JP6146103B2 - Antireflection film, polarizing plate using the same, touch panel substrate, image display device - Google Patents

Description

  The present invention relates to an antireflection film provided for the purpose of preventing external light from being reflected on the surface of a display or the like, a polarizing plate provided with the antireflection film, a touch panel substrate, and an image display device.

  The display is used in an environment where external light or the like enters regardless of whether the display is used indoors or outdoors. Incident light such as external light is specularly reflected on the display surface and the like, and the reflected image thereby mixes with the display image, thereby degrading the screen display quality. Therefore, it is essential to provide an anti-reflection function on the display surface, etc., especially in recent years the spread of mobile terminals, in the daytime outdoors, because it is exposed to strong external light than when used indoors, There is a need for an antireflection film with low reflectance that does not impair visibility even outdoors.

  Further, when an antireflection film is applied to a stationary installation type image display device, most of them are premised on reducing reflected light from a fixed light source. This means that the incident angle of external light does not change. On the other hand, in the case of a mobile terminal, since it is used outdoors or operated at hand, the incidence of external light occurs from various angles, and the viewer often observes the display from various angles. Therefore, when trying to apply an antireflection film to a mobile terminal, it is necessary to consider not only the reflected light from the front but also the reflected light, especially the color of the reflected light, for the light source of all incident angles. .

  On the other hand, for example, for the purpose of suppressing coloring of the antireflection film, a method of forming an antistatic layer made of a conductive metal oxide, a refractive index reducing substance, and an ultraviolet curable resin is shown (for example, a patent). Reference 1).

  Such an antireflection film is provided with a low refractive index layer which is a thin film layer having a film thickness of 200 nm or less on at least the outermost surface, and performs antireflection by optical interference of the low refractive index layer. However, in the case of a one-layer thin film interference type in which reflection is prevented by a single low refractive index layer having the simplest structure, there is nothing that satisfies a reflectance of 1% or less. Furthermore, in order to achieve a reflectance of 0.5% or less, a two-layer thin film interference type in which a high refractive index layer is formed between the support and the low refractive index layer, or between the support and the low refractive index layer. A multilayer thin film interference type antireflection film that prevents reflection by multilayer optical interference, such as a three-layer thin film interference type in which a middle refractive index layer and a high refractive index layer are sequentially formed, is known. In particular, in consideration of productivity and optical characteristics, a two-layer thin film interference type is desirable.

  In order to form a low refractive index layer, many proposals have been made to use a fluorine-containing material or a silicon-containing material as a material having a low refractive index.

  When an organic material having a high refractive index is used when forming the high refractive index layer, there are problems that the upper limit of the refractive index is low and coloring in the visible range is likely to occur. In order to form a high refractive index layer, inorganic fine particles having a high refractive index are usually finely dispersed and introduced into the thin film. A transparent high refractive index layer having a higher refractive index is formed by introducing more inorganic fine particles having a high refractive index into the film while maintaining a fine dispersion state (for example, Patent Documents 2 to 2). 7).

However, there is a problem that the color changes greatly due to slight thickness unevenness of the thin film layer, which is visually detected as unevenness, and that the refractive index and hardness of the low refractive index layer cannot be compatible and the scratch resistance becomes weak. It was.
Furthermore, in the high refractive index layer, there is a problem that the reflection becomes high and conspicuous when minute defects, scratches, etc. of the low refractive index layer occur, and it is necessary to increase the content ratio of particles in the high refractive index layer. There is a problem in that the mechanical strength and durability of the film may be lowered.

  On the other hand, in order to realize high scratch resistance in a thin film having a thickness of 200 nm or less, it is necessary to improve the strength of the film itself.

  To improve the film strength of the outermost low refractive index layer, various methods such as selection of UV curable resin, increase of photopolymerization initiator, addition of silane coupling agent to improve adhesion to the lower layer, etc. It is used. (For example, Patent Documents 8 to 11)

  In general, the mechanical properties are largely governed by the film strength of the outermost low refractive index layer. However, if the mechanical strength of the second high refractive index layer is low, the mechanical characteristics are easily damaged. Therefore, it is necessary to improve the film strength of the high refractive index layer and improve the mechanical strength of the entire antireflection film.

