JP2007188100A - Antireflection film, polarizing plate and image display device - Google Patents
Antireflection film, polarizing plate and image display device Download PDFInfo
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- JP2007188100A JP2007188100A JP2007038330A JP2007038330A JP2007188100A JP 2007188100 A JP2007188100 A JP 2007188100A JP 2007038330 A JP2007038330 A JP 2007038330A JP 2007038330 A JP2007038330 A JP 2007038330A JP 2007188100 A JP2007188100 A JP 2007188100A
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- refractive index
- antireflection film
- film
- index layer
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Images
Abstract
Description
本発明は、反射防止フィルム、それを用いた偏光板、およびそれらを用いた画像表示装置に関する。 The present invention relates to an antireflection film, a polarizing plate using the same, and an image display device using them.
反射防止フィルムは、液晶表示装置（ＬＣＤ）、プラズマディスプレイパネル（ＰＤＰ）、エレクトロルミネッセンスディスプレイ（ＥＬＤ）や陰極管表示装置（ＣＲＴ）のような様々な画像表示装置に設けられている。眼鏡やカメラのレンズにも反射防止フィルムが設けられている。
反射防止フィルムとしては、金属酸化物の透明薄膜を積層させた多層膜が従来から普通に用いられている。複数の透明薄膜を用いるのは、可視域でなるべく広い波長領域での光の反射を防止するためである。金属酸化物の透明薄膜は、化学蒸着（ＣＶＤ）法や物理蒸着（ＰＶＤ）法、特に物理蒸着法の一種である真空蒸着法やスパッタ法により形成されている。金属酸化物の透明薄膜は、反射防止フィルムとして優れた光学的性質を有しているが、蒸着法やスパッタ法による製膜方法は、生産性が低く大量生産に適していない。
The antireflection film is provided in various image display devices such as a liquid crystal display device (LCD), a plasma display panel (PDP), an electroluminescence display (ELD), and a cathode ray tube display device (CRT). Anti-reflection films are also provided on glasses and camera lenses.
As an antireflection film, a multilayer film obtained by laminating a transparent thin film of metal oxide has been conventionally used. The reason for using a plurality of transparent thin films is to prevent reflection of light in a wavelength range as wide as possible in the visible range. The transparent thin film of metal oxide is formed by a chemical vapor deposition (CVD) method or a physical vapor deposition (PVD) method, particularly a vacuum vapor deposition method or a sputtering method which is a kind of physical vapor deposition method. A transparent thin film of metal oxide has excellent optical properties as an antireflection film, but a film formation method by vapor deposition or sputtering is low in productivity and is not suitable for mass production.
蒸着法に代えて、無機微粒子の塗布により反射防止フィルムを形成する方法が提案されている。
特公昭６０−５９２５０号公報は、微細空孔と微粒子状無機物とを有する反射防止層を開示している。反射防止層は、塗布により形成される。微細空孔は、層の塗布後に活性化ガス処理を行ない、ガスが層から離脱することによって形成される。
特開昭５９−５０４０１号公報は、支持体、高屈折率層および低屈折率層の順に積層した反射防止フィルムを開示している。同公報は、支持体と高屈折率層の間に中屈折率層を設けた反射防止フィルムも開示している。低屈折率層は、ポリマーまたは無機微粒子の塗布により形成されている。
Instead of the vapor deposition method, a method of forming an antireflection film by applying inorganic fine particles has been proposed.
Japanese Patent Publication No. 60-59250 discloses an antireflection layer having fine pores and fine inorganic particles. The antireflection layer is formed by coating. The fine pores are formed by performing an activated gas treatment after the application of the layer and releasing the gas from the layer.
Japanese Patent Application Laid-Open No. 59-50401 discloses an antireflection film in which a support, a high refractive index layer and a low refractive index layer are laminated in this order. This publication also discloses an antireflection film in which an intermediate refractive index layer is provided between a support and a high refractive index layer. The low refractive index layer is formed by applying a polymer or inorganic fine particles.
特開平２−２４５７０２号公報は、二種類以上の超微粒子（例えば、ＭｇＦ2とＳｉＯ2）を混在させて、膜厚方向にその混合比を変化させた反射防止フィルムを開示している。混合比を変化させることにより屈折率を変化させ、前記特開昭５９−５０４０１号公報に記載されている高屈折率層と低屈折率層を設けた反射防止フィルムと同様の光学的性質を得ている。超微粒子は、エチルシリケートの熱分解で生じたＳｉＯ2 により接着している。エチルシリケートの熱分解では、エチル部分の燃焼によって、二酸化炭素と水蒸気も発生する。特開平２−２４５７０２号公報の第１図に示されているように、二酸化炭素と水蒸気が層から離脱することにより、超微粒子の間に間隙が生じている。
特開平５−１３０２１号公報は、前記特開平２−２４５７０２号公報記載の反射防止フィルムに存在する超微粒子間隙をバインダーで充填することを開示している。
特開平７−４８５２７号公報は、多孔質シリカよりなる無機微粉末とバインダーとを含有する反射防止フィルムを開示している。
特開平１１−６９０２号公報は、低屈折率層に無機微粒子を少なくとも２個以上積み重ねてミクロボイドを含有させた層を用いた、ウエット塗布による３層構成の反射防止膜を有するフィルムを開示している。オールウエット塗布による安価な製造コストにて、膜強度と反射率の低さを両立した反射防止フィルムを与える技術が公開されている。
JP-A-2-245702 discloses an antireflection film in which two or more kinds of ultrafine particles (for example, MgF 2 and SiO 2 ) are mixed and the mixing ratio is changed in the film thickness direction. By changing the mixing ratio, the refractive index is changed to obtain the same optical properties as the antireflection film provided with the high refractive index layer and the low refractive index layer described in JP-A-59-50401. ing. The ultrafine particles are bonded by SiO 2 generated by the thermal decomposition of ethyl silicate. In the thermal decomposition of ethyl silicate, carbon dioxide and water vapor are also generated by combustion of the ethyl portion. As shown in FIG. 1 of Japanese Patent Application Laid-Open No. 2-245702, a gap is formed between the ultrafine particles by the separation of carbon dioxide and water vapor from the layer.
Japanese Patent Laid-Open No. 5-13021 discloses that the ultrafine particle gap existing in the antireflection film described in Japanese Patent Laid-Open No. 2-245702 is filled with a binder.
Japanese Patent Application Laid-Open No. 7-48527 discloses an antireflection film containing an inorganic fine powder made of porous silica and a binder.
Japanese Patent Application Laid-Open No. 11-6902 discloses a film having an antireflection film having a three-layer structure by wet coating using a layer in which at least two inorganic fine particles are stacked in a low refractive index layer to contain microvoids. Yes. A technique for providing an antireflection film that achieves both low film strength and low reflectance at a low production cost by all wet coating has been disclosed.
上述したような塗布による反射防止フィルムに防眩性を付与する手段としては、表面凹凸を有する支持体上に反射防止層を塗布する方法や、表面凹凸を形成するためのマット粒子を反射防止層を形成する塗布液に添加する方法の他に、特開２０００−２７５４０１号公報、特開２０００−２７５４０４号公報に開示されているような、平滑な反射防止フィルムの作成後に、エンボス法等によって表面凹凸構造を形成する方法がある。 As a means for imparting antiglare properties to the antireflection film by application as described above, a method of applying an antireflection layer on a support having surface irregularities, or a mat particle for forming surface irregularities is used as an antireflection layer. In addition to the method of adding to the coating solution for forming the surface, the surface is formed by an embossing method or the like after the production of a smooth antireflection film as disclosed in JP-A-2000-275401 and JP-A-2000-275404. There is a method of forming an uneven structure.
しかしながら、前記の蒸着法やスパッタ法によって製造されている反射防止フィルムは、４５０ｎｍから６５０ｎｍまでの波長領域での平均反射率が０．４％以下のものは反射光の色味が赤紫色から青紫色に強く着色しており、反射光源が背後にある場合、表示品位を悪化させてしまう問題があった。一方、ウエット塗布によって製造されている反射防止フィルムは、反射光の色味はニュートラルに近いものの、平均反射率が１％を超えてしまい、特に外光が直接表示面に入射するような使用状況下では反射防止性能が不足していた。前記の特開平１１−６９０２号公報の実施例２４はウエット塗布で平均反射率０．３５％と記載されているが、その反射スペクトルより反射光の色味を計算すると、反射光の色味が非常に強い赤紫になることがわかり、実サンプルを作成して目視で判断しても赤紫色に強く着色しておリ、やはり表示品位を損なってしまう問題があった。また、反射光の色味が強いために、反射防止層の僅かな膜厚ムラによって色味が大きくシフトし、目視でムラとして検出されてしまう問題があった。 However, the antireflection film manufactured by the above-described vapor deposition method or sputtering method has a reflectance of 0.4% or less in the wavelength region from 450 nm to 650 nm, and the reflected light has a reddish purple to blue color. When purple is strongly colored and the reflection light source is behind, there is a problem that display quality is deteriorated. On the other hand, the antireflection film manufactured by wet coating is used in such a way that the reflected light color is close to neutral, but the average reflectivity exceeds 1%, and external light is directly incident on the display surface. Below, the antireflection performance was insufficient. In Example 24 of the above-mentioned Japanese Patent Application Laid-Open No. 11-6902, it is described that the average reflectance is 0.35% by wet coating, but when the color of the reflected light is calculated from the reflection spectrum, the color of the reflected light is It turns out that it becomes very strong reddish purple, and even if an actual sample is prepared and judged visually, it is strongly colored reddish purple, and there is still a problem that the display quality is impaired. Further, since the color of the reflected light is strong, there is a problem that the color is greatly shifted due to slight film thickness unevenness of the antireflection layer, and is detected visually as unevenness.
本発明の目的は、以下の手段によって達成された。
（１） 透明支持体上に該支持体よりも屈折率の低い低屈折率層、該低屈折率層と前記透明支持体の間に、低屈折率層側から順に該支持体よりも高い屈折率を有する高屈折率層、該支持体と高屈折率層の中間の屈折率を有する中屈折率層、の実質上３層の屈折率の異なる層を有する反射防止フィルムであって、５度入射における鏡面反射率の４５０ｎｍから６５０ｎｍまでの波長領域での平均値が０．５％以下、且つ、波長３８０ｎｍから７８０ｎｍの領域におけるＣＩＥ標準光源Ｄ６５の５度入射光に対する正反射光の色味が、ＣＩＥ１９７６Ｌ＊ａ＊ｂ＊色空間のａ＊、ｂ＊値がそれぞれ−７≦ａ＊≦７、且つ、−１０≦ｂ＊≦１０の範囲内にあることを特徴とする反射防止フィルム。
（２） 前記反射防止フィルムにおいて、ａ＊、ｂ＊値がそれぞれ０≦ａ＊≦５、且つ、−７≦ｂ＊≦０の範囲内にあることを特徴とする（１）に記載の反射防止フィルム。
（３） 前記反射防止フィルムにおいて、５度入射における鏡面反射率の４５０ｎｍから６５０ｎｍまでの波長領域での平均値が０．４％以下であることを特徴とする（１）または（２）に記載の反射防止フィルム。
（４） 前記反射防止フィルムにおいて、５度入射における鏡面反射率の４５０ｎｍから６５０ｎｍまでの波長領域での平均値が０．３％以下であることを特徴とする（１）または（２）に記載の反射防止フィルム。
（５） 前記反射防止フィルムのそれぞれの層が、膜形成性の溶質と少なくとも１種類の溶媒を含有する塗布組成物の塗布、溶媒の乾燥、熱および／または電離放射線による硬化により形成されたものであることを特徴とする（１）〜（４）いずれか１項に記載の反射防止フィルム。
（６） 前記反射防止フィルムにおいて、設計波長λ（＝５００ｎｍ）に対して中屈折率層が下式（Ｉ）を、高屈折率層が下式（ＩＩ）を、低屈折率層が下式（ＩＩＩ）をそれぞれ満足することを特徴とする（５）に記載の反射防止フィルム。
ｌλ／４×０．８０＜ｎ１ｄ１＜ｌλ／４×１．００ （Ｉ）
ｍλ／４×０．７５＜ｎ２ｄ２＜ｍλ／４×０．９５ （ＩＩ）
ｎλ／４×０．９５＜ｎ３ｄ３＜ｎλ／４×１．０５ （ＩＩＩ）（但し、式中、ｌは１であり、ｎ１は中屈折率層の屈折率であり、そして、ｄ１は中屈折率層の層厚（ｎｍ）であり、ｍは２であり、ｎ２は高屈折率層の屈折率であり、そして、ｄ２は高屈折率層の層厚（ｎｍ）であり、ｎは１であり、ｎ３は低屈折率層の屈折率であり、そして、ｄ３は低屈折率層の層厚（ｎｍ）である）
（７）屈折率が１．４５〜１．５５である透明支持体に対してｎ１が１．６０〜１．６５、ｎ２が１．８５〜１．９５、ｎ３が１．３５〜１．４５の屈折率であることを特徴とする（６）に記載の反射防止フィルム。
（８）屈折率が１．５５〜１．６５である透明支持体に対して ｎ１が１．６５〜１．７５、ｎ２が１．８５〜２．０５、ｎ３が１．３５〜１．４５の屈折率であることを特徴とする（６）に記載の反射防止フィルム。
（９） 前記反射防止フィルムの低屈折率層が、熱または電離放射線硬化性の含フッ素硬化性樹脂からなることを特徴とする（５）〜（８）いずれか１項に記載の反射防止フィルム。
（１０） 前記反射防止フィルムの高屈折率層が、 Ｔｉ、Ｚｒ、Ｉｎ、Ｚｎ、Ｓｎ、Ｓｂの酸化物から選ばれた少なくとも１種の金属酸化物を含有する超微粒子、アニオン性分散剤、３官能以上の重合性基を有する硬化性樹脂および重合開始剤を含む塗布組成物を塗布、溶媒の乾燥、熱および／または電離放射線による硬化により形成されたものであることを特徴とする（５）〜（９）いずれか１項に記載の反射防止フィルム。
（１１） 前記反射防止フィルムの低屈折率層が、動摩擦係数が０．１５以下、純水の接触角が１００度以上であることを特徴とする（９）に記載の反射防止フィルム。
（１２） 前記低屈折率層と前記透明支持体との間に少なくとも１層のハードコート層を有することを特徴とする、（１）〜（１１）いずれか１項に記載の反射防止フィルム。
（１３） 前記低屈折率層と前記透明支持体との間に少なくとも１層の前方散乱層を有することを特徴とする、（１）〜（１２）いずれか１項に記載の反射防止フィルム。
（１４） ＴＤ方向あるいはＭＤ方向に１０ｃｍ離れた任意の２つの場所における波長３８０ｎｍから７８０ｎｍの領域におけるＣＩＥ標準光源Ｄ６５の５度入射光に対する正反射光の色味ムラが、ＣＩＥ１９７６Ｌ＊ａ＊ｂ＊色空間のΔＥａｂ＊値で２未満であることを特徴とするであることを特徴とする（１）〜（１３）いずれか１項に記載の反射防止フィルム。
（１５） トリアセチルセルロースあるいはポリエチレンテレフタレートのいずれかに対して常温常湿で測定した垂直剥離帯電量が−２００ｐｃ（ピコクーロン）／ｃｍ2〜＋２００ｐｃ（ピコクーロン）／ｃｍ2であり、かつ表面抵抗値が１×１０11Ω／□以上であることを特徴とするであることを特徴とする（１）〜（１４）いずれか１項に記載の反射防止フィルム。
（１６） ２枚の表面保護フィルムを偏光子の表面と裏面に貼り合わせた偏光板であり、（１）〜（１５）いずれか１項に記載の反射防止フィルムの低屈折率層を形成後に、アルカリ液中に少なくとも１回浸漬することで、該フィルムの裏面を鹸化処理した反射防止フィルムを少なくとも片面の表面保護フィルムに用いたことを特徴とする偏光板。
（１７） ２枚の表面保護フィルムを偏光子の表面と裏面に貼り合わせた偏光板であり、（１）〜（１５）いずれか１項に記載の反射防止フィルムの低屈折率層を形成する面の形成前または後に、アルカリ液を該反射防止フィルムの低屈折率層を形成する面の反対側の面に塗布し、加熱、水洗および／または中和することで、該フィルムの裏面だけを鹸化処理した反射防止フィルムを少なくとも片面の表面保護フィルムに用いたことを特徴とする偏光板。
