellulose film, and a triacetyl cellulose dope prepared by dissolving triacetyl cellulose in a solvent is used for either single layer casting, multiple layer co-casting or multiple layer sequential casting. The above 1 to 3, which are produced by casting by any casting method8The anti-glare antireflection film according to any one of the above.
  10The triacetyl cellulose dope is a triacetyl cellulose dope prepared by dissolving triacetyl cellulose in a solvent substantially free of dichloromethane by a cooling dissolution method or a high temperature dissolution method.9The antiglare antireflection film as described.
  111 to above10A polarizing plate, wherein the antiglare antireflection film according to any one of the above is used for at least one of the two protective films of the polarizing layer in the polarizing plate.
  121 to above10A liquid crystal display device comprising the antiglare antireflection film described in any one of the above items as an outermost layer of a display.
  13. the above11A liquid crystal display device using the polarizing plate described in 1) such that an antiglare antireflection film as a protective layer of the polarizing plate is an outermost layer of the display.
[0008]
DETAILED DESCRIPTION OF THE INVENTION
A basic configuration of an antiglare antireflection film suitable as an embodiment of the present invention will be described with reference to the drawings.
The embodiment schematically shown in FIG. 1 is an example of the antiglare antireflection film of the present invention. In this case, the antiglare antireflection film 1 has a layer structure in the order of a transparent support 2, a hard coat layer 3, an antiglare hard coat layer 4, and a low refractive index layer 5. Matte particles 6 are dispersed in the antiglare hard coat layer 4 and the refractive index of the material other than the matte particles 6 of the antiglare hard coat layer 4 is in the range of 1.57 to 2.00. The refractive index of the low refractive index layer 5 is preferably in the range of 1.38 to 1.49. The hard coat layer 3 is not essential, but is preferably applied for imparting film strength.
[0009]
As the transparent support of the antiglare antireflection film of the present invention, it is preferable to use a plastic film. Polymers that form plastic films include cellulose esters (eg, triacetyl cellulose, diacetyl cellulose), polyamides, polycarbonates, polyesters (eg, polyethylene terephthalate, polyethylene naphthalate), polystyrenes, polyolefins, norbornene resins (Arton: trade names) , Manufactured by JSR Corporation), amorphous polyolefin (ZEONEX: trade name, manufactured by Nippon Zeon Co., Ltd.), and the like. Of these, triacetyl cellulose, polyethylene terephthalate, and polyethylene naphthalate are preferable, and triacetyl cellulose is particularly preferable.
When the antiglare antireflection film of the present invention is used in a liquid crystal display device, it is disposed on the outermost surface of the display by means such as providing an adhesive layer on one side. When the transparent support is triacetylcellulose, since triacetylcellulose is used as a protective film for protecting the polarizing layer of the polarizing plate, it is costly to use the antiglare antireflection film of the present invention as it is for the protective film. Preferred above.
[0010]
As the transparent support of the antiglare antireflection film of the present invention, a triacetylcellulose dope prepared by dissolving triacetylcellulose in a solvent is cast in a single layer, in a multiple layer co-casting or in a multiple layer sequential casting It is preferable to use a triacetyl cellulose film prepared by casting by any one of the casting methods. In particular, from the viewpoint of environmental conservation, a triacetyl cellulose film prepared using a triacetyl cellulose dope prepared by dissolving triacetyl cellulose in a solvent substantially free of dichloromethane by a cooling dissolution method or a high temperature dissolution method Is preferred.
[0011]
Examples of the single layer casting of triacetyl cellulose include drum casting and band casting disclosed in Japanese Patent Application Laid-Open No. Hei 7-11055, and the like. Casting is disclosed in Japanese Patent Application Laid-Open Nos. 61-94725 and 62-43846. Sequential casting is performed by repeating single layer casting. For each casting, raw material flakes are made of halogenated hydrocarbons (dichloromethane, etc., alcohols (methanol, ethanol, butanol, etc.), esters (methyl formate, methyl acetate, etc.), ethers (dioxane, dioxolane, diethyl ether, etc.) ) Or the like, and a solution (referred to as a dope) to which various additives such as a plasticizer, an ultraviolet absorber, a deterioration preventing agent, a slipping agent, and a peeling accelerator are added as required When a dope supply means (referred to as a die) is cast on a support composed of an endless metal belt of the type or a rotating drum, if a single layer is cast, a single dope is cast into a plurality of layers. If so, a low-concentration dope is co-cast on both sides of a high-concentration cellulose ester dope. Then a method consisting of removing the various solvents is passed through the drying section by the conveying means.
[0012]
A typical solvent for dissolving triacetylcellulose as described above is dichloromethane. Technically, however, halogenated hydrocarbons such as dichloromethane can be used without problems, but when a triacetylcellulose dope prepared by dissolving in a solvent substantially containing dichloromethane is produced by a single layer casting method. Since dichloromethane is released into the atmosphere during the production process, it is preferable that halogenated hydrocarbons such as dichloromethane are not substantially contained from the viewpoint of environmental protection and working environment. “Substantially free” means that the proportion of halogenated hydrocarbon in the organic solvent is less than 5% by weight (preferably less than 2% by weight). In the case of the co-casting method, even if a dope using a solvent substantially containing dichloromethane is cast by a multi-layer co-casting method, the dope having a higher triacetyl cellulose concentration than the outer casting layer is used. As a result, the amount of dichloromethane released into the atmosphere can be reduced. In addition, the casting speed can be increased and the productivity is excellent. Of course, even in the case of the co-casting method, it is preferable that a halogenated hydrocarbon such as dichloromethane is substantially not contained.
When adjusting the dope of triacetyl cellulose using a solvent substantially free of dichloromethane or the like, a special dissolution method as described later is essential.