JP 2005-292510 A JP-A-8-110401 JP-A-11-153703 JP 2001-166102 A JP 2001-188104 A JP 2002-116323 A JP 2002-1565088 A JP 2003-222704 A JP 2007-034213 A Japanese Patent No. 5049542 Japanese Patent Laid-Open No. 2007-229999

  Increasing the refractive index of the high refractive index layer to increase the refractive index of the high refractive index layer can be dealt with by increasing the usage ratio of the high refractive index inorganic fine particles. There are problems such as decline.

  An object of the present invention is an antireflection film that has good mechanical properties, reduces the hue of reflected light from the front, and reduces the tint of reflected light of external light incident from all angles, An object of the present invention is to provide a polarizing plate, a touch panel substrate and an image display device provided with the antireflection film.

  The object of the present invention is achieved by the following antireflection film, a polarizing plate provided with the antireflection film, a touch panel substrate, or an image display device.

That is, the first invention includes a hard coat layer, a high refractive index layer whose refractive index is higher than that of the hard coat layer, and a low refractive index layer whose refractive index is lower than that of the hard coat layer on a transparent film substrate. The high refractive index layer is formed of high refractive index fine particles, inorganic particles, and a first ultraviolet curable material, and the average particle diameter of the inorganic particles is 3 nm or more and 20 nm or less. There, the addition amount of the inorganic particles on the solid content of the high refractive index layer-forming composition state, and are 3 parts by weight or more than 20 parts by weight, the low refractive index layer, the low refractive index particles and the second is formed from an ultraviolet-curable material, the amount of the low refractive index fine particles on the solid content of the low refractive index layer forming composition, and wherein 91 parts by weight or less der Rukoto least 83 parts by weight It is an antireflection film.

  A second invention is the antireflection film according to the first invention, wherein an average luminous reflectance on the surface of the antireflection film is 0.5% or less.

  The third invention is the antireflection film according to the first or second invention, wherein the high refractive index layer contains the high refractive index fine particles in a solid content of 50% by mass or more and 80% by mass or less. It is.

  According to a fourth invention, in any one of the first to third inventions, a refractive index of the high refractive index layer is in a range from 1.55 to 1.75, and a refractive index of the low refractive index layer. Is in the range of 1.25 to 1.35.

  A fifth invention is a polarizing plate characterized by using the antireflection film of any one of the first to fourth inventions.

A sixth invention is a touch panel substrate in which the antireflection film of any one of the first to fourth inventions is used.

A seventh invention is an image display device using the antireflection film of any one of the first to fourth inventions.

  According to the present invention, by installing the antireflection film as described above in an image display device or a liquid crystal display device, the average luminous reflectance on the surface of the antireflection film is within a range of 0.5% or less. Antireflection film with good mechanical strength, which can reduce the hue of reflected light from the front, and reduce the tint of reflected light of external light incident from all angles, the reflection A polarizing plate, a touch panel substrate, and an image display device including a prevention film can be obtained.

It is a schematic cross section of one embodiment of the antireflection film of the present invention.

  Hereinafter, although the antireflection film of the present invention will be described in detail, the present invention is not limited thereto.

  In the present invention, “(meth) acrylate” refers to both “acrylate” and “methacrylate”. For example, “urethane (meth) acrylate” indicates both “urethane acrylate” and “urethane methacrylate”.

  Embodiments of the antireflection film of the present invention include a hard coat layer, a high refractive index layer having a refractive index higher than that of the hard coat layer, and a low refractive index having a refractive index lower than that of the hard coat layer on a transparent film substrate. In the antireflection film having a layer, the high refractive index layer is formed of an ultraviolet curable material, high refractive index fine particles, and non-inorganic particles, and the average particle size of the inorganic particles is 3 nm to 20 nm. The inorganic particles are added in an amount of 3 parts by weight or more and 20 parts by weight or less based on the solid content of the composition for forming a high refractive index layer.

  The antireflection film of this embodiment preferably has an average luminous reflectance on the surface of the antireflection film of 0.5% or less.