（１８） 前記表面保護フィルムのうちの反射防止フィルム以外のフィルムが、該表面保護フィルムの偏光子と反対側の面に光学異方層を含んでなる光学補償層を有する光学補償フィルムであり、該光学異方性層がディスコティック構造単位を有する化合物からなる負の複屈折を有する層であり、該ディスコティック構造単位の円盤面が該表面保護フィルム面に対して傾いており、且つ該ディスコティック構造単位の円盤面と該表面保護フィルム面とのなす角度が、光学異方層の深さ方向において変化していることを特徴とする（１６）または（１７）に記載の偏光板。
（１９） （１６）〜（１８）いずれか１項に記載の偏光板を少なくとも１枚有するＴＮ、ＳＴＮ、ＶＡ、ＩＰＳ、ＯＣＢのモードの透過型、反射型、または半透過型の液晶表示装置。
（２０） （１６）〜（１８）いずれか１項に記載の偏光板を少なくとも１枚有する透過型または半透過型の液晶表示装置であり、視認側とは反対側の偏光板とバックライトとの間に、偏光選択層を有する偏光分離フィルムを配置することを特徴とする液晶表示装置。
（２１）前記透明支持体がポリエチレンテレフタレートフィルム、またはポリエチレンナフタレートフィルムであることを特徴とする（１）〜（１５）いずれか１項に記載の反射防止フィルム。
（２２） （１６）または（１７）に記載の偏光板の反射防止フィルムとは反対側の透明保護フィルムに、λ／４板を配置したことを特徴とする透過または半透過型液晶装置。
（２３） （１６）または（１７）に記載の偏光板の反射防止フィルムとは反対側の透明保護フィルムに、λ／４板を配置したことを特徴とする、有機ＥＬディスプレイ装置。
The object of the present invention has been achieved by the following means.
(1) A low refractive index layer having a refractive index lower than that of the support on the transparent support, and a refractive index higher than that of the support in order from the low refractive index layer side between the low refractive index layer and the transparent support. An antireflective film comprising substantially three layers having different refractive indexes, a high refractive index layer having a refractive index, and a medium refractive index layer having a refractive index intermediate between the support and the high refractive index layer, The average value of the specular reflectance at incidence in the wavelength region from 450 nm to 650 nm is 0.5% or less, and the color of the regular reflection light with respect to the 5 degree incident light of the CIE standard light source D65 in the wavelength range from 380 nm to 780 nm is An antireflection film, wherein the a * and b * values of the CIE 1976 L * a * b * color space are in the range of −7 ≦ a * ≦ 7 and −10 ≦ b * ≦ 10, respectively.
(2) The reflection according to (1), wherein the antireflection film has a * and b * values in a range of 0 ≦ a * ≦ 5 and −7 ≦ b * ≦ 0, respectively. Prevention film.
(3) In the antireflection film, the average value in the wavelength region from 450 nm to 650 nm of the specular reflectance at 5 degrees incidence is 0.4% or less. (1) or (2) Antireflection film.
(4) In the antireflection film, an average value in a wavelength region from 450 nm to 650 nm of a specular reflectance at 5 degrees incidence is 0.3% or less, and (1) or (2) Antireflection film.
(5) Each layer of the antireflection film is formed by coating a coating composition containing a film-forming solute and at least one solvent, drying the solvent, curing by heat and / or ionizing radiation The antireflection film as described in any one of (1) to (4), wherein
(6) In the antireflection film, the medium refractive index layer is represented by the following formula (I), the high refractive index layer is represented by the following formula (II), and the low refractive index layer is represented by the following formula with respect to the design wavelength λ (= 500 nm). Each of (III) is satisfied, The antireflection film as described in (5) characterized by the above-mentioned.
lλ / 4 × 0.80 <n1d1 <lλ / 4 × 1.00 (I)
mλ / 4 × 0.75 <n2d2 <mλ / 4 × 0.95 (II)
nλ / 4 × 0.95 <n3d3 <nλ / 4 × 1.05 (III) (where, l is 1, n1 is the refractive index of the medium refractive index layer, and d1 is medium refractive) The layer thickness (nm) of the refractive index layer, m is 2, n2 is the refractive index of the high refractive index layer, and d2 is the layer thickness (nm) of the high refractive index layer, and n is 1. N3 is the refractive index of the low refractive index layer, and d3 is the layer thickness (nm) of the low refractive index layer)
(7) n1 is 1.60 to 1.65, n2 is 1.85 to 1.95, and n3 is 1.35 to 1.45 with respect to the transparent support having a refractive index of 1.45 to 1.55. The antireflective film according to (6), which has a refractive index of
(8) For a transparent support having a refractive index of 1.55 to 1.65, n1 is 1.65 to 1.75, n2 is 1.85 to 2.05, and n3 is 1.35 to 1.45. The antireflective film according to (6), which has a refractive index of
(9) The antireflective film according to any one of (5) to (8), wherein the low refractive index layer of the antireflective film is made of a heat- or ionizing radiation-curable fluorine-containing curable resin. .
(10) The antireflective film has a high refractive index layer, ultrafine particles containing at least one metal oxide selected from oxides of Ti, Zr, In, Zn, Sn, and Sb, an anionic dispersant, It is formed by applying a coating composition containing a curable resin having a tri- or higher functional polymerizable group and a polymerization initiator, drying the solvent, curing by heat and / or ionizing radiation (5 ) To (9) The antireflection film as described in any one of the above.
(11) The antireflective film according to (9), wherein the low refractive index layer of the antireflective film has a dynamic friction coefficient of 0.15 or less and a pure water contact angle of 100 degrees or more.
(12) The antireflection film as described in any one of (1) to (11), wherein at least one hard coat layer is provided between the low refractive index layer and the transparent support.
(13) The antireflection film as described in any one of (1) to (12), wherein the antireflection film has at least one forward scattering layer between the low refractive index layer and the transparent support.
(14) CIE 1976 L * a * b * CIE 1976 L * a * b * is the irregular color tone of specularly reflected light with respect to 5 degree incident light of the CIE standard light source D65 in the wavelength range of 380 nm to 780 nm in any two
(15) The vertical peel charge amount measured at normal temperature and humidity with respect to either triacetyl cellulose or polyethylene terephthalate is −200 pc (picocoulomb) / cm 2 to +200 pc (picocoulomb) / cm 2 , and the surface resistance value is The antireflection film as described in any one of (1) to (14), which is characterized by being 1 × 10 11 Ω / □ or more.
(16) A polarizing plate in which two surface protective films are bonded to the front and back surfaces of a polarizer, and after the formation of the low refractive index layer of the antireflection film according to any one of (1) to (15) A polarizing plate characterized in that an antireflection film obtained by saponifying the back surface of the film by dipping at least once in an alkaline solution is used as a surface protective film on at least one side.
(17) A polarizing plate in which two surface protective films are bonded to the front and back surfaces of a polarizer, and the low refractive index layer of the antireflection film according to any one of (1) to (15) is formed. Before or after the formation of the surface, an alkali solution is applied to the surface opposite to the surface on which the low refractive index layer of the antireflective film is formed, heated, washed with water and / or neutralized, so that only the back surface of the film is coated. A polarizing plate comprising a saponified antireflection film as a surface protective film on at least one side.
(18) Of the surface protective film, a film other than the antireflection film is an optical compensation film having an optical compensation layer comprising an optical anisotropic layer on a surface opposite to the polarizer of the surface protective film, The optically anisotropic layer is a layer having negative birefringence made of a compound having a discotic structural unit, the disc surface of the discotic structural unit is inclined with respect to the surface protective film surface, and the disco The polarizing plate according to (16) or (17), wherein an angle formed by the disk surface of the tick structural unit and the surface protective film surface changes in the depth direction of the optically anisotropic layer.
(19) A TN, STN, VA, IPS, OCB mode transmissive, reflective, or transflective liquid crystal display device comprising at least one polarizing plate according to any one of (16) to (18). .
(20) A transmissive or semi-transmissive liquid crystal display device having at least one polarizing plate according to any one of (16) to (18), a polarizing plate and a backlight on the opposite side to the viewing side A liquid crystal display device comprising a polarization separation film having a polarization selection layer disposed between the two.
(21) The antireflection film as described in any one of (1) to (15), wherein the transparent support is a polyethylene terephthalate film or a polyethylene naphthalate film.
(22) A transmissive or transflective liquid crystal device, wherein a λ / 4 plate is disposed on a transparent protective film opposite to the antireflection film of the polarizing plate according to (16) or (17).
(23) An organic EL display device, wherein a λ / 4 plate is disposed on a transparent protective film opposite to the antireflection film of the polarizing plate according to (16) or (17).
本発明の反射防止フィルムは、４５０ｎｍから６５０ｎｍまでの平均反射率が０．５％以下であるため、液晶ディスプレイに適用したとき、反射光の映り込みによる視認性の悪化が高いレベルで防止される。さらに、波長３８０ｎｍから７８０ｎｍの領域におけるＣＩＥ標準光源Ｄ６５の５度入射光に対する正反射光の色味で評価した時に、 ＣＩＥ１９７６Ｌ＊ａ＊ｂ＊色空間のａ＊、ｂ＊値がそれぞれ−７≦ａ＊≦７、−１０≦ｂ＊≦１０の範囲内にあるため、ディスプレイに向かう使用者の背面の蛍光灯等、輝度の高い光源がディスプレイ表面に映りこんだときにも赤紫色や青紫色に着色することがなく、表示品位の低下が少ないと同時に膜厚ムラに対する色味ムラが小さく製造得率が高い。また、垂直剥離帯電量が小さいため、表面抵抗値が高くても防塵性に優れる。また、種々のモードの液晶表示装置に用いる偏光板、有機ＥＬに用いる偏光板とλ／４板を組み合わせた表面保護板、ＰＥＴフィルムに適用した平面ＣＲＴあるいはＰＤＰ用表面保護板等、様々なディスプレイに用いることができる。 Since the antireflection film of the present invention has an average reflectance from 450 nm to 650 nm of 0.5% or less, when applied to a liquid crystal display, deterioration of visibility due to reflection of reflected light is prevented at a high level. . Furthermore, when evaluated with the color of specularly reflected light with respect to 5 ° incident light of the CIE standard light source D65 in the wavelength range of 380 nm to 780 nm, the a * and b * values of the CIE 1976 L * a * b * color space are −7 ≦ Since it is in the range of a * ≦ 7 and −10 ≦ b * ≦ 10, even when a bright light source such as a fluorescent lamp on the back of the user heading to the display is reflected on the display surface, red purple or blue purple In addition, there is little deterioration in display quality, and at the same time, the color unevenness with respect to the film thickness unevenness is small and the production yield is high. Further, since the vertical peeling charge amount is small, the dust resistance is excellent even if the surface resistance value is high. Various displays such as polarizing plates used in liquid crystal display devices of various modes, surface protective plates combining polarizing plates used in organic EL and λ / 4 plates, and flat CRT or PDP surface protective plates applied to PET films. Can be used.
本発明の反射防止フィルムの基本的な構成を図面を引用しながら説明する。 The basic structure of the antireflection film of the present invention will be described with reference to the drawings.