[0013]
The first dissolution method is called a cooling dissolution method and will be described below. First, triacetyl cellulose is gradually added to a solvent at a temperature around room temperature (-10 to 40 ° C.) while stirring. The mixture is then cooled to -100 to -10 ° C (preferably -80 to -10 ° C, more preferably -50 to -20 ° C, most preferably -50 to -30 ° C). The cooling can be performed, for example, in a dry ice / methanol bath (−75 ° C.) or a cooled diethylene glycol solution (−30 to −20 ° C.). When cooled in this manner, the mixture of triacetyl cellulose and solvent solidifies. Furthermore, when this is heated to 0 to 200 ° C. (preferably 0 to 150 ° C., more preferably 0 to 120 ° C., most preferably 0 to 50 ° C.), a solution in which triacetyl cellulose flows in the solvent is obtained. The temperature can be raised by simply leaving it at room temperature or in a warm bath.
[0014]
The second method is called a high temperature melting method and will be described below. First, triacetyl cellulose is gradually added to a solvent at a temperature around room temperature (-10 to 40 ° C.) while stirring. The triacetyl cellulose solution of the present invention is preferably swollen beforehand by adding triacetyl cellulose to a mixed solvent containing various solvents. In this method, the dissolution concentration of triacetylcellulose is preferably 30% by weight or less, but is preferably as high as possible from the viewpoint of drying efficiency during film formation. Next, the organic solvent mixed solution is heated to 70 to 240 ° C. under a pressure of 0.2 MPa to 30 MPa (preferably 80 to 220 ° C., more preferably 100 to 200 ° C., most preferably 100 to 190 ° C.). Next, since these heated solutions cannot be applied as they are, it is necessary to cool them below the lowest boiling point of the solvent used. In that case, it is common to cool to -10-50 degreeC and to return to a normal pressure. For cooling, the high-pressure and high-temperature vessel or line containing the triacetylcellulose solution may be left at room temperature, and more preferably, the apparatus may be cooled using a coolant such as cooling water.
[0015]
The antiglare antireflection film of the present invention has an antiglare hard coat layer on a transparent support, and further has a low refractive index layer thereon, but if necessary, a lower layer of the antiglare hard coat layer A smooth hard coat layer can be provided.
[0016]
In the antiglare antireflection film of the present invention, an inorganic filler is added to all layers on the support for the purpose of improving the film strength. The inorganic filler added to each layer may be the same or different, and it is preferable that the type, addition amount, etc. are appropriately adjusted according to the required performance such as refractive index, film strength, film thickness, and coating property of each layer. .
The shape of the inorganic filler used in the present invention is not particularly limited, and for example, any of a spherical shape, a plate shape, a fiber shape, a rod shape, an irregular shape, a hollow shape, and the like are preferably used. preferable.
Further, the kind of the inorganic filler is not particularly limited, but an amorphous one is preferably used, and is preferably made of a metal oxide, nitride, sulfide or halide. Particularly preferred.
[0017]
As metal atoms of the metal oxide, Na, K, Mg, Ca, Ba, Al, Zn, Fe, Cu, Ti, Sn, In, W, Y, Sb, Mn, Ga, V, Nb, Ta, Examples include Ag, Si, B, Bi, Mo, Ce, Cd, Be, Pb, and Ni.
In order to obtain a transparent cured film, the average particle diameter of the inorganic filler is preferably set to a value within the range of 0.001 to 0.2 μm, more preferably 0.001 to 0.1 μm, and still more preferably. 0.001 to 0.06 μm. Here, the average particle diameter of the particles is measured by a Coulter counter.
Although the usage method of the inorganic filler in this invention is not restrict | limited in particular, For example, it can use in a dry state or can also be used in the state disperse | distributed to water or the organic solvent.
In the present invention, it is also preferable to use a dispersion stabilizer in combination for the purpose of suppressing aggregation and sedimentation of the inorganic filler. As the dispersion stabilizer, polyvinyl alcohol, polyvinyl pyrrolidone, cellulose derivative, polyamide, phosphate ester, polyether, surfactant, silane coupling agent, titanium coupling agent and the like can be used. In particular, a silane coupling agent is preferable because the film after curing is strong. Although the addition amount of the silane coupling agent as a dispersion stabilizer is not particularly limited, for example, the value is preferably 1 part by weight or more with respect to 100 parts by weight of the inorganic filler. Also, the method of adding the dispersion stabilizer is not particularly limited, but a hydrolyzed one can be added, or a dispersion stabilizer silane coupling agent and an inorganic filler are mixed. Thereafter, a method of further hydrolysis and condensation can be employed, but the latter is more preferable.
The inorganic filler suitable for each layer will be described later.
[0018]
The antiglare hard coat layer of the present invention will be described below.
The antiglare hard coat layer is formed from a binder for imparting hard coat properties, mat particles for imparting antiglare properties, and an inorganic filler for increasing the refractive index, preventing cross-linking shrinkage, and increasing the strength. The
The binder is preferably a polymer having a saturated hydrocarbon chain or a polyether chain as a main chain, and more preferably a polymer having a saturated hydrocarbon chain as a main chain.
The binder polymer preferably has a crosslinked structure.
As the binder polymer having a saturated hydrocarbon chain as a main chain, a polymer of an ethylenically unsaturated monomer is preferable. As the binder polymer having a saturated hydrocarbon chain as the main chain and having a crosslinked structure, a (co) polymer of monomers having two or more ethylenically unsaturated groups is preferable.
In order to obtain a high refractive index, the monomer structure preferably contains an aromatic ring or at least one atom selected from halogen atoms other than fluorine, sulfur atoms, phosphorus atoms, and nitrogen atoms.
[0019]
Examples of the monomer having two or more ethylenically unsaturated groups include esters of polyhydric alcohol and (meth) acrylic acid (eg, ethylene glycol di (meth) acrylate, 1,4-dichlorohexane diacrylate, pentaerythritol tetra). (Meth) acrylate), pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, Pentaerythritol hexa (meth) acrylate, 1,3,5-cyclohexanetriol triacrylate, polyurethane polyacrylate, polyester polyacrylate), vinylbenzene and derivatives thereof (Eg, 1,4-divinylbenzene, 4-vinylbenzoic acid-2-acryloyl ethyl ester, 1,4-divinylcyclohexanone), vinyl sulfone (eg, divinyl sulfone), acrylamide (eg, methylene bisacrylamide) and methacryl Amides are mentioned.