  When the average luminous reflectance is 0.5% or more, the antireflection effect is insufficient and reflection of external light tends to occur.

  In the antireflection film of this embodiment, the high refractive index layer preferably contains high refractive index fine particles in a solid content of 50% by mass or more and 80% by mass or less.

  When the content of the high refractive index fine particles is below the lower limit, the refractive index of the high refractive index layer is lowered, so that the refractive index difference of the hard coat layer is almost eliminated and the role as the high refractive index layer cannot be achieved. When the content of the high refractive index fine particles exceeds the above upper limit, the amount of the metal fine particles in the coating liquid for forming the high refractive index layer is too large, so that the mechanical strength is significantly lowered.

  Further, in the antireflection film of the present embodiment, the refractive index of the high refractive index layer is in the range from 1.55 to 1.75, and the refractive index of the low refractive index layer is from 1.25 to 1.35. It is preferable that it exists in the range.

  The layer structure of the antireflection film will be described in detail. For the antireflection film of the present invention, a multilayer structure in which a hard coat layer is applied on a transparent film substrate and a high refractive index layer and a low refractive index layer are sequentially laminated can be used. At this time, the number of layers of the high refractive index layer and the low refractive index layer is not limited. However, when considering the cost, good product production rate, etc., as shown in FIG. 1, the antireflection film (10) of the present invention has a hard coat layer (12) applied on the transparent film substrate (11). Furthermore, when a high refractive index layer (13) is applied on the hard coat layer (12) and a low refractive index layer (14) is laminated on the high refractive index layer (13), it is suitably used as an antireflection film. be able to.

At this time, by adjusting the film thickness and refractive index of each layer, the a ^* value and b ^* value, which are hue parameters of the reflected light, can be adjusted to the intended ones.

(High refractive index layer)
Next, the high refractive index layer having a higher refractive index than the transparent resin film will be described. The high refractive index layer in the present invention refers to a layer having a refractive index higher than that of the transparent film substrate. The preferable refractive index of the high refractive index layer of the present invention is preferably in the range of 1.5 to 2.2 when measured at 23 ° C. and a wavelength of 550 nm. From the viewpoint of suppressing coloring of the antireflection film, it is particularly preferably in the range of 1.55 to 1.75. The means for adjusting the refractive index of the high refractive index layer is dominated by the type and addition amount of the high refractive fine particles.

  The film thickness of the high refractive index layer is preferably in the range of 5 nm to 1 μm, more preferably in the range of 10 nm to 0.3 μm, and more preferably in the range of 30 nm to 0. Most preferably, it is in the range of 2 μm.

  The average particle size of the highly refractive fine particles is preferably in the range of 30 nm to 150 nm. When the average particle diameter of the high refractive fine particles exceeds 150 nm, light is remarkably reflected by Rayleigh scattering, and the high and low refractive index layers tend to be whitened to reduce the transparency of the antireflection film. On the other hand, when the average particle diameter of the highly refractive fine particles is less than 30 nm, problems such as insufficient conductivity and aggregation of particles in the high refractive index layer due to aggregation of particles occur.

  The average particle diameter means a 50% particle diameter (d50, that is, a median diameter) when particles in a solution are measured by a dynamic light scattering method and the particle diameter distribution is expressed by a cumulative distribution.

  Next, specific examples of high refractive index fine particles used for adjusting the refractive index of the high refractive index layer will be shown. Specific examples of the high refractive index fine particles include oxides or composite oxides such as Ti, Zr, Ta, In, Nd, Sn, Sb, Zn, La, W, Ce, Nb, V, Sm, and Y, and sulfides. The particle | grains which have as a main component are mentioned. Here, the main component refers to a component having the largest content among the components constituting the particles. More preferable inorganic fine particles in the present invention are particles mainly composed of an oxide or composite oxide containing at least one metal element selected from Ti, Zr, Ta, In, and Sn.