［反射防止フィルムの形成］
図１は、本発明に用いられる反射防止フィルムの基本的な層構成を示す断面模式図である。透明支持体（１）、ハードコート層（２）、中屈折率層（３）、高屈折率層（４）、そして低屈折率層（５）の順序の層構成を有する。このような３層構成の反射防止フィルムは、中屈折率層、高屈折率層、低屈折率層のそれぞれの層の光学膜厚、すなわち屈折率と膜厚の積が設計波長λに対してｎλ／４前後、またはその倍数であることが好ましいことが特開昭５９−５０４０１号公報に記載されている。
しかしながら、本発明の低反射率且つ反射光の色味が低減された反射率特性を実現するためには、特に設計波長λ（＝５００ｎｍ）に対して中屈折率層が下式（Ｉ）を、高屈折率層が下式（ＩＩ）を、低屈折率層が下式（ＩＩＩ）をそれぞれ満足する必要がある。
[Formation of antireflection film]
FIG. 1 is a schematic cross-sectional view showing a basic layer structure of an antireflection film used in the present invention. It has a layer structure in the order of a transparent support (1), a hard coat layer (2), a medium refractive index layer (3), a high refractive index layer (4), and a low refractive index layer (5). Such an antireflection film having a three-layer structure has an optical film thickness of each of a medium refractive index layer, a high refractive index layer and a low refractive index layer, that is, the product of the refractive index and the film thickness with respect to the design wavelength λ. JP-A-59-50401 describes that nλ / 4 is preferably around or a multiple thereof.
However, in order to realize the low reflectance and the reflectance characteristics of the reflected light of the present invention, the middle refractive index layer has the following formula (I) particularly for the design wavelength λ (= 500 nm). The high refractive index layer must satisfy the following formula (II), and the low refractive index layer must satisfy the following formula (III).
ｌλ／４×０．８０＜ｎ１ｄ１＜ｌλ／４×１．００ （Ｉ） lλ / 4 × 0.80 <n1d1 <lλ / 4 × 1.00 (I)
ｍλ／４×０．７５＜ｎ２ｄ２＜ｍλ／４×０．９５ （ＩＩ） mλ / 4 × 0.75 <n2d2 <mλ / 4 × 0.95 (II)
ｎλ／４×０．９５＜ｎ３ｄ３＜ｎλ／４×１．０５ （ＩＩＩ） nλ / 4 × 0.95 <n3d3 <nλ / 4 × 1.05 (III)
式中、ｌは１であり、ｎ１は中屈折率層の屈折率であり、そして、ｄ１は中屈折率層の層厚（ｎｍ）であり、ｍは２であり、ｎ２は高屈折率層の屈折率であり、そして、ｄ２は高屈折率層の層厚（ｎｍ）であり、ｎは１であり、ｎ３は低屈折率層の屈折率であり、そして、ｄ３は低屈折率層の層厚（ｎｍ）である。さらに、例えばトリアセチルセルロース（屈折率：１．４９）からなるような屈折率が１．４５〜１．５５の透明支持体に対しては、ｎ１は１．６０〜１．６５、ｎ２は１．８５〜１．９５、ｎ３は１．３５〜１．４５の屈折率である必要があり、例えばポリエチレンテレフタレート（屈折率：１．６６）からなるような屈折率が１．５５〜１．６５の透明支持体に対しては、 ｎ１は１．６５〜１．７５、ｎ２は１．８５〜２．０５、ｎ３は１．３５〜１．４５の屈折率である必要がある。上記のような屈折率を有する中屈折率層や高屈折率層の素材が選択できない場合には、設定屈折率よりも高い屈折率を有する層と低い屈折率を有する層を複数層組み合わせた等価膜の原理を用いて、実質的に設定屈折率の中屈折率層あるいは高屈折率層と光学的に等価な層を形成できることは公知であり、本発明の反射率特性を実現するためにも用いることができる。本発明の「実質的に３層」とは、このような等価膜を用いた４層、５層の屈折率の異なる項からなる反射防止層も含むものである。 In the formula, l is 1, n1 is the refractive index of the medium refractive index layer, d1 is the layer thickness (nm) of the medium refractive index layer, m is 2, and n2 is the high refractive index layer. And d2 is the thickness (nm) of the high refractive index layer, n is 1, n3 is the refractive index of the low refractive index layer, and d3 is the low refractive index layer. Layer thickness (nm). Furthermore, for example, n1 is 1.60 to 1.65 and n2 is 1 for a transparent support having a refractive index of 1.45 to 1.55 made of triacetylcellulose (refractive index: 1.49). .85 to 1.95, n3 must have a refractive index of 1.35 to 1.45, for example, a refractive index of 1.55 to 1.65 made of polyethylene terephthalate (refractive index: 1.66). N1 must have a refractive index of 1.65 to 1.75, n2 must have a refractive index of 1.85 to 2.05, and n3 must have a refractive index of 1.35 to 1.45. When materials of medium refractive index layer and high refractive index layer having the above refractive index cannot be selected, an equivalent combination of a layer having a refractive index higher than the set refractive index and a layer having a low refractive index is combined. It is known that a film layer can be used to form a layer that is optically equivalent to a medium refractive index layer or a high refractive index layer having a set refractive index, and also to realize the reflectance characteristics of the present invention. Can be used. The “substantially three layers” of the present invention includes an antireflection layer composed of terms having different refractive indexes of four layers and five layers using such an equivalent film.
上記のような層構成とすることで達成される本特許の反射率特性は、低反射と反射光の色味の低減を両立することができるため、例えば液晶表示装置の最表面に適用した場合、これまでにない視認性の高さを有する表示装置が得られる。５度入射における鏡面反射率の４５０ｎｍから６５０ｎｍまでの波長領域での平均値が０．５％以下であることによって、表示装置表面での外光の反射による視認性の低下が充分なレベルまで防止できる。平均値は好ましくは０．４％以下であり、より好ましくは０．３％以下である。また、波長３８０ｎｍから７８０ｎｍの領域におけるＣＩＥ標準光源Ｄ６５の５度入射光に対する正反射光の色味が、ＣＩＥ１９７６Ｌ＊ａ＊ｂ＊色空間のａ＊、ｂ＊値がそれぞれ−７≦ａ＊≦７、且つ、−１０≦ｂ＊≦１０の範囲内とすることで、従来の多層反射防止フィルムで問題となっていた赤紫色から青紫色の反射光の色味が低減され、さらに０≦ａ＊≦５、且つ、−７≦ｂ＊≦０の範囲内とすることで大幅に低減され、液晶表示装置に適用した場合、室内の蛍光灯のような、輝度の高い外光が僅かに映り込んだ場合の色味がニュートラルで、気にならない。詳しくはａ＊＞７では赤味が強く、ａ＊＜−７ではシアン味が強くなり、好ましくない。またｂ＊＜−７では青味が強く、ｂ＊＞０では黄味が強くなり好ましくない。鏡面反射率及び色味の測定は、分光光度計Ｖ−５５０（日本分光（株）製）にアダプターＡＲＶ−４７４を装着して、３８０〜７８０ｎｍの波長領域において、入射角５°における出射角−５度の鏡面反射率を測定し、４５０〜６５０ｎｍの平均反射率を算出し、反射防止性を評価することができる。さらに、測定された反射スペクトルから、ＣＩＥ標準光源Ｄ６５の５度入射光に対する正反射光の色味を表わすＣＩＥ１９７６Ｌ＊ａ＊ｂ＊色空間のＬ＊値、ａ＊値、ｂ＊値を算出し、反射光の色味を評価することができる。 The reflectance characteristics of this patent achieved by using the layer configuration as described above can achieve both low reflection and a reduction in the color of reflected light. For example, when applied to the outermost surface of a liquid crystal display device A display device having unprecedented visibility can be obtained. The average value of the specular reflectivity at 5 degrees incidence in the wavelength region from 450 nm to 650 nm is 0.5% or less, thereby preventing a reduction in visibility due to reflection of external light on the display device surface to a sufficient level. it can. The average value is preferably 0.4% or less, more preferably 0.3% or less. In addition, the color of the specularly reflected light with respect to the incident light of 5 degrees of the CIE standard light source D65 in the wavelength range of 380 nm to 780 nm indicates that the a * and b * values of the CIE1976L * a * b * color space are −7 ≦ a * ≦ 7 and by making it within the range of −10 ≦ b * ≦ 10, the tint of reflected light from red purple to blue purple, which has been a problem in the conventional multilayer antireflection film, is reduced, and further 0 ≦ a * ≤ 5 and -7 ≤ b * ≤ 0, greatly reduced. When applied to a liquid crystal display device, high brightness external light such as indoor fluorescent lamps is slightly reflected. The color is neutral and I don't mind. Specifically, when a *> 7, redness is strong, and when a * <− 7, cyan is strong, which is not preferable. Further, b * <− 7 is not preferable because bluish color is strong, and b *> 0 is not preferable because yellow color becomes strong. The specular reflectance and color are measured by attaching an adapter ARV-474 to a spectrophotometer V-550 (manufactured by JASCO Corporation), and in the wavelength region of 380 to 780 nm, the output angle at an incident angle of 5 °. The antireflection property can be evaluated by measuring the specular reflectance of 5 degrees, calculating the average reflectance of 450 to 650 nm. Further, CIE 1976 L * a * b * color space L * value, a * value, and b * value representing the color of the specularly reflected light with respect to the 5 degree incident light of the CIE standard light source D65 are calculated from the measured reflection spectrum. The color of reflected light can be evaluated.
さらに、上記のように反射光の色味が大幅に低減されたことで、反射防止層の膜厚ムラに起因する反射光の色味ムラも大幅に低減される。すなわち、膜厚ムラの許容範囲が広がることになり、製造得率が上がり、コストの更なる低減が可能となる。定量的には、ＴＤ方向（支持体長手方向と直交する方向）あるいはＭＤ方向（支持体長手方向）に１０ｃｍ離れた任意の２つの場所における波長３８０ｎｍから７８０ｎｍの領域におけるＣＩＥ標準光源Ｄ６５の５度入射光に対する正反射光の色味ムラで表すことができ、ＣＩＥ１９７６Ｌ＊ａ＊ｂ＊色空間のΔＥａｂ＊値で２未満であることが好ましく、１．５未満であると完全に人間の目でムラを検出できなくなり、より好ましい。
Furthermore, since the color of the reflected light is greatly reduced as described above, the color unevenness of the reflected light due to the film thickness unevenness of the antireflection layer is also greatly reduced. That is, the allowable range of film thickness unevenness is widened, the manufacturing yield is increased, and the cost can be further reduced. Quantitatively, 5 degrees of the CIE standard light source D65 in the wavelength range of 380 nm to 780 nm in any two
本発明の反射防止フィルムは、トリアセチルセルロース（ＴＡＣ）あるいはポリエチレンテレフタレート（ＰＥＴ）のいずれかに対して常温常湿で測定した垂直剥離帯電が−２００ｐｃ（ピコクーロン）／ｃｍ2〜＋２００ｐｃ（ピコクーロン）／ｃｍ2であることが、防塵性の観点から好ましい。より好ましくは−１００ｐｃ／ｃｍ〜＋１００ｐｃ／ｃｍ2であり、さらに好ましくは−５０ｐｃ／ｃｍ2〜＋５０ｐｃ／ｃｍ2であり、最も好ましくは０ｐｃ／ｃｍ2である。ここで、単位のｐｃ（ピコクーロン）は、１０-12クーロンである。
さらに好ましくは、常温１０％ＲＨで測定した垂直剥離帯電が−１００ｐｃ／ｃｍ2〜＋１００ｐｃ／ｃｍ2であり、さらに好ましくは−５０ｐｃ／ｃｍ2〜＋５０ｐｃ／ｃｍ2であり、最も好ましくは０ｐｃ／ｃｍ2である。
The antireflection film of the present invention has a vertical peeling charge of −200 pc (picocoulomb) / cm 2 to +200 pc (picocoulomb) / measured at normal temperature and humidity with respect to either triacetylcellulose (TAC) or polyethylene terephthalate (PET). It is preferable that it is cm < 2 > from a dust-proof viewpoint. More preferably, it is −100 pc / cm to +100 pc / cm 2 , further preferably −50 pc / cm 2 to +50 pc / cm 2 , and most preferably 0 pc / cm 2 . Here, the unit pc (picocoulomb) is 10 −12 coulomb.
More preferably, the vertical peel charge measured at room temperature of 10% RH is −100 pc / cm 2 to +100 pc / cm 2 , more preferably −50 pc / cm 2 to +50 pc / cm 2 , most preferably 0 pc / cm 2. 2 .
垂直剥離帯電の測定方法は以下の通りである。
測定サンプルはあらかじめ測定温度湿度の環境下で２時間以上放置しておく。測定装置は測定サンプルを置く台と相手のフィルムを保持して測定サンプルに上から圧着と剥離を繰り返せるヘッドからなり、このヘッドに帯電量を測定するエレクトロメーターがつながっている。測定する反射防止フィルムを台に乗せ、ヘッドにＴＡＣあるいはＰＥＴを装着する。測定部分を除電したのち、ヘッドを測定サンプルに圧着させ剥離させることを繰り返し、１回目の剥離時と５回目の剥離時の帯電の値を読み、これを平均する。サンプルを変えて３サンプルでこれを繰り返し、全てを平均したものを垂直剥離帯電とする。
The measurement method of the vertical peeling charge is as follows.
The measurement sample is left in advance for 2 hours or more in an environment of measurement temperature and humidity. The measuring device is composed of a table on which a measurement sample is placed and a head that can hold a partner film and repeatedly press and peel the measurement sample from above, and an electrometer for measuring the charge amount is connected to the head. Place the antireflection film to be measured on the table and attach TAC or PET to the head. After neutralizing the measurement portion, the head is pressure-bonded to the measurement sample and peeled off repeatedly, and the charge values at the first peeling and the fifth peeling are read and averaged. This is repeated for three samples by changing the sample, and the average of all the samples is defined as vertical peeling charge.
相手フィルムや測定サンプルの種類によってプラスに帯電する場合とマイナスに帯電する場合があるが、問題となるのは絶対値の大きさである。
また、一般的に低湿度の環境下の方が帯電の絶対値は大きくなる。本発明の反射防止フィルムはこの絶対値も小さい。
Depending on the type of the counterpart film or measurement sample, there are cases where it is positively charged and negatively charged, but the problem is the magnitude of the absolute value.