[0020]
Specific examples of the high refractive index monomer include bis (4-methacryloylthiophenyl) sulfide, vinyl naphthalene, vinyl phenyl sulfide, 4-methacryloxyphenyl-4′-methoxyphenyl thioether, and the like.
[0021]
Polymerization of the monomer having an ethylenically unsaturated group can be performed by irradiation with ionizing radiation or heating in the presence of a photo radical initiator or a thermal radical initiator.
Accordingly, a coating liquid containing a monomer having an ethylenically unsaturated group, a photo radical initiator or a thermal radical initiator, mat particles, and an inorganic filler is prepared, and the coating liquid is applied on a transparent support and then ionizing radiation or heat is applied. The antiglare antireflection film can be formed by curing by the polymerization reaction.
[0022]
The polymer having a polyether as the main chain is preferably a ring-opening polymer of a polyfunctional epoxy compound. The ring-opening polymerization of the polyfunctional epoxy compound can be performed by irradiation with ionizing radiation or heating in the presence of a photoacid generator or a thermal acid generator.
Therefore, a coating liquid containing a polyfunctional epoxy compound, a photoacid generator or a thermal acid generator, matte particles and an inorganic filler is prepared, and the coating liquid is applied on a transparent support and then subjected to a polymerization reaction by ionizing radiation or heat. It can be cured to form an antiglare antireflection film.
[0023]
Instead of or in addition to a monomer having two or more ethylenically unsaturated groups, a monomer having a crosslinkable functional group is used to introduce a crosslinkable functional group into the polymer, and by reaction of this crosslinkable functional group, A crosslinked structure may be introduced into the binder polymer.
Examples of the crosslinkable functional group include isocyanate group, epoxy group, aziridine group, oxazoline group, aldehyde group, carbonyl group, hydrazine group, carboxyl group, methylol group and active methylene group. Vinylsulfonic acid, acid anhydride, cyanoacrylate derivative, melamine, etherified methylol, ester and urethane, and metal alkoxide such as tetramethoxysilane can also be used as a monomer for introducing a crosslinked structure. A functional group that exhibits crosslinkability as a result of the decomposition reaction, such as a block isocyanate group, may be used. That is, in the present invention, the crosslinkable functional group may not react immediately but may exhibit reactivity as a result of decomposition.
These binder polymers having a crosslinkable functional group can form a crosslinked structure by heating after coating.
[0024]
For the purpose of imparting antiglare properties, the antiglare hard coat layer contains matte particles having an average particle diameter of 1 to 10 μm, preferably 1.5 to 7.0 μm, such as inorganic compound particles or resin particles. .
Specific examples of the mat particles include silica particles and TiO.₂Preferred examples include particles of inorganic compounds such as particles; resin particles such as crosslinked acrylic particles, crosslinked styrene particles, melamine resin particles, and benzoguanamine resin particles. Of these, crosslinked styrene particles are preferred.
As the shape of the mat particle, either a true sphere or an indefinite shape can be used.
Further, two or more different kinds of mat particles may be used in combination.
The amount of mat particles in the formed anti-glare hard coat layer is preferably 10 to 1000 mg / m.², More preferably 30-100 mg / m²It is contained in the antiglare hard coat layer so as to be.
Further, in a particularly preferred embodiment, cross-linked styrene particles are used as the matte particles, and the cross-linked styrene particles having a particle size larger than a half of the film thickness of the antiglare hard coat layer are 40 to 100 of the entire cross-linked styrene particles. %. Here, the particle size distribution of the mat particles is measured by a Coulter counter method, and the measured distribution is converted into a particle number distribution.
[0025]
In order to increase the refractive index of the antiglare hard coat layer, in addition to the above mat particles, at least one metal selected from titanium, zirconium, aluminum, indium, zinc, tin and antimony is used. It is preferable that an inorganic filler which is made of an oxide and has an average particle diameter of 0.001 to 0.2 μm or less, preferably 0.001 to 0.1 μm, more preferably 0.001 to 0.06 μm or less is contained. .
Specific examples of the inorganic filler used in the antiglare hard coat layer include TiO₂, ZrO₂, Al₂O_Three, In₂O_ThreeZnO, SnO₂, Sb₂O_ThreeAnd ITO. TiO₂And ZrO₂Is particularly preferable in terms of increasing the refractive index. The surface of the inorganic filler is preferably subjected to a silane coupling treatment or a titanium coupling treatment, and a surface treatment agent having a functional group capable of reacting with a binder species on the filler surface is preferably used.
The amount of these inorganic fillers added is preferably 10 to 90% of the total mass of the antiglare hard coat layer, more preferably 20 to 80%, and particularly preferably 30 to 75%.
Such a filler does not scatter because the particle size is sufficiently smaller than the wavelength of light, and a dispersion in which the filler is dispersed in a binder polymer behaves as an optically uniform substance.
[0026]
The total refractive index of the mixture of binder and inorganic filler in the antiglare hard coat layer of the present invention is preferably 1.57 to 2.00, more preferably 1.60 to 1.80. In order to make the refractive index within the above range, the kind and amount ratio of the binder and the inorganic filler may be appropriately selected. How to select can be easily known experimentally in advance.
[0027]
The film thickness of the antiglare hard coat layer is preferably 1 to 10 μm, and more preferably 1.2 to 6 μm.
[0028]
In the antiglare antireflection film of the present invention, a smooth hard coat layer is coated between the transparent support and the antiglare hard coat layer as necessary for the purpose of improving the film strength.
The material used for the smooth hard coat layer is the same as that described in the anti-glare hard coat layer except that no mat particles for imparting anti-glare properties are used, and is formed from a binder and an inorganic filler.