  The high refractive index fine particles may contain various elements in the particles (hereinafter, these elements may be referred to as containing elements). Examples of the contained element include Li, Si, Al, B, Ba, Co, Fe, Hg, Ag, Pt, Au, Cr, Bi, P, and S. In order to increase the conductivity of particles in tin oxide and indium oxide, it is preferable to contain contained elements such as Sb, Nb, P, B, In, V, and halogen, and in particular, those containing antimony are the most. preferable.

The high refractive index fine particles may be surface treated. The surface treatment is a modification of the particle surface using an inorganic compound and / or an organic compound, whereby the wettability of the surface of the inorganic fine particles is adjusted to form fine particles in an organic solvent, and a high refractive index layer. The dispersibility and dispersion stability in the forming composition are improved, which is preferable. Examples of inorganic compounds that are physicochemically adsorbed on the particle surfaces include silicon-containing inorganic compounds (SiO _{2 and the} like), aluminum-containing inorganic compounds [Al ₂ O ₃ , Al (OH) _{3 and the} like], and cobalt. Inorganic compounds containing (CoO ₂ , Co ₂ O ₃ , Co ₃ O ₄ etc.), inorganic compounds containing zirconium [ZrO ₂ , Zr (OH) ₄ etc.], inorganic compounds containing iron (Fe ₂ O ₃ etc.) ) And the like.

  As examples of organic compounds used for the surface treatment, conventionally known surface modifiers of inorganic fillers such as metal oxides and inorganic pigments can be used. For example, it is described in “Pigment Dispersion Stabilization and Surface Treatment Technology / Evaluation”, Chapter 1 (Technical Information Association, published in 2001).

  Specifically, an organic compound having a polar group having an affinity for the surface of the inorganic fine particles and a coupling compound can be mentioned. Examples of the polar group having affinity with the surface of the inorganic fine particles include a carboxy group, a phosphono group, a hydroxy group, a mercapto group, a cyclic acid anhydride group, an amino group, and the like, and a compound containing at least one kind in the molecule is preferable. . For example, long-chain aliphatic carboxylic acids (eg, stearic acid, lauric acid, oleic acid, linoleic acid, linolenic acid, etc.), poly (meth) acrylate compounds of polyols (eg, pentaerythritol tri (meth) acrylate, dipentaerythritol pentane) (Meth) acrylate, ECH (epichlorohydrin) modified glycerol tri (meth) acrylate, etc.), phosphono group-containing compound (for example, EO (ethylene oxide) modified tri (meth) acrylate), alkanolamine (ethylenediamine EO adduct (5) Mol)) and the like.

  As a coupling compound, a conventionally well-known organometallic compound is mentioned, A silane coupling agent, a titanate coupling agent, an aluminate coupling agent, etc. are contained. Silane coupling agents are most preferred. Specific examples include compounds described in paragraph numbers “0011” to “0015” in JP-A-2002-9908 and 2001-310423. Two or more kinds of these surface treatments can be used in combination.

  The high refractive index fine particles used in the present invention are also preferably fine particles having a core / shell structure in which a shell made of another inorganic compound is formed using this as a core. The shell is preferably an oxide composed of at least one element selected from Al, Si, and Zr. Specifically, for example, the contents described in JP-A-2001-166104 can be mentioned.

  The shape of the inorganic fine particles used in the present invention is not particularly limited, but is preferably a rice grain shape, a spherical shape, a cubic shape, a spindle shape or an indefinite shape. The inorganic fine particles in the present invention may be used alone or in combination of two or more.

  In the present invention, the high refractive index layer preferably contains 50 to 80 parts by weight of high refractive index fine particles in the solid content. If it is less than 50 parts by weight, it will be difficult to obtain a sufficiently high refractive index, and if it exceeds 80 parts by weight, it will cause insufficient hardness, etc., and it will cause the appearance failure due to dropout of particles and adhesion to the film surface during coating. It is not preferable.

  The inorganic particles added to the high refractive index layer of the present invention have a refractive index in the range of 1.40 to 2.50, and are characterized by silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, calcium carbonate , Talc, clay, calcined kaolin, calcined calcium silicate, hydrated calcium silicate, aluminum silicate, magnesium silicate and calcium phosphate can be used. Of these, silicon dioxide is particularly preferable.