In general, the absolute value of charging is larger in a low humidity environment. The antireflection film of the present invention has a small absolute value.
本発明の反射防止フィルムは、常温常湿及び常温１０％ＲＨでの垂直剥離帯電の絶対値が小さいので防塵性に優れる。
垂直剥離帯電の値を上記の範囲とするには、反射防止フィルム表面の各種元素の割合を調節することによって行われる。
The antireflection film of the present invention is excellent in dust resistance since the absolute value of the vertical peeling charge at normal temperature and normal humidity and normal temperature of 10% RH is small.
In order to set the value of the vertical peeling charge within the above range, the ratio of various elements on the surface of the antireflection film is adjusted.
本発明の反射防止フィルムの表面抵抗値は、１×１０11Ω／□以上、好ましくは１×１０12Ω／□以上である。表面抵抗値の測定方法はＪＩＳに記載されている円電極法である。即ち、電圧印加後、１分後の電流値を読み、表面抵抗値（ＳＲ）を求める。
本発明では、表面抵抗値を小さくすること、例えば１×１０10Ω／□以下にすることで防塵性（ゴミ付着防止性）を良くする方法とは考え方が根本的に異なる。この方法は画像表示品位が落ちるため採用せず、本発明では上記した方法で垂直剥離帯電の絶対値を小さくしているので、表面抵抗値を小さくする必要がなく、表面抵抗値を１×１０11Ω／□以上とすることができ画像表示品位が落ちない。
The surface resistance value of the antireflection film of the present invention is 1 × 10 11 Ω / □ or more, preferably 1 × 10 12 Ω / □ or more. The measuring method of the surface resistance value is a circular electrode method described in JIS. That is, the current value one minute after voltage application is read to determine the surface resistance value (SR).
In the present invention, the idea is fundamentally different from the method of improving the dust resistance (dust adhesion preventing property) by reducing the surface resistance value, for example, 1 × 10 10 Ω / □ or less. This method is not adopted because the image display quality is deteriorated. In the present invention, the absolute value of the vertical peeling charge is reduced by the above-described method. Therefore, it is not necessary to reduce the surface resistance value, and the surface resistance value is 1 × 10. 11 Ω / □ or higher, and image display quality does not deteriorate.
本発明の反射防止フィルムに用いる透明支持体としては、プラスチックフィルムを用いることが好ましい。プラスチックフィルムの材料の例には、セルロースエステル（例、トリアセチルセルロース、ジアセチルセルロース、プロピオニルセルロース、ブチリルセルロース、アセチルプロピオニルセルロース、ニトロセルロース）、ポリアミド、ポリカーボネート、ポリエステル（例、ポリエチレンテレフタレート、ポリエチレンナフタレート、ポリ−１，４−シクロヘキサンジメチレンテレフタレート、ポリエチレン−１，２−ジフェノキシエタン−４，４'−ジカルボキシレート、ポリブチレンテレフタレート）、ポリスチレン（例、シンジオタクチックポリスチレン）、ポリオレフィン（例、ポリプロピレン、ポリエチレン、ポリメチルペンテン）、ポリスルホン、ポリエーテルスルホン、ポリアリレート、ポリエーテルイミド、ポリメチルメタクリレートおよびポリエーテルケトンが含まれる。
特に液晶表示装置や有機ＥＬ表示装置等に用いるために本発明の反射防止フィルムを偏光板の表面保護フィルムの片側として用いる場合にはトリアセチルセルロースが好ましく用いられる。トリアセチルセルロースフィルムとしては、ＴＡＣ−ＴＤ８０Ｕ（富士写真フィルム（株）製）等の公知のもの、公開技報番号２００１−１７４５にて公開されたものが好ましく用いられる。また、平面ＣＲＴやＰＤＰ等に用いるためにガラス基板等に張り合わせて用いる場合にはポリエチレンテレフタレート、あるいははポリエチレンナフタレートが好ましい。
透明支持体の光透過率は、８０％以上であることが好ましく、８６％以上であることがさらに好ましい。透明支持体のヘイズは、２．０％以下であることが好ましく、１．０％以下であることがさらに好ましい。透明支持体の屈折率は、１．４乃至１．７であることが好ましい。本発明の透明支持体の厚みは特に限定されないが、３０〜１５０μｍが好ましく、４０〜１３０μｍがより好ましく、７０〜１２０μｍが更に好ましい。
As the transparent support used in the antireflection film of the present invention, it is preferable to use a plastic film. Examples of plastic film materials include cellulose esters (eg, triacetyl cellulose, diacetyl cellulose, propionyl cellulose, butyryl cellulose, acetyl propionyl cellulose, nitrocellulose), polyamides, polycarbonates, polyesters (eg, polyethylene terephthalate, polyethylene naphthalate). , Poly-1,4-cyclohexanedimethylene terephthalate, polyethylene-1,2-diphenoxyethane-4,4′-dicarboxylate, polybutylene terephthalate), polystyrene (eg, syndiotactic polystyrene), polyolefin (eg, Polypropylene, polyethylene, polymethylpentene), polysulfone, polyethersulfone, polyarylate, polyetherimide, polymethylmethene Tacrylate and polyether ketone are included.
In particular, when the antireflection film of the present invention is used as one side of a surface protective film of a polarizing plate for use in a liquid crystal display device, an organic EL display device or the like, triacetyl cellulose is preferably used. As the triacetyl cellulose film, a known film such as TAC-TD80U (manufactured by Fuji Photo Film Co., Ltd.) or a film disclosed in the public technical report number 2001-1745 is preferably used. In addition, polyethylene terephthalate or polyethylene naphthalate is preferable when it is used by being bonded to a glass substrate or the like for use in a flat CRT or PDP.
The light transmittance of the transparent support is preferably 80% or more, and more preferably 86% or more. The haze of the transparent support is preferably 2.0% or less, and more preferably 1.0% or less. The refractive index of the transparent support is preferably 1.4 to 1.7. The thickness of the transparent support of the present invention is not particularly limited, but is preferably 30 to 150 μm, more preferably 40 to 130 μm, and still more preferably 70 to 120 μm.
中屈折率層および高屈折率層は、屈折率の高い無機微粒子、熱または電離放射線硬化性のモノマー、開始剤および溶媒を含有する塗布組成物の塗布、溶媒の乾燥、熱および／または電離放射線による硬化によって形成される。無機微粒子としては、 Ｔｉ、Ｚｒ、Ｉｎ、Ｚｎ、Ｓｎ、Ｓｂの酸化物から選ばれた少なくとも１種の金属酸化物からなるものが好ましい。このようにして形成された中屈折率層および高屈折率層は、高屈折率を有するポリマー溶液を塗布、乾燥したものと比較して、耐傷性や密着性に優れる。分散液安定性や、硬化後の膜強度等を確保するために、特開平１１−１５３７０３号公報や特許番号ＵＳ６２１０８５８Ｂ１等に記載されているような、多官能（メタ）アクリレートモノマーとアニオン性基含有（メタ）アクリレート分散剤とが塗布組成物中に含まれることが好ましい。 The medium refractive index layer and the high refractive index layer are coated with a coating composition containing inorganic fine particles with a high refractive index, thermal or ionizing radiation-curable monomer, initiator and solvent, drying of the solvent, heat and / or ionizing radiation. It is formed by curing. As the inorganic fine particles, those composed of at least one metal oxide selected from Ti, Zr, In, Zn, Sn, and Sb oxides are preferable. The medium refractive index layer and the high refractive index layer thus formed are excellent in scratch resistance and adhesion as compared with those obtained by applying and drying a polymer solution having a high refractive index. In order to ensure dispersion stability, film strength after curing, etc., it contains a polyfunctional (meth) acrylate monomer and an anionic group as described in JP-A-11-153703, Patent No. US6210858B1, etc. It is preferable that a (meth) acrylate dispersant is contained in the coating composition.
無機微粒子の平均粒径は、コールターカウンター法で測定したときの平均粒径で１から１００ｎｍであることが好ましい。１ｎｍ以下では、比表面積が大きすぎるために、分散液中での安定性に乏しく、好ましくない。１００ｎｍ以上では、バインダとの屈折率差に起因する可視光の散乱が発生し、好ましくない。高屈折率層および中屈折率層のヘイズは、３％以下であることが好ましく、１％以下であることがより好ましく、０．５％以下であることが更に好ましい。 The average particle diameter of the inorganic fine particles is preferably 1 to 100 nm as an average particle diameter measured by a Coulter counter method. If it is 1 nm or less, the specific surface area is too large, so that the stability in the dispersion is poor, which is not preferable. When the thickness is 100 nm or more, scattering of visible light due to a difference in refractive index from the binder occurs, which is not preferable. The haze of the high refractive index layer and the medium refractive index layer is preferably 3% or less, more preferably 1% or less, and still more preferably 0.5% or less.
低屈折率層には、熱または電離放射線により硬化する含フッ素化合物が用いられる。該硬化物の動摩擦係数は好ましくは０．０３〜０．１５、純水に対する接触角は好ましくは１００〜１２０度である。動摩擦係数が０．１５より高いと、表面を擦った時に傷つきやすくなり、好ましくない。また、純水に対する接触角が１００度未満では指紋や油汚れ等が付着しやすくなるため、防汚性の観点で好ましくない。
該硬化性の含フッ素高分子化合物としてはパーフルオロアルキル基含有シラン化合物（例えば（ヘプタデカフルオロ−１，１，２，２−テトラデシル）トリエトキシシラン）等の他、含フッ素モノマーと架橋性基付与のためのモノマーを構成単位とする含フッ素共重合体が挙げられる。
含フッ素モノマー単位の具体例としては、例えばフルオロオレフィン類（例えばフルオロエチレン、ビニリデンフルオライド、テトラフルオロエチレン、ヘキサフルオロエチレン、ヘキサフルオロプロピレン、パーフルオロ−２，２−ジメチル−１，３−ジオキソール等）、（メタ）アクリル酸の部分または完全フッ素化アルキルエステル誘導体類（例えばビスコート６ＦＭ（大阪有機化学製）やＭ−２０２０（ダイキン製）等）、完全または部分フッ素化ビニルエーテル類等であり、これらのなかでも低屈折率、モノマーの扱いやすさの観点で特にヘキサフルオロプロピレンが好ましい。
架橋性基付与のためのモノマーとしてはグリシジルメタクリレートのように分子内にあらかじめ架橋性官能基を有する（メタ）アクリレートモノマーの他、カルボキシル基やヒドロキシル基、アミノ基、スルホン酸基等を有する（メタ）アクリレートモノマー（例えば（メタ）アクリル酸、メチロール（メタ）アクリレート、ヒドロキシアルキル（メタ）アクリレート、アリルアクリレート等）が挙げられる。後者は共重合の後、架橋構造を導入できることが特開平１０−２５３８８号公報および特開平１０−１４７７３９号公報により開示されており、特に好ましい。
For the low refractive index layer, a fluorine-containing compound that is cured by heat or ionizing radiation is used. The dynamic friction coefficient of the cured product is preferably 0.03 to 0.15, and the contact angle with respect to pure water is preferably 100 to 120 degrees. When the coefficient of dynamic friction is higher than 0.15, the surface tends to be damaged when rubbed, which is not preferable. In addition, when the contact angle with respect to pure water is less than 100 degrees, fingerprints, oil stains, and the like are likely to adhere, which is not preferable from the viewpoint of antifouling properties.
Examples of the curable fluorine-containing polymer compound include perfluoroalkyl group-containing silane compounds (for example, (heptadecafluoro-1,1,2,2-tetradecyl) triethoxysilane), fluorine-containing monomers and crosslinkable groups. Examples thereof include a fluorine-containing copolymer having a monomer for imparting as a structural unit.
Specific examples of the fluorine-containing monomer unit 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 Chemicals) and M-2020 (manufactured by Daikin)), fully or partially fluorinated vinyl ethers, etc. Of these, hexafluoropropylene is particularly preferred from the viewpoint of low refractive index and ease of handling of the monomer.
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.). JP-A-10-25388 and JP-A-10-147739 disclose that the latter can introduce a crosslinked structure after copolymerization, and is particularly preferable.
また上記含フッ素モノマーを構成単位とするポリマーだけでなく、フッ素原子を含有しないモノマーとの共重合体を用いてもよい。併用可能なモノマー単位には特に限定はなく、例えばオレフィン類（エチレン、プロピレン、イソプレン、塩化ビニル、塩化ビニリデン等）、アクリル酸エステル類（アクリル酸メチル、アクリル酸メチル、アクリル酸エチル、アクリル酸２−エチルヘキシル）、メタクリル酸エステル類（メタクリル酸メチル、メタクリル酸エチル、メタクリル酸ブチル、エチレングリコールジメタクリレート等）、スチレン誘導体（スチレン、ジビニルベンゼン、ビニルトルエン、α−メチルスチレン等）、ビニルエーテル類（メチルビニルエーテル等）、ビニルエステル類（酢酸ビニル、プロピオン酸ビニル、桂皮酸ビニル等）、アクリルアミド類（Ｎ−ｔｅｒｔブチルアクリルアミド、Ｎ−シクロヘキシルアクリルアミド等）、メタクリルアミド類、アクリロ二トリル誘導体等を挙げることができ、特開平１０−２５３８８号公報および特開平１０−１４７７３９号公報により開示されている。 Further, not only a polymer having the above-mentioned fluorine-containing monomer as a structural unit but also a copolymer with a monomer not containing a fluorine atom may be used. There are no particular limitations on the monomer units that can be used in combination. For example, olefins (ethylene, propylene, isoprene, vinyl chloride, vinylidene chloride, etc.), acrylic esters (methyl acrylate, methyl acrylate, ethyl acrylate, acrylic acid 2) -Ethylhexyl), methacrylates (methyl methacrylate, ethyl methacrylate, butyl methacrylate, ethylene glycol dimethacrylate, etc.), styrene derivatives (styrene, divinylbenzene, vinyltoluene, α-methylstyrene, etc.), vinyl ethers (methyl) Vinyl ether), vinyl esters (vinyl acetate, vinyl propionate, vinyl cinnamate, etc.), acrylamides (N-tertbutylacrylamide, N-cyclohexylacrylamide, etc.), methacrylamides, Krilo can be exemplified nitrile derivatives, disclosed by Japanese Patent Laid-Open 10-25388 and JP-10-147739 JP.