In the smooth hard coat layer of the present invention, silica and alumina are preferable as the inorganic filler from the viewpoint of strength and versatility, and silica is particularly preferable. Further, the surface of the inorganic filler is preferably subjected to silane coupling treatment, and a surface treatment agent having a functional group capable of reacting with the binder species on the filler surface is preferably used.
The amount of these inorganic fillers added is preferably 10 to 90% of the total mass of the hard coat layer, more preferably 20 to 80%, and particularly preferably 30 to 75%.
The film thickness of the smooth hard coat layer is preferably 1 to 10 μm, more preferably 1.2 to 6 μm.
[0029]
The low refractive index layer of the present invention will be described below.
The refractive index of the low refractive index layer of the antiglare antireflection film of the present invention is 1.38 to 1.49, preferably 1.38 to 1.44.
Further, the low refractive index layer preferably satisfies the following formula (I) from the viewpoint of reducing the reflectance.
(Mλ / 4) × 0.7 <n₁d₁<(Mλ / 4) × 1.3 ...... Formula (I)
Where m is a positive odd number and n₁Is the refractive index of the low refractive index layer and d₁Is the film thickness (nm) of the low refractive index layer. Further, λ is a wavelength and is a value in the range of 500 to 550 nm.
In addition, satisfy | filling said numerical formula (I) means that m (positive odd number, usually 1) which satisfy | fills numerical formula (I) exists in the said wavelength range.
[0030]
The material for forming the low refractive index layer of the present invention will be described below.
In the low refractive index layer, as a low refractive index binder, a fluorine-containing compound crosslinked by heat or ionizing radiation having a dynamic friction coefficient of 0.03 to 0.15 and a contact angle of 90 to 120 ° with water, and an inorganic material for improving film strength A binder made of a filler is preferably used. In this case, the inorganic filler is dispersed in the fluorine-containing compound crosslinked by heat or ionizing radiation.
[0031]
As the crosslinkable fluorine-containing compound before crosslinking used for the low refractive index layer, in addition to a perfluoroalkyl group-containing silane compound (for example, (heptadecafluoro-1,1,2,2-tetradecyl) triethoxysilane), Examples thereof include a fluorine-containing copolymer of a fluorine-containing monomer and a monomer for imparting a crosslinkable group.
Specific examples of the fluorine-containing monomer include, for example, fluoroolefins (for example, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, hexafluoroethylene, hexafluoropropylene, perfluoro-2,2-dimethyl-1,3-dioxole, etc.) , (Meth) acrylic acid partial or fully fluorinated alkyl ester derivatives (for example, Biscoat 6FM (manufactured by Osaka Organic Chemical Co., Ltd.) and M-2020 (manufactured by Daikin)), fully or partially fluorinated vinyl ethers, and the like.
As a monomer for imparting a crosslinkable group, in addition to a (meth) acrylate monomer having a crosslinkable functional group in the molecule like glycidyl methacrylate, it has a carboxyl group, a hydroxyl group, an amino group, a sulfonic acid group, etc. ) Acrylate monomers (for example, (meth) acrylic acid, methylol (meth) acrylate, hydroxyalkyl (meth) acrylate, allyl acrylate, etc.). It is described in JP-A-10-25388 and JP-A-10-147739 that the latter can introduce a crosslinked structure after copolymerization.
[0032]
Moreover, not only the copolymer of the said fluorine-containing monomer and the monomer for crosslinkable group provision but the copolymer by which the monomer other than these was copolymerized may be used. The monomer that can be used in combination is not particularly limited. For example, olefins (ethylene, propylene, isoprene, vinyl chloride, vinylidene chloride, etc.), acrylic esters (methyl acrylate, methyl acrylate, ethyl acrylate, 2-acrylic acid 2- Ethyl hexyl), methacrylates (methyl methacrylate, ethyl methacrylate, butyl methacrylate, ethylene glycol dimethacrylate, etc.), styrene derivatives (styrene, divinylbenzene, vinyl toluene, α-methylstyrene, etc.), vinyl ethers (methyl vinyl ether) Etc.), vinyl esters (vinyl acetate, vinyl propionate, vinyl cinnamate, etc.), acrylamides (N-tertbutylacrylamide, N-cyclohexylacrylamide, etc.), methacrylamides, B nitrile derivatives, and the like.
[0033]
As the inorganic filler used in the low refractive index layer, those having a low refractive index are preferably used. Preferred inorganic fillers are silica and magnesium fluoride, and silica is particularly preferable.
The average particle size of the inorganic filler is preferably 0.001 to 0.2 μm, and more preferably 0.001 to 0.05 μm. The particle diameter of the filler is preferably as uniform (monodispersed) as possible.
The addition amount of the inorganic filler is preferably 5 to 90% by mass, more preferably 10 to 70% by mass, and particularly preferably 10 to 50% by mass based on the total weight of the low refractive index layer.
The inorganic filler is preferably used after being subjected to a surface treatment. The surface treatment method includes physical surface treatment such as plasma discharge treatment and corona discharge treatment and chemical surface treatment using a coupling agent, but the use of a coupling agent is preferred. As the coupling agent, an organoalkoxy metal compound (eg, titanium coupling agent, silane coupling agent) is preferably used. When the inorganic filler is silica, silane coupling treatment is particularly effective.
[0034]
The antiglare antireflection film of the present invention can be formed by the following method, but is not limited to this method.
First, a coating liquid containing components for forming each layer is prepared. Next, a coating solution for forming an antiglare hard coat layer is prepared by a dip coating method, an air knife coating method, a curtain coating method, a roller coating method, a wire bar coating method, a gravure coating method or an extrusion coating method (USA). (See Japanese Patent No. 2681294), coated on a transparent support, heated and dried. Thereafter, the monomer for forming the antiglare hard coat layer is polymerized and cured by light irradiation or heating. Thereby, an anti-glare hard coat layer is formed.