  The average particle size of the inorganic particles in the high refractive index layer of the present invention is characterized by being in the range of 3 nm to 20 nm. This is because if the average particle size of the inorganic particles is less than 3 nm, sufficient properties cannot be obtained in antifouling properties and mechanical properties. If inorganic particles having an average particle size exceeding 20 nm are added, the surface roughness is increased. This is because deterioration occurs in haze, total light transmittance, antifouling property and mechanical properties.

  Further, the ratio of the inorganic particles in the high refractive index layer of the present invention is characterized by being in the range of 3 parts by weight or more and 20 parts by weight or less with respect to the solid content of the composition for forming a high refractive index layer. This is because if it is less than 3 parts by weight, sufficient antifouling properties and mechanical properties cannot be obtained, and if it exceeds 20 parts by weight, a sufficiently high refractive index cannot be obtained, and as an antireflection film This is because the average luminous reflectance is 0.5% or more.

  Further, the high refractive index layer can contain an ultraviolet curable resin as a binder of high refractive index fine particles in order to improve the film formability and physical properties of the coating film.

  An acrylic material can be used as such an ultraviolet curable resin. Acrylic materials include monofunctional, bifunctional or trifunctional or higher (meth) acrylate compounds such as acrylic acid or methacrylic acid ester of polyhydric alcohol, diisocyanate and polyhydric alcohol, and hydroxyester of acrylic acid or methacrylic acid, etc. A polyfunctional urethane (meth) acrylate compound as synthesized from the above can be used. In addition to these, as the ultraviolet-type material, a polyether resin having an acrylate functional group, a polyester resin, an epoxy resin, an alkyd resin, a spiroacetal resin, a polybutadiene resin, a polythiol polyene resin, or the like can be used.

  Examples of the monofunctional (meth) acrylate compound include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl ( (Meth) acrylate, t-butyl (meth) acrylate, glycidyl (meth) acrylate, acryloylmorpholine, N-vinylpyrrolidone, tetrahydrofurfuryl acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isobornyl (meth) ) Acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, benzyl (Meth) acrylate, 2-ethoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, ethyl carbitol (meth) acrylate, phosphoric acid (meth) acrylate, ethylene oxide modified phosphoric acid (meth) acrylate, phenoxy (meta) ) Acrylate, ethylene oxide modified phenoxy (meth) acrylate, propylene oxide modified phenoxy (meth) acrylate, nonylphenol (meth) acrylate, ethylene oxide modified nonylphenol (meth) acrylate, propylene oxide modified nonylphenol (meth) acrylate, methoxydiethylene glycol (meth) Acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypropylene glycol (meth) acrylate 2- (meth) acryloyloxyethyl-2-hydroxypropyl phthalate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2- (meth) acryloyloxyethyl hydrogen phthalate, 2- (meth) acryloyloxypropyl hydrogen Phthalate, 2- (meth) acryloyloxypropyl hexahydrohydrogen phthalate, 2- (meth) acryloyloxypropyl tetrahydrohydrogen phthalate, dimethylaminoethyl (meth) acrylate, trifluoroethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate , Hexafluoropropyl (meth) acrylate, octafluoropropyl (meth) acrylate, octafluoropropyl (meth) acrylate, 2 -Adamantane derivative mono (meth) acrylates such as adamantyl acrylate having a monovalent mono (meth) acrylate derived from adamantane and adamantanediol.

  Examples of the bifunctional (meth) acrylate compound include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, butanediol di (meth) acrylate, hexanediol di (meth) acrylate, and nonanediol di (meth). ) Acrylate, ethoxylated hexanediol di (meth) acrylate, propoxylated hexanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (Meth) acrylate, neopentyl glycol di (meth) acrylate, ethoxylated neopentyl glycol di (meth) acrylate, tripropylene glycol Ruji (meth) acrylate, di (meth) acrylate, such as hydroxypivalic acid neopentyl glycol di (meth) acrylate.