さらに耐傷性を付与するために動摩擦係数を低下させる手段として、滑り性を良化できる共重合単位を導入することができる。主鎖中にポリジメチルシロキサンセグメントを導入する方法が特開平１１−２２８６３１号公報に開示されており、特に好ましい。 Furthermore, a copolymer unit capable of improving slipperiness can be introduced as a means for reducing the dynamic friction coefficient in order to impart scratch resistance. A method of introducing a polydimethylsiloxane segment into the main chain is disclosed in JP-A-11-228631 and is particularly preferred.
低屈折率層の形成に用いる含フッ素樹脂には、耐傷性を付与するためにＳｉの酸化物超微粒子を添加して用いるのが好ましい。反射防止性の観点からは屈折率が低いほど好ましいが、含フッ素樹脂の屈折率を下げていくと耐傷性が悪化する。そこで、含フッ素樹脂の屈折率とＳｉの酸化物超微粒子の添加量を最適化することにより、耐傷性と低屈折率のバランスの最も良い点を見出すことができる。
Ｓｉの酸化物超微粒子としては、市販の有機溶剤に分散されたシリカゾルをそのまま塗布組成物に添加しても、市販の各種シリカ紛体を有機溶剤に分散して使用してもよい。
In order to impart scratch resistance to the fluorine-containing resin used for forming the low refractive index layer, it is preferable to add and use Si oxide ultrafine particles. From the viewpoint of antireflection properties, the lower the refractive index, the better. However, as the refractive index of the fluororesin is lowered, the scratch resistance deteriorates. Therefore, by optimizing the refractive index of the fluorine-containing resin and the addition amount of Si oxide ultrafine particles, it is possible to find the best point of the balance between scratch resistance and low refractive index.
As the ultrafine particles of Si, silica sol dispersed in a commercially available organic solvent may be added to the coating composition as it is, or various commercially available silica powders may be dispersed in an organic solvent.
反射防止フィルムには、さらに、ハードコート層、前方散乱層、帯電防止層、下塗り層や保護層を設けてもよい。
ハードコート層は、透明支持体に耐傷性を付与するために設ける。ハードコート層は、透明支持体とその上の層との接着を強化する機能も有する。ハードコート層は、多官能アクリルモノマー、ウレタンアクリレート、エポキシアクリレート等のオリゴマー、各種重合開始剤を溶媒に溶解した組成物に、必要に応じてシリカ、アルミナ等の無機フィラーを添加して得られた塗布組成物の塗布、溶媒の乾燥、熱および／または電離放射線により硬化することで好ましく形成される。詳細については後述する。
ハードコート層の厚さは、１〜３０μｍであることが好ましく、１〜２０μｍであることがさらに好ましく、２〜１５μｍであることが最も好ましい。
ハードコート層の鉛筆硬度はＨ以上であることが好ましく、２Ｈ以上であることがさらに好ましく、３Ｈ以上であることが最も好ましい。
ハードコート層の屈折率は、１．４５〜２．０の範囲が好ましく、１．５〜１．８の範囲がさらに好ましい。
ハードコート層は二酸化珪素を主とする無機化合物からなる層、飽和炭化水素またはポリエーテルを主鎖として有するポリマー等の有機化合物からなる層、あるいは無機／有機化合物のハイブリッド化された層として形成できる。飽和炭化水素を主鎖として有するポリマーからなる層であることが特に好ましい。ポリマーは架橋していることが好ましい。飽和炭化水素を主鎖として有するポリマーは、エチレン性不飽和モノマーの重合反応により得ることが好ましい。架橋しているバインダーポリマーを得るためには、二以上のエチレン性不飽和基を有するモノマーを用いることが好ましい。
The antireflection film may further be provided with a hard coat layer, a forward scattering layer, an antistatic layer, an undercoat layer and a protective layer.
The hard coat layer is provided for imparting scratch resistance to the transparent support. The hard coat layer also has a function of strengthening the adhesion between the transparent support and the layer thereon. The hard coat layer was obtained by adding an inorganic filler such as silica or alumina to a composition in which a polyfunctional acrylic monomer, an oligomer such as urethane acrylate or epoxy acrylate, or various polymerization initiators were dissolved in a solvent. It is preferably formed by applying a coating composition, drying a solvent, curing by heat and / or ionizing radiation. Details will be described later.
The thickness of the hard coat layer is preferably 1 to 30 μm, more preferably 1 to 20 μm, and most preferably 2 to 15 μm.
The pencil hardness of the hard coat layer is preferably H or higher, more preferably 2H or higher, and most preferably 3H or higher.
The refractive index of the hard coat layer is preferably in the range of 1.45 to 2.0, and more preferably in the range of 1.5 to 1.8.
The hard coat layer can be formed as a layer composed of an inorganic compound mainly composed of silicon dioxide, a layer composed of a saturated hydrocarbon or an organic compound such as a polymer having a polyether as a main chain, or a hybrid layer of inorganic / organic compounds. . A layer made of a polymer having a saturated hydrocarbon as the main chain is particularly preferred. The polymer is preferably crosslinked. The polymer having a saturated hydrocarbon as the main chain is preferably obtained by a polymerization reaction of an ethylenically unsaturated monomer. In order to obtain a crosslinked binder polymer, it is preferable to use a monomer having two or more ethylenically unsaturated groups.
二以上のエチレン性不飽和基を有するモノマーの例には、多価アルコールと（メタ）アクリル酸とのエステル（例、エチレングリコールジ（メタ）アクリレート、１，４−ジクロヘキサンジアクリレート、ペンタエリスリトールテトラ（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、トリメチロールプロパントリ（メタ）アクリレート、トリメチロールエタントリ（メタ）アクリレート、ジペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、ペンタエリスリトールヘキサ（メタ）アクリレート、１，２，３−シクロヘキサンテトラメタクリレート、ポリウレタンポリアクリレート、ポリエステルポリアクリレート）、ビニルベンゼンおよびその誘導体（例、１，４−ジビニルベンゼン、４−ビニル安息香酸−２−アクリロイルエチルエステル、１，４−ジビニルシクロヘキサノン）、ビニルスルホン（例、ジビニルスルホン）、アクリルアミド（例、メチレンビスアクリルアミド）およびメタクリルアミドが含まれる。
ポリエーテルを主鎖として有するポリマーは、多官能エポシキ化合物の開環重合反応により合成することが好ましい。
これらのエチレン性不飽和基を有するモノマーは、塗布後電離放射線または熱による重合反応により硬化させる必要がある。
Examples of monomers having two or more ethylenically unsaturated groups include esters of polyhydric alcohols 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, 1,2,3-cyclohexanetetramethacrylate, polyurethane polyacrylate, polyester polyacrylate), vinylbenzene and its derivatives (examples) 1,4-divinylbenzene, 4-vinylbenzoic acid-2-acryloylethyl ester, 1,4-divinylcyclohexanone), vinyl sulfone (eg, divinyl sulfone), acrylamide (eg, methylenebisacrylamide) and methacrylamide are included .
The polymer having a polyether as the main chain is preferably synthesized by a ring-opening polymerization reaction of a polyfunctional epoxy compound.
These monomers having an ethylenically unsaturated group need to be cured by a polymerization reaction by ionizing radiation or heat after coating.
二以上のエチレン性不飽和基を有するモノマーの代わりまたはそれに加えて、架橋性基の反応により、架橋構造をバインダーポリマーに導入してもよい。架橋性官能基の例には、イソシアナート基、エポキシ基、アジリジン基、オキサゾリン基、アルデヒド基、カルボニル基、ヒドラジン基、カルボキシル基、メチロール基および活性メチレン基が含まれる。ビニルスルホン酸、酸無水物、シアノアクリレート誘導体、メラミン、エーテル化メチロール、エステルおよびウレタン、テトラメトキシシランのような金属アルコキシドも、架橋構造を導入するためのモノマーとして利用できる。ブロックイソシアナート基のように、分解反応の結果として架橋性を示す官能基を用いてもよい。また、本発明において架橋基とは、上記化合物に限らず上記官能基が分解した結果反応性を示すものであってもよい。
これら架橋基を有する化合物は塗布後熱などによって架橋させる必要がある。
Instead of or in addition to the monomer having two or more ethylenically unsaturated groups, a crosslinked structure may be introduced into the binder polymer by the reaction of a crosslinkable group. 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. In the present invention, the cross-linking group is not limited to the above compound, and may be one showing reactivity as a result of decomposition of the functional group.
These compounds having a crosslinking group need to be crosslinked by heat after application.
更にハードコート層には、屈折率の調節や膜の硬化強度を高めるために無機の微粒子を添加しても良い。無機の微粒子としては平均粒子サイズが０．００１〜０．５μｍのものが好ましく、０．００１〜０．２μｍのものが特に好ましい。
無機微粒子としては二酸化珪素粒子、二酸化チタン粒子、酸化アルミニウム粒子、酸化錫粒子、炭酸カルシウム粒子、硫酸バリウム粒子、タルク、カオリンおよび硫酸カルシウム粒子があげられ、二酸化珪素粒子、二酸化チタン粒子、酸化アルミニウム粒子が特に好ましい。
無機微粒子の添加量は、ハードコート層の全質量の１０〜９０質量％であることが好ましく、２０〜８０質量％であると更に好ましく、３０〜６０質量％が特に好ましい。
Further, inorganic fine particles may be added to the hard coat layer in order to adjust the refractive index and increase the curing strength of the film. The inorganic fine particles preferably have an average particle size of 0.001 to 0.5 μm, particularly preferably 0.001 to 0.2 μm.
Examples of inorganic fine particles include silicon dioxide particles, titanium dioxide particles, aluminum oxide particles, tin oxide particles, calcium carbonate particles, barium sulfate particles, talc, kaolin and calcium sulfate particles. Silicon dioxide particles, titanium dioxide particles, aluminum oxide particles Is particularly preferred.
The addition amount of the inorganic fine particles is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and particularly preferably 30 to 60% by mass with respect to the total mass of the hard coat layer.
前方散乱層は、液晶表示装置に適用した場合の、上下左右方向に視角を傾斜させたときの視野角改良効果を付与するために設ける。上記ハードコート層中に屈折率の異なる微粒子を分散することで、ハードコート機能と兼ねることもできる。 The forward scattering layer is provided in order to give a viewing angle improvement effect when the viewing angle is inclined in the vertical and horizontal directions when applied to a liquid crystal display device. By dispersing fine particles having different refractive indexes in the hard coat layer, it can also serve as a hard coat function.
本発明の塗布組成物のウエット塗布による多層反射防止フィルムに表面凹凸によって背景の映り込みをぼかす、防眩性を付与する場合には、一般に用いられているようなマット粒子等を含有する表面凹凸を有する層の上に反射防止層を形成するよりも、エンボス法等によって反射防止層形成後に表面凹凸構造を形成したほうが、膜厚均一性が良化するため、反射防止性能が向上するので好ましい。 In the case of imparting anti-glare properties to blur the reflection of the background by surface irregularities on the multilayer antireflection film by wet coating of the coating composition of the present invention, the surface irregularities containing mat particles etc. that are generally used It is preferable to form the surface uneven structure after forming the antireflection layer by an embossing method or the like rather than forming an antireflection layer on the layer having, because the film thickness uniformity improves and the antireflection performance improves. .
反射防止フィルムの各層は、ディップコート法、エアーナイフコート法、カーテンコート法、ローラーコート法、ワイヤーバーコート法、グラビアコート、マイクログラビア法やエクストルージョンコート法（米国特許２６８１２９４号明細書）により、塗布により形成することができる。ウエット塗布量を最小化することで乾燥ムラをなくす観点でマイクログラビア法およびグラビア法が好ましく、幅方向の膜厚均一性の観点で特にグラビア法が好ましい。２層以上の層を同時に塗布してもよい。同時塗布の方法については、米国特許２７６１７９１号、同２９４１８９８号、同３５０８９４７号、同３５２６５２８号の各明細書および原崎勇次著、コーティング工学、２５３頁、朝倉書店（１９７３）に記載がある。 Each layer of the antireflection film is formed 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, a micro gravure method or an extrusion coating method (US Pat. No. 2,681,294). It can be formed by coating. The microgravure method and the gravure method are preferable from the viewpoint of eliminating drying unevenness by minimizing the wet coating amount, and the gravure method is particularly preferable from the viewpoint of film thickness uniformity in the width direction. Two or more layers may be applied simultaneously. The method of simultaneous application is described in US Pat. Nos. 2,761,791, 2,941,898, 3,508,947, and 3,526,528 and Yuji Harasaki, Coating Engineering, page 253, Asakura Shoten (1973).
本発明の反射防止フィルムを偏光子の表面保護フィルムの片側として用いる場合には、透明支持体の反射防止層が形成される面とは反対側の面をアルカリによって鹸化処理することが必要である。アルカリ鹸化処理の具体的手段としては、以下の２つから選択することができる。汎用のトリアセチルセルロースフィルムと同一の工程で処理できる点で（１）が優れているが、反射防止膜面まで鹸化処理されるため、表面がアルカリ加水分解されて膜が劣化する点、鹸化処理液が残ると汚れになる点が問題になり得る。その場合には、特別な工程となるが、（２）が優れる。
（１）透明支持体上に反射防止層を形成後に、アルカリ液中に少なくとも１回浸漬することで、該フィルムの裏面を鹸化処理する。
（２）透明支持体上に反射防止層を形成する前または後に、アルカリ液を該反射防止フィルムの反射防止フィルムを形成する面とは反対側の面に塗布し、加熱、水洗および／または中和することで、該フィルムの裏面だけを鹸化処理する。
When the antireflection film of the present invention is used as one side of the surface protective film of the polarizer, it is necessary to saponify the surface of the transparent support opposite to the surface on which the antireflection layer is formed with an alkali. . Specific means for the alkali saponification treatment can be selected from the following two. (1) is superior in that it can be processed in the same process as a general-purpose triacetylcellulose film, but since the surface of the antireflection film is saponified, the surface is alkali-hydrolyzed and the film deteriorates. The point that it becomes dirty when the liquid remains can be a problem. In that case, although it becomes a special process, (2) is excellent.