Here, if necessary, smooth hard coat layer application and curing may be performed by the same method before application of the antiglare hard coat layer.
Next, a coating solution for forming a low refractive index layer is applied on the antiglare hard coat layer in the same manner, and light irradiation or heating is performed to form the low refractive index layer.
Thus, the anti-glare antireflection film of the present invention is obtained.
[0035]
The antiglare antireflection film of the present invention thus formed has a haze value of 3 to 20%, preferably 4 to 15%, and an average reflectance of 450 nm to 650 nm of 1.8. % Or less, preferably 1.5% or less.
When the antiglare antireflection film of the present invention has a haze value and an average reflectance within the above range, good antiglare and antireflection properties can be obtained without causing deterioration of the transmitted image.
[0036]
The polarizing plate of this invention uses the said anti-glare antireflection film for at least one of the two protective films of the polarizing layer. By using the antiglare antireflection film of the present invention as the outermost layer, reflection of external light and the like can be prevented, and a polarizing plate having excellent scratch resistance, antifouling property and the like can be obtained. Moreover, the manufacturing cost can be reduced because the antiglare antireflection film also serves as a protective film in the polarizing plate of the present invention.
[0037]
The antiglare antireflection film of the present invention can be applied to an image display device such as a liquid crystal display device (LCD), a plasma display panel (PDP), an electroluminescence display (ELD), or a cathode ray tube display device (CRT). it can. Since the antiglare antireflection film of the present invention has a transparent support, the transparent support side is adhered to the image display surface of the image display device.
[0038]
【Example】
In order to describe the present invention in detail, examples will be described below, but the present invention is not limited thereto.
[0039]
(Preparation of coating liquid A for hard coat layer)
150 g of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.) was dissolved in 206 g of a mixed solvent of methyl ethyl ketone / cyclohexanone = 50/50%. To the obtained solution, 333 g of silica sol 30% methyl ethyl ketone dispersion (MEK-ST, manufactured by Nissan Chemical Co., Ltd., average particle size of about 15 nm), 7.5 g of photopolymerization initiator (Irgacure 907, manufactured by Ciba Geigy) and photosensitizer A solution of 5.0 g (Kayacure DETX, Nippon Kayaku Co., Ltd.) dissolved in 49 g of methyl ethyl ketone was added.
[0040]
(Preparation of coating liquid B for hard coat layer)
347 g of commercially available silica-containing UV curable hard coat liquid (Desolite Z7526, manufactured by JSR Corporation, solid content concentration 72%, silica content 38%, average particle size of about 20 nm) was mixed with 403 g of methyl ethyl ketone / cyclohexanone = 50/50% mixed solvent Diluted.
[0041]
(Preparation of coating liquid C for hard coat layer)
500 g of commercially available alumina-containing UV curable hard coat liquid (Desolite KZ7951, manufactured by JSR, solid content concentration 50%, alumina content 50%, average particle size of about 20 nm) with 250 g of mixed solvent of methyl ethyl ketone / cyclohexanone = 50/50% Diluted.
[0042]
(Preparation of coating liquid D for hard coat layer: for comparison)
250 g of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.) was dissolved in 439 g of a mixed solvent of methyl ethyl ketone / cyclohexanone = 50/50%. A solution obtained by dissolving 7.5 g of a photopolymerization initiator (Irgacure 907, manufactured by Ciba Geigy) and 5.0 g of a photosensitizer (Kayacure DETX, manufactured by Nippon Kayaku Co., Ltd.) in 49 g of methyl ethyl ketone was added to the obtained solution. added.
[0043]
(Preparation of coating solution A for antiglare hard coat layer)
A mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate in 278 g of a commercially available zirconia-containing UV curable hard coat liquid (Desolite Z7401, manufactured by JSR, solid content concentration 48%, zirconia content 71%, average particle size about 20 nm) 117 g of DPHA (manufactured by Nippon Kayaku Co., Ltd.) and 7.5 g of a photopolymerization initiator (Irgacure 907, Ciba Geigy) were diluted with 355 g of a mixed solvent of methyl ethyl ketone / cyclohexanone = 50/50%. The refractive index of the coating film obtained by applying this solution and curing with ultraviolet rays was 1.61.
Furthermore, 10 g of crosslinked polystyrene particles having an average particle diameter of 2 μm (trade name: SX-200H, manufactured by Soken Chemical Co., Ltd.) was added to this solution, and the mixture was stirred and dispersed at 5000 rpm for 1 hour with a high-speed dispaper. A coating solution for the antiglare hard coat layer was prepared by filtration through a polypropylene filter.
[0044]
(Preparation of coating solution B for antiglare hard coat layer)
Commercially available zirconia-containing UV curable hard coat solution (Desolite Z7401, manufactured by JSR, solid concentration 48%, zirconia content 71%, average particle size of about 20 nm) 521 g, photopolymerization initiator (Irgacure 907, manufactured by Ciba Geigy) 7 0.5 g was diluted with 229 g of a mixed solvent of methyl ethyl ketone / cyclohexanone = 50/50%. The refractive index of the coating film obtained by applying this solution and curing with ultraviolet rays was 1.73.
Further, 10 g of benzoguanamine-formaldehyde resin particles having an average particle diameter of 2 μm (trade name: Epester MS, manufactured by Nippon Shokubai Co., Ltd.) were added to this solution, and the mixture was stirred and dispersed at 5000 rpm for 1 hour with a high speed dispaper, and then the pore diameter was 30 μm. The coating liquid of the anti-glare hard coat layer was prepared by filtering with a polypropylene filter.
[0045]
(Preparation of coating solution C for antiglare hard coat layer)
  Mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, Nippon Kayaku Co., Ltd.) 75 g, bis (4-methacryloylthiophenyl) sulfide (MPSMA, Sumitomo Seika Co., Ltd.) 75 g, average particle 100 g of alumina particles having a diameter of 33 nm (manufactured by CI Chemical Co., Ltd.) were dissolved in 439 g of a mixed solvent of methyl ethyl ketone / cyclohexanone = 50/50%. In the obtained solution, a solution obtained by dissolving 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 Co., Ltd.) in 49 g of methyl ethyl ketone. added. The refractive index of the coating film obtained by applying this solution and curing with ultraviolet rays was 1.60. Furthermore, 10 g of crosslinked polystyrene particles having an average particle diameter of 2 μm (trade name: SX-200H, manufactured by Soken Chemical Co., Ltd.) was added to this solution, and the mixture was stirred and dispersed at 5000 rpm for 1 hour with a high-speed dispaper. Filter with a polypropylene filterAntiglareA coating solution for the hard coat layer was prepared.
[0046]
(Preparation of coating solution D for antiglare hard coat layer: for comparison)
  439 g of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, Nippon Kayaku Co., Ltd.) 125 g, bis (4-methacryloylthiophenyl) sulfide (MPSMA, Sumitomo Seika Co., Ltd.) 125 g In a mixed solvent of methyl ethyl ketone / cyclohexanone = 50/50%. In the obtained solution, a solution obtained by dissolving 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 Co., Ltd.) in 49 g of methyl ethyl ketone. added. The refractive index of the coating film obtained by applying this solution and curing with ultraviolet rays was 1.60. Furthermore, 10 g of crosslinked polystyrene particles having an average particle diameter of 2 μm (trade name: SX-200H, manufactured by Soken Chemical Co., Ltd.) was added to this solution, and the mixture was stirred and dispersed at 5000 rpm for 1 hour with a high-speed dispaper. Filter with a polypropylene filterAntiglareA coating solution for the hard coat layer was prepared.
[0047]
(Preparation of coating solution A for low refractive index layer)
Thermally crosslinkable fluorine-containing polymer having a refractive index of 1.42 (JN-7228, solid content concentration 6%, manufactured by JSR Corporation) 210 g silica sol (MEK-ST, average particle size 10-20 nm, solid content concentration 30%, (Nissan Chemical Co., Ltd.) 15.2 g and 2-butanone 174 g were added. After stirring, the mixture was filtered through a polypropylene filter having a pore size of 1 μm to prepare a coating solution for a low refractive index layer.
[0048]
(Preparation of coating solution B for low refractive index layer)
Addition of 4.6 g of magnesium fluoride particles having an average particle diameter of 30 nm and 185 g of methyl isobutyl ketone to 210 g of a heat-crosslinkable fluorine-containing polymer having a refractive index of 1.40 (JN-7223, solid concentration 6%, manufactured by JSR Corporation) After stirring, the mixture was filtered through a polypropylene filter having a pore size of 5 μm to prepare a coating solution for a low refractive index layer.
[0049]
(Preparation of coating solution C for low refractive index layer: for comparison)
120 g of 2-butanone was added to 280 g of heat-crosslinkable fluoropolymer having a refractive index of 1.42 (JN-7228, solid concentration 6%, manufactured by JSR Corporation), and after stirring, filtered through a polypropylene filter having a pore size of 1 μm. Thus, a coating solution for a low refractive index layer was prepared.
[0050]
[Example 1]
The above-mentioned anti-glare hard coat layer coating solution A was applied to an 80 μm-thick triacetyl cellulose film (TAC-TD80U, manufactured by Fuji Photo Film Co., Ltd.) using a bar coater and dried at 120 ° C. After that, using an air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) of 160 W / cm, ultraviolet rays are emitted at an illuminance of 400 mW / cm.², Irradiation amount 300mJ / cm²The coating layer was cured by irradiation with an antiglare hard coat layer having a thickness of 2.5 μm.
On top of this, the coating liquid A for the low refractive index layer was applied using a bar coater, dried at 80 ° C., and then thermally crosslinked at 120 ° C. for 10 minutes to form a low refractive index layer having a thickness of 0.096 μm. Formed.
[0051]
[Examples 2 to 4]
A sample was prepared in the same manner as in Example 1 except that the coating solution for antiglare hard coat layer and the coating solution for low refractive index layer were changed to the coating solutions shown in Table 1.
[0052]
[Comparative Examples 1 and 2]
A comparative sample was prepared in the same manner as in Example 1 except that the antiglare hard coat layer coating solution and the low refractive index layer coating solution were changed to the coating solutions shown in Table 1.
[0053]
[Example 5]
The above-mentioned coating liquid A for hard coat layer was applied to an 80 μm thick triacetylcellulose film (TAC-TD80U, manufactured by Fuji Photo Film Co., Ltd.) using a bar coater, dried at 120 ° C., and then 160 W / Using an air-cooled metal halide lamp (made by Eye Graphics Co., Ltd.)², Irradiation amount 300mJ / cm²Was applied to cure the coating layer, and a hard coat layer having a thickness of 2.5 μm was formed.
On top of that, the anti-glare hard coat layer coating solution A is applied using a bar coater, dried and UV cured under the same conditions as the hard coat layer, and an anti-glare property having a thickness of about 2.5 μm. A hard coat layer was formed.
On top of this, the coating liquid A for the low refractive index layer was applied using a bar coater, dried at 80 ° C., and then thermally crosslinked at 120 ° C. for 10 minutes to form a low refractive index layer having a thickness of 0.096 μm. Formed.
[0054]
[Examples 6 and 7]
A sample was prepared in the same manner as in Example 5 except that the hard coat layer coating solution, the antiglare hard coat layer coating solution and the low refractive index layer coating solution were changed to the coating solutions shown in Table 1.
[0055]
[Comparative Examples 3 and 4]
A comparative sample was prepared in the same manner as in Example 5 except that the hard coating layer coating solution, the antiglare hard coating layer coating solution and the low refractive index layer coating solution were changed to the coating solutions shown in Table 1.
[0056]
[Table 1]

[0057]
(Evaluation of antireflection film)
About the obtained film, the following items were evaluated.