(1) After the antireflection layer is formed on the transparent support, the back surface of the film is saponified by immersing it in an alkaline solution at least once.
(2) Before or after the formation of the antireflection layer on the transparent support, the alkaline liquid is applied to the surface of the antireflection film opposite to the surface on which the antireflection film is formed, and is heated, washed and / or washed. By summing, only the back surface of the film is saponified.
偏光子には、ヨウ素系偏光子、二色性染料を用いる染料系偏光子やポリエン系偏光子がある。ヨウ素系偏光子および染料系偏光子は、一般にポリビニルアルコール系フィルム（以下、ＰＶＡと記載する）が好ましく用いられる。ＰＶＡは通常、ポリ酢酸ビニルをケン化したものであるが、変性ＰＶＡも用いることができる。ＰＶＡを染色して偏光膜が得られる。染色を行う例としては、ヨウ素−ヨウ化カリウム水溶液にＰＶＡフィルムを浸漬させる方法、ヨウ素あるいは染料溶液の塗布あるいは噴霧など任意の手段で行うことができる。ＰＶＡを延伸して偏光膜を製造する過程では、ＰＶＡを架橋させる添加物、例えばホウ酸類を用いることが好ましい。偏光板の透過率は、波長５５０ｎｍの光において、３０乃至５０％の範囲にあることが好ましく、３５乃至５０％の範囲にあることがさらに好ましい。偏光度は、波長５５０ｎｍの光において、９０乃至１００％の範囲にあることが好ましく、９５乃至１００％の範囲にあることがさらに好ましく、９９乃至１００％の範囲にあることが最も好ましい。 Examples of the polarizer include an iodine polarizer, a dye polarizer using a dichroic dye, and a polyene polarizer. In general, a polyvinyl alcohol film (hereinafter referred to as PVA) is preferably used as the iodine polarizer and the dye polarizer. PVA is usually saponified polyvinyl acetate, but modified PVA can also be used. A polarizing film is obtained by dyeing PVA. Examples of dyeing can be performed by any means such as a method of immersing a PVA film in an iodine-potassium iodide aqueous solution, application or spraying of iodine or a dye solution. In the process of producing a polarizing film by stretching PVA, it is preferable to use an additive that crosslinks PVA, for example, boric acids. The transmittance of the polarizing plate is preferably in the range of 30 to 50% and more preferably in the range of 35 to 50% with respect to light having a wavelength of 550 nm. The degree of polarization is preferably in the range of 90 to 100%, more preferably in the range of 95 to 100%, and most preferably in the range of 99 to 100% in light having a wavelength of 550 nm.
本発明の反射防止フィルムは、偏光子の表面保護フィルムの片側として用いた場合、 ツイステットネマチック（ＴＮ）、スーパーツイステットネマチック（ＳＴＮ）、バーティカルアライメント（ＶＡ）、インプレインスイッチング（ＩＰＳ）、オプティカリーコンペンセイテットベンドセル（ＯＣＢ）等のモードの透過型、反射型、または半透過型の液晶表示装置に好ましく用いることができる。また、透過型または半透過型の液晶表示装置に用いる場合には、市販の輝度向上フィルム（偏光選択層を有する偏光分離フィルム、例えば住友３Ｍ（株）製のＤ−ＢＥＦなど）と併せて用いることにより、さらに視認性の高い表示装置を得ることができる。また、透過型、反射型、および半透過型の液晶表示装置において液晶セルの全面に空気を介してアクリル板等の前面板を配する場合には、液晶セル表面側の偏光板だけでなく、前面板の内側及び／または外側に粘着剤等を介して貼り付けること、界面の反射を低減することができるため好ましい。また、λ／４板と組み合わせることで、反射型または半透過型のＬＣＤや、有機ＥＬディスプレイ用表面保護板として用いることができる。さらに、ＰＥＴ、ＰＥＮ等の透明支持体上に本発明の反射防止層を形成して、ＰＤＡ、携帯電話の表面保護板、タッチパネル、プラズマディスプレイパネル（ＰＤＰ）や陰極管表示装置（ＣＲＴ）のような画像表示装置に適用できる。 The antireflection film of the present invention, when used as one side of the surface protective film of a polarizer, is twisted nematic (TN), super twisted nematic (STN), vertical alignment (VA), in-plane switching (IPS), optical It can be preferably used for a transmissive, reflective, or transflective liquid crystal display device of a mode such as a curry compensate bend cell (OCB). When used in a transmissive or transflective liquid crystal display device, it is used in combination with a commercially available brightness enhancement film (a polarized light separation film having a polarization selective layer, such as D-BEF manufactured by Sumitomo 3M Co., Ltd.). Thus, a display device with higher visibility can be obtained. In addition, when a front plate such as an acrylic plate is arranged over the entire surface of the liquid crystal cell in a transmissive, reflective, and transflective liquid crystal display device, not only the polarizing plate on the liquid crystal cell surface side, Adhering to the inner side and / or the outer side of the front plate via an adhesive or the like and reducing reflection at the interface are preferable. Further, by combining with a λ / 4 plate, it can be used as a reflective or transflective LCD or a surface protection plate for an organic EL display. In addition, the antireflection layer of the present invention is formed on a transparent support such as PET or PEN, and the surface protection plate of a PDA, a cellular phone, a touch panel, a plasma display panel (PDP), or a cathode ray tube display (CRT). It can be applied to various image display devices.
以下に、実施例をもって本発明を説明するが、本発明はこれらに限定されるものではない。（ハードコート層用塗布液Ａの調整）
ジペンタエリスリトールペンタアクリレートとジペンタエリスリトールヘキサアクリレートの混合物（ＤＰＨＡ、日本化薬（株）製）３０６質量部を、１６質量部のメチルエチルケトンと２２０質量部のシクロヘキサノンの混合溶媒に溶解した。得られた溶液に、光重合開始剤（イルガキュア９０７、チバガイギー社製）７．５質量部をを加え、溶解するまで攪拌した後に、４５０質量部の ＭＥＫ−ＳＴ（平均粒径１０〜２０ｎｍ、固形分濃度３０質量％のＳｉＯ2 ゾルのメチルエチルケトン分散物、日産化学（株）製）を添加し、撹拌して混合物を得、孔径３μｍのポリプロピレン製フィルター（ＰＰＥ−０３）で濾過してハードコート層用塗布液Ａを調製した。
EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples. (Adjustment of coating liquid A for hard coat layer)
306 parts by mass of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.) was dissolved in a mixed solvent of 16 parts by mass of methyl ethyl ketone and 220 parts by mass of cyclohexanone. After adding 7.5 parts by mass of a photopolymerization initiator (Irgacure 907, manufactured by Ciba Geigy) to the resulting solution and stirring until dissolved, 450 parts by mass of MEK-ST (average particle size of 10 to 20 nm, solid A 30 wt% SiO 2 sol methyl ethyl ketone dispersion (manufactured by Nissan Chemical Co., Ltd.) was added and stirred to obtain a mixture, which was filtered through a polypropylene filter (PPE-03) having a pore size of 3 μm and a hard coat layer Coating solution A was prepared.
（ハードコート層用塗布液Ｂの調整）
上記ハードコート層用塗布液Ａ（溶剤乾燥し、紫外線硬化後の屈折率：１．５１）１０００質量部に、平均粒径１．３μｍの架橋ポリスチレンからなる前方散乱性付与粒子（ＳＸ−１３０Ｈ、屈折率：１．６１、綜研化学（株）製）１５０質量部を追添加し、エアディスパーにて１０分間攪拌して混合物を得、孔径３μｍのポリプロピレン製フィルター（ＰＰＥ−０３）で濾過して、前方散乱性を付与した、ハードコート層用塗布液Ｂを調製した。
(Adjustment of coating liquid B for hard coat layer)
Forward scattering property-imparting particles (SX-130H, made of crosslinked polystyrene having an average particle size of 1.3 μm) in 1000 parts by mass of the coating liquid A for hard coat layer (solvent-dried, refractive index after UV curing: 1.51). 150 parts by mass (refractive index: 1.61, manufactured by Soken Chemical Co., Ltd.) was added, and the mixture was stirred for 10 minutes with an air disper to obtain a mixture, which was filtered through a polypropylene filter (PPE-03) having a pore size of 3 μm. Then, a coating liquid B for hard coat layer having forward scattering properties was prepared.
（ハードコート層用塗布液Ｃの調整）
ジペンタエリスリトールペンタアクリレートとジペンタエリスリトールヘキサアクリレートの混合物（ＤＰＨＡ、日本化薬（株）製）９１質量部、粒径約３０ｎｍの酸化ジルコニウム超微粒子分散物含有ハードコート塗布液（デソライトＺ−７４０１、ＪＳＲ（株）製）２１８質量部を、５２質量部のメチルエチルケトン／シクロヘキサノン＝５４／４６質量％の混合溶剤に溶解した。得られた溶液に、光重合開始剤（イルガキュア９０７、チバファインケミカルズ（株）製）１０質量部を加え、撹拌して混合物を得、孔径３μｍのポリプロピレン製フィルター（ＰＰＥ−０３）で濾過してハードコート層用塗布液Cを調製した。
(Adjustment of coating liquid C for hard coat layer)
91 parts by mass of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.), zirconium oxide ultrafine particle dispersion containing a particle size of about 30 nm (Desolite Z-7401, 218 parts by mass of JSR Corporation) was dissolved in a mixed solvent of 52 parts by mass of methyl ethyl ketone / cyclohexanone = 54/46% by mass. To the obtained solution, 10 parts by mass of a photopolymerization initiator (Irgacure 907, manufactured by Ciba Fine Chemicals Co., Ltd.) is added and stirred to obtain a mixture, which is filtered through a polypropylene filter (PPE-03) having a pore size of 3 μm. A coating layer coating solution C was prepared.
（二酸化チタン分散物の調製）
二酸化チタン超微粒子（ＴＴＯ−５５Ｂ、石原テクノ（株）製）３０質量部、ジメチルアミノエチルアクリレート（ＤＭＡＥＡ、興人（株）製）１質量部、リン酸基含有アニオン性分散剤（ＫＡＹＡＲＡＤ ＰＭ−２１、日本化薬（株）製）６質量部およびシクロヘキサノン６３質量部を、サンドグラインダーによって、コールター法で測定した平均粒径が４２ｎｍになるまで分散し、二酸化チタン分散物を調製した。
(Preparation of titanium dioxide dispersion)
Titanium dioxide ultrafine particles (TTO-55B, manufactured by Ishihara Techno Co., Ltd.) 30 parts by mass, dimethylaminoethyl acrylate (DMAEA, manufactured by Kojin Co., Ltd.) 1 part by mass, phosphate group-containing anionic dispersant (KAYARAD PM- 21, Nippon Kayaku Co., Ltd.) 6 parts by mass and cyclohexanone 63 parts by mass were dispersed with a sand grinder until the average particle size measured by the Coulter method was 42 nm to prepare a titanium dioxide dispersion.
（中屈折率層用塗布液Ａの調製）
シクロヘキサノン７５質量部およびメチルエチルケトン１９質量部に、光重合開始剤（イルガキュア９０７、チバガイギー社製）０．１１質量部および光増感剤（カヤキュアーＤＥＴＸ、日本化薬（株）製）０．０４質量部を溶解した。さらに、二酸化チタン分散物３．１質量部およびジペンタエリスリトールペンタアクリレートとジペンタエリスリトールヘキサアクリレートの混合物（ＤＰＨＡ、日本化薬（株）製）２．１質量部を加え、室温で３０分間撹拌した後、孔径３μｍのポリプロピレン製フィルター（ＰＰＥ−０３）で濾過して、中屈折率層用塗布液を調製した。
(Preparation of coating liquid A for medium refractive index layer)
To 75 parts by mass of cyclohexanone and 19 parts by mass of methyl ethyl ketone, 0.11 part by mass of photopolymerization initiator (Irgacure 907, manufactured by Ciba Geigy) and 0.04 parts by mass of photosensitizer (Kayacure DETX, manufactured by Nippon Kayaku Co., Ltd.) Was dissolved. Further, 3.1 parts by mass of titanium dioxide dispersion and 2.1 parts by mass of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, Nippon Kayaku Co., Ltd.) were added and stirred at room temperature for 30 minutes. Then, it filtered with the polypropylene filter (PPE-03) with a hole diameter of 3 micrometers, and prepared the coating liquid for middle refractive index layers.
（中屈折率層用塗布液Ｂの調製）
シクロヘキサノン７５０質量部、メチルエチルケトン１９０質量部に、光重合開始剤（イルガキュア９０７、チバガイギー社製）１．２質量部および光増感剤（カヤキュアーＤＥＴＸ、日本化薬（株）製）０．４質量部を溶解した。さらに、二酸化チタン分散物１０５質量部およびジペンタエリスリトールペンタアクリレートとジペンタエリスリトールヘキサアクリレートの混合物（ＤＰＨＡ、日本化薬（株）製）２１質量部を加え、室温で３０分間撹拌した後、孔径３μｍのポリプロピレン製フィルター（ＰＰＥ−０３）で濾過して、中屈折率層用塗布液Ｂを調製した。
(Preparation of coating liquid B for medium refractive index layer)
750 parts by mass of cyclohexanone, 190 parts by mass of methyl ethyl ketone, 1.2 parts by mass of photopolymerization initiator (Irgacure 907, manufactured by Ciba Geigy) and 0.4 parts by mass of photosensitizer (Kayacure DETX, manufactured by Nippon Kayaku Co., Ltd.) Was dissolved. Further, 105 parts by mass of titanium dioxide dispersion and 21 parts by mass of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.) were added and stirred for 30 minutes at room temperature. Was filtered using a polypropylene filter (PPE-03) to prepare a coating solution B for medium refractive index layer.