(1) Average reflectance
Using a spectrophotometer (manufactured by JASCO Corporation), the spectral reflectance at an incident angle of 5 ° was measured in a wavelength region of 380 to 780 nm. The average reflectance of 450-650 nm was used for the result.
(2) Haze
The haze of the obtained film was measured using a haze meter MODEL 1001DP (manufactured by Nippon Denshoku Industries Co., Ltd.).
(3) Pencil hardness evaluation
The pencil hardness evaluation described in JIS K 5400 was performed as an index of scratch resistance. The antireflection film was conditioned at a temperature of 25 ° C. and a humidity of 60% RH for 2 hours, and then subjected to a load of 1 kg using a 3H test pencil specified in JIS S 6006 and evaluated as follows.
○: No scratch is observed in the evaluation of n = 5
Δ: 1 or 2 scratches in the evaluation of n = 5
X: 3 or more scratches in the evaluation of n = 5
[0058]
(4) Contact angle and fingerprint adhesion evaluation
As an index of surface contamination resistance, the optical material was conditioned for 2 hours at a temperature of 25 ° C. and a humidity of 60% RH, and then the contact angle with water was measured. Further, after the fingerprint was attached to the surface of the sample, the state when the sample was wiped with a cleaning cloth was observed, and the fingerprint adhesion was evaluated as follows.
○: Fingerprints can be wiped off completely
Δ: Some fingerprints are visible
×: Fingerprints are hardly wiped off
[0059]
(5) Dynamic friction coefficient measurement
The coefficient of dynamic friction was evaluated as an index of surface slipperiness. As the dynamic friction coefficient, a sample was conditioned at 25 ° C. and a relative humidity of 60% for 2 hours, and then a value measured with a HEIDON-14 dynamic friction measuring machine at a 5 mmφ stainless steel ball, a load of 100 g, and a speed of 60 cm / min was used.
(6) Anti-glare evaluation
Bare fluorescent light (8000 cd / m) without louver on the anti-glare film²) And the degree of blur of the reflected image was evaluated according to the following criteria.
◎: I do not know the outline of the fluorescent lamp
○: Slightly understand the outline of the fluorescent lamp
Δ: The fluorescent lamp is blurred, but the outline can be identified
×: Fluorescent lamp is hardly blurred
(7) Glitter evaluation
A fluorescent lamp diffused light with a louver was projected on the produced antiglare film, and surface glare was evaluated according to the following criteria.
○: Almost no glare
Δ: Slight glare
×: There is glare of a size that can be identified with the eyes
[0060]
Table 2 shows the results of Examples and Comparative Examples. Examples 1-7 were all excellent in antireflection performance, and all the performances required for an antiglare antireflection film such as pencil hardness, fingerprint adhesion, antiglare property, and glare were good.
In Comparative Example 1, since no inorganic filler was present in the low refractive index layer, the pencil hardness was poor and the scratch resistance was insufficient.
In Comparative Examples 2 and 3, since no inorganic filler was present in the antiglare hard coat layer, the pencil hardness was poor and the scratch resistance was insufficient.
In Comparative Example 4, since no inorganic filler was present in the hard coat layer, the pencil hardness was poor and the scratch resistance was insufficient.
[0061]
[Table 2]

[0062]
[Example 8]
Antiglare antireflection polarizing plates were prepared using the films of Examples 1 to 7. Using this polarizing plate, a liquid crystal display device in which an antireflection layer was disposed on the outermost layer was created. As a result, there was no reflection of external light, and excellent contrast was obtained. It had visibility.
[0063]
[Create transparent support]
[0064]
(1) Preparation of three-layer co-cast triacetyl cellulose film A
[0065]
(Preparation of triacetyl cellulose dope A1)
  A raw material consisting of 17.4 parts by weight of triacetyl cellulose, 2.6 parts by weight of triphenyl phosphate, 66 parts by weight of dichloromethane, 5.8 parts by weight of methanol, and 8.2 parts by weight of normal butanol was mixed and dissolved while stirring. , Triacetylcellulose dope A1Was prepared.
[0066]
(Preparation of triacetyl cellulose dope A2)
A raw material composed of 24 parts by weight of triacetyl cellulose, 4 parts by weight of triphenyl phosphate, 66 parts by weight of dichloromethane and 6 parts by weight of methanol was mixed and dissolved while stirring to prepare triacetyl cellulose dope A2.
[0067]
(Creation of three-layer co-cast triacetyl cellulose film A)
In accordance with Japanese Patent Laid-Open No. 11-254594, etc., a three-layer co-casting die is used so that the dope A1 is co-cast on both sides of the dope A2. The film was peeled off from the drum and dried to prepare a three-layer co-cast triacetyl cellulose film of 10 μm, 60 μm, and 10 μm from the drum surface side. In this film, no clear interface was formed between the respective layers.
[0068]
(2) Preparation of triacetyl cellulose film B by low-temperature dissolution method
[0069]
(Preparation of triacetylcellulose dope B)
20 parts by weight of triacetyl cellulose, 48 parts by weight of methyl acetate, 20 parts by weight of cyclohexanone, 5 parts by weight of methanol, 5 parts by weight of ethanol, 2 parts by weight of triphenyl phosphate / biphenyl diphenyl phosphate (1/2), silica (particle size 20 nm) 0.1 part by weight, 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-tert-butylanilino) -1,3,5-triazine 0.2 part by weight Was added, and the heterogeneous gel solution obtained by stirring was cooled at −70 ° C. for 6 hours, and then heated to 50 ° C. and stirred to prepare Dope B.
[0070]
(Preparation of triacetyl cellulose film B by low-temperature dissolution method)
According to Japanese Patent Laid-Open No. 7-11055, the triacetyl cellulose dope B was cast as a single layer drum to prepare a triacetyl cellulose film B having a thickness of 80 μm.
[0071]
(3) Preparation of triacetyl cellulose film C by high temperature dissolution method
[0072]
(Preparation of triacetyl cellulose dope C)
After heating the heterogeneous gel-like solution obtained in the same manner as the above triacetylcellulose dope B in a stainless steel sealed container at 1 MPa and 180 ° C. for 5 minutes, the whole container is put into a 50 ° C. water bath and cooled. A triacetyl cellulose dope C was prepared.
[0073]
(Preparation of triacetyl cellulose film C by high temperature dissolution method)
According to Japanese Patent Laid-Open No. 7-11055, the triacetylcellulose dope C was cast as a single layer drum to prepare a triacetylcellulose film C having a thickness of 80 μm.
[0074]
[Examples 9 to 17, Comparative Examples 5 to 9]
The triacetyl cellulose films having a thickness of 80 μm in Examples 1 to 7 and Comparative Examples 1 to 4 are shown in Table 3. An antiglare antireflection film was produced in the same manner except that the coating liquids A to D and the coating liquids A to C for the low refractive index layer were changed.
[0075]
[Table 3]

[0076]
Table 4 shows the results of performing the above-described evaluation in the same manner.
[0077]
[Table 4]

[0078]
All of Examples 9 to 17 were excellent in antireflection performance, and all the performances required for an antiglare antireflection film such as pencil hardness, fingerprint adhesion, antiglare property, and glare were good.
In Comparative Examples 5 and 9, since no inorganic filler was present in the low refractive index layer, the pencil hardness was poor and the scratch resistance was insufficient.
In Comparative Examples 6 and 7, since no inorganic filler was present in the antiglare hard coat layer, the pencil hardness was poor and the scratch resistance was insufficient.
In Comparative Example 8, since no inorganic filler was present in the hard coat layer, the pencil hardness was poor and the scratch resistance was insufficient.
[0079]
[Example 10]
An antiglare antireflection polarizing plate was prepared using the films of Examples 1 to 9. Using this polarizing plate, a liquid crystal display device in which an antireflection layer was disposed on the outermost layer was created. As a result, there was no reflection of external light, and excellent contrast was obtained. It had visibility.
[0080]
【The invention's effect】
The antiglare antireflection film of the present invention can be produced simply and inexpensively by simply forming an antiglare hard coat layer and a low refractive index layer on a support, and has sufficient antireflection performance and scratch resistance. Furthermore, it has antifouling properties.
An object of the present invention is to provide a polarizing plate and a liquid crystal display device using such an excellent antiglare antireflection film of the present invention.
[Brief description of the drawings]
FIG. 1 is a schematic cross-sectional view showing the layer structure of an antiglare antireflection film.
[Explanation of symbols]
1 Anti-glare anti-reflection film
2 Transparent support
3 Hard coat layer
4 Anti-glare hard coat layer
5 Low refractive index layer
6 Matt particles

Claims (13)

In the antiglare antireflection film having an antiglare hard coat layer and a low refractive index layer having a refractive index of 1.38 to 1.49 on the transparent support,
All layers contain inorganic filler ,
The particle size of the inorganic filler contained in the antiglare hard coat layer is 1 to 100 nm,
The film thickness of the antiglare hard coat layer is 1 to 10 μm,
The antiglare hard coat layer contains matte particles having an average particle diameter of 1.0 to 10.0 μm,
The inorganic filler contained in the antiglare hard coat layer is an oxide of at least one metal selected from zirconium, titanium, aluminum, indium, zinc, tin, and antimony, and the content thereof is antiglare. An antiglare antireflection film characterized by being 30 to 75% of the total mass of the hard coat layer . The antiglare antireflection film according to claim 1 , further comprising a hard coat layer containing an inorganic filler in a lower layer of the antiglare hard coat layer. The antiglare layer according to claim 1 or 2 , wherein the antiglare hard coat layer contains a binder and an inorganic filler, and the refractive index of the mixture of the binder and the inorganic filler is 1.57 to 2.00. Antireflection film. The low refractive index layer is composed of a fluorine-containing compound crosslinked with heat or ionizing radiation and an inorganic filler, has a dynamic friction coefficient of 0.03 to 0.15, and a contact angle with water of 90 to 120 °. The anti-glare antireflection film according to any one of claims 1 to 3 . Inorganic filler contained in the low refractive index layer is silica or magnesium fluoride, claim 1-4, characterized in that the content is 15 to 40% of the total mass of the low refractive index layer The antiglare antireflection film described in 1. Inorganic filler contained in the hard coat layer is silica or alumina, proof of any of claims 2-5, characterized in that the content is 30 to 70% of the total mass of the hard coat layer Dazzling antireflection film. The antiglare antireflection film according to any one of claims 1 to 6 , wherein the haze is 3.0 to 20.0%, and the average reflectance at 450 to 650 nm is 1.8% or less. The antiglare antireflection film according to any one of claims 1 to 7 , wherein a material of the transparent support is triacetylcellulose, polyethylene terephthalate, or polyethylene naphthalate. The transparent support is a triacetyl cellulose film, and the triacetyl cellulose dope prepared by dissolving triacetyl cellulose in a solvent is either a single layer casting, a multiple layer co-casting or a multiple layer sequential casting The antiglare antireflection film according to any one of claims 1 to 8 , wherein the antiglare antireflection film is produced by casting using a casting method. Claim the triacetyl cellulose dope, the triacetyl cellulose cooling dissolution method or a high temperature dissolution method, characterized in that it is a triacetyl cellulose dope prepared by dissolving in a solvent containing no dichloromethane is substantially 9 The antiglare antireflection film as described. A polarizing plate characterized by using at least one of the two protective films of a polarizing layer in a polarizing plate antiglare antireflection film according to any of claims 1-10. The liquid crystal display device characterized by using the antiglare and antireflection film as described in the outermost layer of the display in any of claims 1-10. A liquid crystal display device comprising the polarizing plate according to claim 11 so that an antiglare antireflection film as a protective layer of the polarizing plate is an outermost layer of the display.

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