（高屈折率層用塗布液の調製）
シクロヘキサノン５４質量部およびメチルエチルケトン１８質量部に、光重合開始剤（イルガキュア９０７、チバガイギー社製）０．１３質量部および光増感剤（カヤキュアーＤＥＴＸ、日本化薬（株）製）０．０４質量部を溶解した。さらに、二酸化チタン分散物２６．４質量部およびジペンタエリスリトールペンタアクリレートとジペンタエリスリトールヘキサアクリレートの混合物（ＤＰＨＡ、日本化薬（株）製）１．６質量部を加え、室温で３０分間撹拌した後、孔径３μｍのポリプロピレン製フィルター（ＰＰＥ−０３）で濾過して、高屈折率層用塗布液を調製した。
(Preparation of coating solution for high refractive index layer)
54 parts by mass of cyclohexanone and 18 parts by mass of methyl ethyl ketone, 0.13 parts by mass of photopolymerization initiator (Irgacure 907, manufactured by Ciba Geigy) and 0.04 parts by mass of photosensitizer (Kayacure DETX, manufactured by Nippon Kayaku Co., Ltd.) Was dissolved. Furthermore, 26.4 parts by mass of titanium dioxide dispersion and 1.6 parts by mass of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.) were added and stirred at room temperature for 30 minutes. Then, it filtered with the filter (PPE-03) made from a polypropylene with the hole diameter of 3 micrometers, and prepared the coating liquid for high refractive index layers.
（低屈折率層用塗布液の調製）
屈折率１．４２であり、熱架橋性含フッ素ポリマーの６質量パーセントのメチルエチルケトン溶液（ＪＮ−７２２８、ＪＳＲ（株）製）を溶媒置換して、メチルイソブチルケトン８５質量％、２−ブタノール１５質量％からなる混合溶媒中に固形分１０質量％を含有するポリマー溶液を得た。このポリマー溶液７０質量部にＭＥＫ−ＳＴ（平均粒径１０〜２０ｎｍ、固形分濃度３０質量％のＳｉＯ2ゾルのメチルエチルケトン分散物、日産化学（株）製）１０質量部、およびメチルイソブチルケトン４２質量部およびシクロヘキサノン２８質量部を添加、攪拌の後、孔径３μｍのポリプロピレン製フィルター（ＰＰＥ−０３）でろ過して、低屈折率層用塗布液を調製した。
(Preparation of coating solution for low refractive index layer)
A 6 mass percent methyl ethyl ketone solution (JN-7228, manufactured by JSR Corporation) of a thermally crosslinkable fluorine-containing polymer having a refractive index of 1.42 is solvent-substituted, and methyl isobutyl ketone 85 mass%, 2-butanol 15 mass A polymer solution containing 10% by mass of solid content in a mixed solvent consisting of% was obtained. To 70 parts by mass of this polymer solution, 10 parts by mass of MEK-ST (Methyl ethyl ketone dispersion of SiO 2 sol having an average particle diameter of 10 to 20 nm and a solid concentration of 30% by mass, manufactured by Nissan Chemical Co., Ltd.), and 42 parts by mass of methyl isobutyl ketone And 28 parts by mass of cyclohexanone were added and stirred, and then filtered through a polypropylene filter (PPE-03) having a pore size of 3 μm to prepare a coating solution for a low refractive index layer.
［実施例１］
（反射防止フィルムの作成）
８０μｍの厚さのトリアセチルセルロースフィルム（ＴＡＣ−ＴＤ８０Ｕ、富士写真フィルム（株）製、屈折率：１．４７）に、上記のハードコート層用塗布液Ａを、グラビアコーターを用いて塗布し、１００℃で２分間乾燥した。次に紫外線を照射して、塗布層を硬化させ、ハードコート層（屈折率：１．５１、膜厚：６μｍ）を形成した。
続いて、上記の中屈折率層用塗布液Ａをグラビアコーターを用いて塗布し、１００℃で乾燥した後、紫外線を照射して塗布層を硬化させ、中屈折率層（屈折率：１．６３、膜厚：６７ｎｍ）を設けた。
中屈折率層の上に、上記の高屈折率層用塗布液をグラビアコーターを用いて塗布し、１００℃で乾燥した後、紫外線を照射して塗布層を硬化させ、高屈折率層（屈折率：１．９０、膜厚：１０７ｎｍ）を設けた。
さらに高屈折率層の上に、上記の低屈折率層用塗布液をグラビアコーターを用いて塗布し、１２０℃で８分間、塗布層を硬化させ、低屈折率層（屈折率：１．４３、膜厚：８６ｎｍ ）を設けた。このようにして反射防止フィルムを作成した。
[Example 1]
(Creation of antireflection film)
The above-mentioned coating liquid A for hard coat layer was applied to a triacetyl cellulose film (TAC-TD80U, manufactured by Fuji Photo Film Co., Ltd., refractive index: 1.47) with a thickness of 80 μm using a gravure coater, Dry at 100 ° C. for 2 minutes. Next, the coating layer was cured by irradiating with ultraviolet rays to form a hard coat layer (refractive index: 1.51, film thickness: 6 μm).
Subsequently, the above-described coating liquid A for the medium refractive index layer was applied using a gravure coater, dried at 100 ° C., then irradiated with ultraviolet rays to cure the coating layer, and the medium refractive index layer (refractive index: 1.. 63, film thickness: 67 nm).
On the medium refractive index layer, the above high refractive index layer coating solution is applied using a gravure coater, dried at 100 ° C., then irradiated with ultraviolet rays to cure the coated layer, and the high refractive index layer (refractive (Rate: 1.90, film thickness: 107 nm).
Further, the coating solution for the low refractive index layer is applied on the high refractive index layer using a gravure coater, and the coating layer is cured at 120 ° C. for 8 minutes to obtain a low refractive index layer (refractive index: 1.43). , Film thickness: 86 nm). In this way, an antireflection film was prepared.
（反射防止フィルムの評価）
得られたフィルムについて、以下の項目の評価を行った。その結果を表１にまとめる。
（１）鏡面反射率及び色味
分光光度計Ｖ−５５０（日本分光（株）製）にアダプターＡＲＶ−４７４を装着して、３８０〜７８０ｎｍの波長領域において、入射角５°における出射角−５度の鏡面反射率を測定し、４５０〜６５０ｎｍの平均反射率を算出し、反射防止性を評価した。さらに、測定された反射スペクトルから、ＣＩＥ標準光源Ｄ６５の５度入射光に対する正反射光の色味を表わすＣＩＥ１９７６Ｌ＊ａ＊ｂ＊色空間のＬ＊値、ａ＊値、ｂ＊値を算出し、反射光の色味を評価した。
（２）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２Ｈ〜５Ｈの試験用鉛筆を用いて、５００ｇの荷重にて、以下のとおりの判定で評価し、ＯＫとなる最も高い硬度を評価値とした。
ｎ＝５の評価において傷なし〜傷１つ ：ＯＫ
ｎ＝５の評価において傷が３つ以上 ：ＮＧ
（３）接触角測定
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、純水の接触角を測定し、指紋付着性の指標とした。
（４）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。
（５）垂直剥離帯電量測定
本文中に記載した通りの方法で垂直剥離帯電量を測定した。
（６）表面抵抗値
円電極法により表面抵抗値を測定した。
(Evaluation of antireflection film)
About the obtained film, the following items were evaluated. The results are summarized in Table 1.
(1) Specular reflectance and tint A spectrophotometer V-550 (manufactured by JASCO Corp.) is fitted with an adapter ARV-474, and an emission angle of -5 at an incident angle of 5 ° in a wavelength range of 380 to 780 nm. The specular reflectivity was measured, the average reflectivity of 450 to 650 nm was calculated, and the antireflection property was evaluated. Further, CIE 1976 L * a * b * color space L * value, a * value, and b * value representing the color of the specularly reflected light with respect to the 5 degree incident light of the CIE standard light source D65 are calculated from the measured reflection spectrum. The color of reflected light was evaluated.
(2) Pencil hardness evaluation Pencil hardness evaluation described in JIS K 5400 was performed as an index of scratch resistance. After conditioning the antireflection film at a temperature of 25 ° C. and a humidity of 60% RH for 2 hours, it was evaluated using the 2H-5H test pencil specified in JIS S 6006 at a load of 500 g as follows. Then, the highest hardness that is OK was taken as the evaluation value.
In evaluation of n = 5, no scratch to one scratch: OK
In evaluation of n = 5, 3 or more scratches: NG
(3) Contact angle measurement As an index of surface contamination resistance, the optical material was conditioned at a temperature of 25 ° C. and a humidity of 60% RH for 2 hours, and then the contact angle of pure water was measured to obtain an index of fingerprint adhesion. .
(4) Dynamic friction coefficient measurement The dynamic friction coefficient 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.
(5) Measurement of vertical peeling charge amount The vertical peeling charge amount was measured by the method described in the text.
(6) Surface resistance value The surface resistance value was measured by the circular electrode method.
［比較例］
物理蒸着法により、実施例１のハードコート上に順次、酸化チタン（屈折率：２．３９）２５ｎｍと酸化ケイ素（屈折率１．４７）２５ｎｍの２層からなる実質上中屈折率層、酸化チタン４６ｎｍからなる高屈折率層、酸化ケイ素９７ｎｍからなる低屈折率層を形成し、反射防止フィルムを作成し、実施例１と同様の評価を行った。
図２に本発明の実施例１および比較例１の反射防止フィルムの波長３８０ｎｍから７８０ｎｍまでにおける反射率スペクトルを示した。
[Comparative example]
By means of physical vapor deposition, a substantially middle refractive index layer consisting of two layers of titanium oxide (refractive index: 2.39) 25 nm and silicon oxide (refractive index 1.47) 25 nm is sequentially formed on the hard coat of Example 1 and oxidized. A high refractive index layer composed of 46 nm of titanium and a low refractive index layer composed of 97 nm of silicon oxide were formed to produce an antireflection film, and the same evaluation as in Example 1 was performed.
FIG. 2 shows the reflectance spectra of the antireflection films of Example 1 and Comparative Example 1 of the present invention at wavelengths from 380 nm to 780 nm.
［実施例２］
実施例１で作成した反射防止フィルムを、２．０規定、５５℃のＮａＯＨ水溶液中に２分間浸漬してフィルムの裏面のトリアセチルセルロース面を鹸化処理し、８０μｍの厚さのトリアセチルセルロースフィルム（ＴＡＣ−ＴＤ８０Ｕ、富士写真フィルム（株）製）を同条件で鹸化処理したフィルムとでポリビニルアルコールにヨウ素を吸着させ、延伸して作成した偏光子の両面を接着、保護して偏光板を作成した。このようにして作成した偏光板を、反射防止膜側が最表面となるように透過型ＴＮ液晶表示装置搭載のノートパソコンの液晶表示装置（偏光選択層を有する偏光分離フィルムである住友３Ｍ（株）製のＤ−ＢＥＦをバックライトと液晶セルとの間に有する）の視認側の偏光板と貼り代えたところ、背景の映りこみが極めて少なく、表示品位の非常に高い表示装置が得られた。
[Example 2]
The antireflective film prepared in Example 1 was immersed in a 2.0 normal, 55 ° C. NaOH aqueous solution for 2 minutes to saponify the triacetyl cellulose surface on the back side of the film, and a triacetyl cellulose film having a thickness of 80 μm. (TAC-TD80U, manufactured by Fuji Photo Film Co., Ltd.) with a film saponified under the same conditions, iodine is adsorbed onto polyvinyl alcohol, and stretched to bond and protect both sides of the polarizer to create a polarizing plate did. The thus-prepared polarizing plate is a liquid crystal display device of a notebook computer equipped with a transmission type TN liquid crystal display device (Sumitomo 3M Co., Ltd., which is a polarization separation film having a polarization selection layer) so that the antireflection film side is the outermost surface. When the polarizing plate on the viewing side of D-BEF made of the product between the backlight and the liquid crystal cell was replaced, a display device with very high display quality was obtained with very little background reflection.
［実施例３］
実施例２の鹸化処理を、１．０規定のＫＯＨ水溶液を＃３バーにて反射防止フィルムの裏面に塗布し、膜面温度６０℃にて１０秒間処理した後に水洗、乾燥して行った以外は実施例２と同様にして、液晶表示装置に貼り付けたところ、実施例２と同様の表示品位の高い表示装置が得られた。
[Example 3]
The saponification treatment of Example 2 was performed except that a 1.0 N KOH aqueous solution was applied to the back surface of the antireflection film with a # 3 bar, treated at a film surface temperature of 60 ° C. for 10 seconds, washed with water and dried. Was affixed to a liquid crystal display device in the same manner as in Example 2, and a display device with high display quality similar to that in Example 2 was obtained.
［実施例４］
実施例３の反射防止フィルムを貼り付けた透過型ＴＮ液晶セルの視認側の偏光板の液晶セル側の保護フィルムおよびバックライト側の偏光板の液晶セル側の保護フィルムに、ディスコティック構造単位の円盤面が透明支持体面に対して傾いており、且つ該ディスコティック構造単位の円盤面と透明支持体面とのなす角度が、光学異方層の深さ方向において変化している光学補償層を有する視野角拡大フィルム（ワイドビューフィルムＳＡ−１２Ｂ、富士写真フィルム（株）製）を用いたところ、明室でのコントラストに優れ、且つ、上下左右の視野角が非常に広く、極めて視認性に優れ、表示品位の高い液晶表示装置が得られた。
[Example 4]
In the protective film on the liquid crystal cell side of the polarizing plate on the viewing side and the protective film on the liquid crystal cell side of the polarizing plate on the backlight side of the transmission type TN liquid crystal cell to which the antireflection film of Example 3 was attached, the discotic structural unit The disc surface is inclined with respect to the transparent support surface, and the angle formed by the disc surface of the discotic structural unit and the transparent support surface has an optical compensation layer that varies in the depth direction of the optical anisotropic layer. When a viewing angle widening film (wide view film SA-12B, manufactured by Fuji Photo Film Co., Ltd.) is used, it has excellent contrast in a bright room, very wide viewing angles in the vertical and horizontal directions, and extremely excellent visibility. A liquid crystal display device with high display quality was obtained.
［実施例５］
実施例１のハードコート用塗布液Ａの代わりにハードコート層用塗布液Ｂを用いた以外は実施例１と同様にして、前方散乱機能を有する反射防止フィルムを作成し、実施例４と同様にして、最表面側にこの前方散乱性反射防止フィルムを、液晶セル側に視野角拡大フィルムワイドビューフィルム（ＷＶ−１２Ａ、富士写真フィルム（株）製）を有する偏光板を配置した透過型ＴＮ液晶表示装置を作成した。
このようにして作成した液晶表示装置は、実施例４と比較して、下方向に視角を倒した時の階調反転が起こる限界角が４０度から６０度まで改善され、視認性、表示品位において大変優れたものであった。
[Example 5]
An antireflection film having a forward scattering function was prepared in the same manner as in Example 1 except that the hard coat layer coating solution B was used instead of the hard coat coating solution A in Example 1, and the same as in Example 4. Then, a transmission type TN in which the forward scattering antireflection film is disposed on the outermost surface side and a polarizing plate having a viewing angle widening film wide view film (WV-12A, manufactured by Fuji Photo Film Co., Ltd.) is disposed on the liquid crystal cell side. A liquid crystal display device was created.
In the liquid crystal display device thus produced, the limit angle at which gradation inversion occurs when the viewing angle is tilted downward is improved from 40 degrees to 60 degrees as compared with the fourth embodiment, and the visibility and display quality are improved. It was very good.
［実施例６］
実施例３の反射防止層を有する偏光板を最表面に配し、アクリル前面板の内側と外側の両面に実施例１で作成した反射防止フィルムを粘着剤を介して貼り合わせて、前面板を最表面に配した半透過型液晶表示装置を具備する携帯電話を作成したところ、前面板のない反射防止処理した液晶表示装置と遜色のない、視認性の高い表示装置が得られえた。
また、前面板の内側だけに実施例１の反射防止フィルムを貼り合せたもの、なにも貼り合せなかったもの、及び前面板にも液晶セルにも反射防止のないものを同時に作成した結果、反射防止フィルムの枚数の減少とともに視認性が悪化し、反射防止なしのものは蛍光灯等の映りこんだところの文字が完全に読めなくなった。
[Example 6]
The polarizing plate having the antireflection layer of Example 3 is disposed on the outermost surface, and the antireflection film prepared in Example 1 is bonded to both the inner and outer surfaces of the acrylic front plate via an adhesive, and the front plate is attached. When a mobile phone having a transflective liquid crystal display device arranged on the outermost surface was produced, a highly visible display device that was comparable to an antireflection liquid crystal display device without a front plate could be obtained.
In addition, as a result of simultaneously creating an antireflection film of Example 1 only on the inner side of the front plate, one that was not bonded, and one that was not antireflection on the front plate and the liquid crystal cell, Visibility deteriorated with a decrease in the number of antireflection films, and characters without reflection were completely unreadable when reflected in a fluorescent lamp or the like.
［実施例７］
実施例１で作成した反射防止フィルムを有機ＥＬ表示装置の表面のガラス板に粘着剤を介して貼り合わせたところ、ガラス表面での反射が抑えられ、視認性の高い表示装置が得られた。
[Example 7]
When the antireflection film prepared in Example 1 was bonded to the glass plate on the surface of the organic EL display device via an adhesive, reflection on the glass surface was suppressed, and a display device with high visibility was obtained.
［実施例８］
実施例３で作成した片面反射防止フィルム付き偏光板の反射防止膜を有している側の反対面にλ／４板を張り合わせ、有機ＥＬ表示装置の表面のガラス板に貼り付けたところ、表面反射および、表面ガラスの内部からの反射がカットされ、極めて視認性の高い表示が得られた。
[Example 8]
When a λ / 4 plate is pasted on the opposite surface of the polarizing plate with the single-side antireflection film prepared in Example 3 on the side having the antireflection film, and attached to the glass plate on the surface of the organic EL display device, the surface The reflection and the reflection from the inside of the surface glass were cut, and a display with extremely high visibility was obtained.
［実施例９］
片面下塗り層を有し、厚み１８８μｍのポリエチレンテレフタレートフィルム（コスモシャインＡ４１００、帝人（株）製、屈折率：１．６５）の下塗り面にハードコート用塗布液Cを実施例１と同様にして塗布、溶媒の乾燥、紫外線硬化を行い、ハードコート層（屈折率：１．６１、膜厚：８μｍ）を形成した。
続いて、上記の中屈折率層用塗布液Ｂをグラビアコーターを用いて塗布し、１００℃で乾燥した後、紫外線を照射して塗布層を硬化させ、中屈折率層（屈折率：１．７０、膜厚：７０ｎｍ）を設けた。
中屈折率層の上に、上記の高屈折率層用塗布液をグラビアコーターを用いて塗布し、１００℃で乾燥した後、紫外線を照射して塗布層を硬化させ、高屈折率層（屈折率：１．９０、膜厚：１２０ｎｍ）を設けた。
さらに高屈折率層の上に、上記の低屈折率層用塗布液をグラビアコーターを用いて塗布し、１２０℃で８分間、塗布層を硬化させ、低屈折率層（屈折率：１．４３、膜厚：９０ｎｍ ）を設けた。このようにして反射防止フィルムを作成し、実施例１と同様の評価を行った。反射光の色味が著しく低減され、また、鉛筆高度が非常に高く、フラットＣＲＴ、およびＰＤＰの最表面に貼り付けたところ、低反射、反射光の色味低減、および高い膜硬度を同時に満足した表示装置が得られた。
[Example 9]
A hard coat coating solution C was applied to the undercoat surface of a polyethylene terephthalate film (Cosmo Shine A4100, manufactured by Teijin Ltd., refractive index: 1.65) having a single-side undercoat layer and a thickness of 188 μm in the same manner as in Example 1. Then, the solvent was dried and UV-cured to form a hard coat layer (refractive index: 1.61, film thickness: 8 μm).
Subsequently, the above-described coating liquid B for medium refractive index layer was applied using a gravure coater, dried at 100 ° C., then irradiated with ultraviolet rays to cure the coated layer, and the medium refractive index layer (refractive index: 1.. 70, film thickness: 70 nm).
On the medium refractive index layer, the above high refractive index layer coating solution is applied using a gravure coater, dried at 100 ° C., then irradiated with ultraviolet rays to cure the coated layer, and the high refractive index layer (refractive (Rate: 1.90, film thickness: 120 nm).
Further, the coating solution for the low refractive index layer is applied on the high refractive index layer using a gravure coater, and the coating layer is cured at 120 ° C. for 8 minutes to obtain a low refractive index layer (refractive index: 1.43). , Film thickness: 90 nm). In this way, an antireflection film was prepared and evaluated in the same manner as in Example 1. The color of reflected light is remarkably reduced, and the pencil height is very high, and when applied to the outermost surface of flat CRT and PDP, low reflection, reduced color of reflected light, and high film hardness are satisfied at the same time. A display device was obtained.
実施例１および９の反射防止フィルムは、低反射率と色味低減が両立され、非常に好ましい反射特性を有するだけでなく、動摩擦が低いため、耐傷性に優れ、純水の接触角が高いことから、撥水、撥油性に優れるため、防汚性に優れ、さらに、鉛筆硬度が高く、傷がつき難い。さらに、ＴＤ方向、ＭＤ方向に１０ｃｍ離れた任意の２つの場所における波長３８０ｎｍから７８０ｎｍの領域におけるＣＩＥ標準光源Ｄ６５の５度入射光に対する正反射光の色味ムラが、ＣＩＥ１９７６Ｌ＊ａ＊ｂ＊色空間のΔＥａｂ＊値で０〜１．５の範囲に入っているため、場所違いでの反射光の色味の均一性が高い。また、表面抵抗値はいずれも１×１０12Ω／□以上であったが垂直剥離帯電が＋１２０ｐｃ（ピコクーロン）／ｃｍ2であり、防塵性に優れていた。
比較例の反射防止フィルムは、反射光が赤紫色に強く着色しておリ、表示品位に劣っていた。また、動摩擦が高いため、耐傷性に劣り、純水の接触角が低く、防汚性が悪いものであった。
The antireflection films of Examples 1 and 9 have both low reflectance and color reduction, have not only very favorable reflection characteristics, but also low dynamic friction, so they have excellent scratch resistance and a high pure water contact angle. Therefore, since it is excellent in water and oil repellency, it is excellent in antifouling property, has a high pencil hardness, and is hardly scratched. Furthermore, the CIE 1976 L * a * b * color is a non-uniform color tone of specularly reflected light with respect to 5 ° incident light of the CIE standard light source D65 in the wavelength range of 380 nm to 780 nm in any two
The antireflection film of the comparative example was inferior in display quality because the reflected light was strongly colored reddish purple. Further, since the dynamic friction was high, the scratch resistance was poor, the contact angle of pure water was low, and the antifouling property was poor.
［実施例１０］
実施例２の偏光子に、以下の方法で作製した偏光子を用いる以外は、実施例２と同様にして、偏光板を作成した。反射防止性能は実施例１と同一であったが、得られた偏光子の吸収軸方向は、長手方向に対し４５゜傾斜しており、偏光板を各サイズに打ち抜く際に発生する打ち抜き屑が減少した。（偏光子の作製）
ＰＶＡフィルムをヨウ素５．０ｇ／ｌ、ヨウ化カリウム１０．０ｇ／ｌの水溶液に２５℃にて９０秒浸漬し、さらにホウ酸１０ｇ／ｌの水溶液に２５℃にて６０秒浸漬後、米国特許公開第２００２−８８４０Ａ１号のFig.２の形態のテンター延伸機に導入し、７．０倍に一旦延伸した後５．３倍まで収縮させ、以降幅を一定に保ち、７０℃で乾燥した後テンターより離脱した。左右のテンタークリップの搬送速度差は、０．０５％未満であり、導入されるフィルムの中心線と次工程に送られるフィルムの中心線のなす角は、０゜であった。ここでFig.2中｜Ｌ１−Ｌ２｜、Ｗとも０．７ｍであった。テンター出口におけるシワ、フィルム変形は観察されなかった。この偏光子の５５０ｎｍにおける透過率は４３．３％、偏光度は９９．９８％であった。
[Example 10]
A polarizing plate was produced in the same manner as in Example 2 except that the polarizer produced in the following method was used as the polarizer in Example 2. The antireflection performance was the same as in Example 1, but the absorption axis direction of the obtained polarizer was inclined by 45 ° with respect to the longitudinal direction, and punching dust generated when punching the polarizing plate into each size was found. Diminished. (Production of polarizer)
The PVA film was immersed in an aqueous solution of 5.0 g / l iodine and 10.0 g / l potassium iodide at 25 ° C. for 90 seconds, and further immersed in an aqueous solution of boric acid 10 g / l for 60 seconds at 25 ° C. Introduced in the tenter drawing machine in the form of Fig. 2 of the published No. 2002-8840A1, once stretched to 7.0 times and then shrunk to 5.3 times, and thereafter kept constant in width and dried at 70 ° C. I left the tenter. The difference in transport speed between the left and right tenter clips was less than 0.05%, and the angle between the center line of the introduced film and the center line of the film sent to the next process was 0 °. In FIG. 2, both | L1-L2 | and W were 0.7 m. Wrinkles and film deformation at the tenter exit were not observed. The transmittance of this polarizer at 550 nm was 43.3%, and the degree of polarization was 99.98%.
１ 透明支持体
２ ハードコート層
３ 中屈折率層
４ 高屈折率層
５ 低屈折率層
DESCRIPTION OF SYMBOLS 1
Claims (23)
ｌλ／４×０．８０＜ｎ１ｄ１＜ｌλ／４×１．００ （Ｉ）
ｍλ／４×０．７５＜ｎ２ｄ２＜ｍλ／４×０．９５ （ＩＩ）
ｎλ／４×０．９５＜ｎ３ｄ３＜ｎλ／４×１．０５ （ＩＩＩ）（但し、式中、ｌは１であり、ｎ１は中屈折率層の屈折率であり、そして、ｄ１は中屈折率層の層厚（ｎｍ）であり、ｍは２であり、ｎ２は高屈折率層の屈折率であり、そして、ｄ２は高屈折率層の層厚（ｎｍ）であり、ｎは１であり、ｎ３は低屈折率層の屈折率であり、そして、ｄ３は低屈折率層の層厚（ｎｍ）である） In the antireflection film, the medium refractive index layer is represented by the following formula (I), the high refractive index layer is represented by the following formula (II), and the low refractive index layer is represented by the following formula (III) with respect to the design wavelength λ (= 500 nm). The antireflection film according to claim 5, wherein:
lλ / 4 × 0.80 <n1d1 <lλ / 4 × 1.00 (I)
mλ / 4 × 0.75 <n2d2 <mλ / 4 × 0.95 (II)
nλ / 4 × 0.95 <n3d3 <nλ / 4 × 1.05 (III) (where, l is 1, n1 is the refractive index of the medium refractive index layer, and d1 is medium refractive) The layer thickness (nm) of the refractive index layer, m is 2, n2 is the refractive index of the high refractive index layer, and d2 is the layer thickness (nm) of the high refractive index layer, and n is 1. N3 is the refractive index of the low refractive index layer, and d3 is the layer thickness (nm) of the low refractive index layer)
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| JP2007272244A (en) | 2007-10-18 |
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