  Examples of the trifunctional or higher functional (meth) acrylate compound include trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, and tris 2-hydroxy. Ethyl isocyanurate tri (meth) acrylate, tri (meth) acrylate such as glycerin tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, etc. Trifunctional (meth) acrylate compounds, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol te Trifunctional or higher polyfunctionality such as la (meth) acrylate, dipentaerythritol penta (meth) acrylate, ditrimethylolpropane penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ditrimethylolpropane hexa (meth) acrylate ( Examples thereof include a (meth) acrylate compound and a polyfunctional (meth) acrylate compound obtained by substituting a part of these (meth) acrylates with an alkyl group or ε-caprolactone.

  Among acrylic materials, polyfunctional urethane acrylates can be suitably used because the desired molecular weight and molecular structure can be designed and the physical properties of the formed hard coat layer can be easily balanced. . The urethane acrylate is obtained by reacting a polyhydric alcohol, a polyvalent isocyanate, and a hydroxyl group-containing acrylate. Specifically, Kyoeisha Chemical Co., Ltd., UA-306H, UA-306T, UA-306l, etc., Nippon Synthetic Chemical Co., Ltd., UV-1700B, UV-6300B, UV-7600B, UV-7605B, UV-7640B, UV -7650B, etc., manufactured by Shin-Nakamura Chemical Co., Ltd., U-4HA, U-6HA, UA-100H, U-6LPA, U-15HA, UA-32P, U-324A, etc., manufactured by Daicel UCB, Ebecryl-1290, Ebecryl -1290K, Ebecryl-5129, etc., manufactured by Negami Kogyo Co., Ltd., UN-3220HA, UN-3220HB, UN-3220HC, UN-3220HS, etc. can be mentioned, but not limited thereto.

  In addition to these, as an ultraviolet curable material, polyether resins, polyester resins, epoxy resins, alkyd resins, spiroacetal resins, polybutadiene resins, polythiol polyene resins having an acrylate functional group can be used. The material is not particularly limited.

  In the present invention, the high refractive index layer preferably contains an ultraviolet curable resin in a solid content of 15 parts by weight or more and 45 parts by weight or less.

  Moreover, since an ultraviolet curable material is hardened | cured by an ultraviolet-ray, a photoinitiator is added to the coating liquid for hard-coat layer formation. The photopolymerization initiator may be any one that generates radicals when irradiated with ultraviolet rays. Specific examples include acetophenone compounds, benzoin compounds, benzophenone compounds, oxime ester compounds, thioxanthone compounds, Examples include triazine compounds, phosphine compounds, quinone compounds, borate compounds, carbazole compounds, imidazole compounds, titanocene compounds, and the like. Examples of acetophenone compounds include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, and 1-hydroxy. Cyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane- Examples include 1-one. Examples of benzoin compounds include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzyl dimethyl ketal. Examples of the benzophenone compounds include benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, and the like. Examples of oxime ester compounds include etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (0-acetyloxime), 1,2-octadione- Examples thereof include 1- [4- (phenylthio)-, 2- (O-benzoyloxime)] and the like. Examples of the thioxanthone compound include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone and the like. Examples of triazine compounds include 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, and 2- (p-methoxyphenyl) -4,6-bis. (Trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-pienyl-4,6-bis (trichloromethyl) -s-triazine, 2 , 4-Bis (trichloromethyl) -6-styryl s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxy-naphth-1) -Yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, 2,4-trichloromethyl (4 ' Methoxystyryl) -6-triazine and the like. Examples of the phosphine compound include bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide and 2,4,6-trimethylbenzoyldiphenylphosphine oxide. Examples of the quinone compound include 9,10-phenanthrenequinone, camphorquinone, and ethylanthraquinone. A photoinitiator may be used independently and may be used in combination of 2 or more type.

  The content of the photopolymerization initiator can be used in the solid content of 0.01 to 20 parts by weight, preferably 0.05 to 5 parts by weight.

  Further, other additives may be added to the coating solution for forming a high refractive index layer. Examples of the additive include a defoaming agent, a leveling agent, an antioxidant, an ultraviolet absorber, a light stabilizer, and a polymerization inhibitor.

  An organic solvent is preferably used when applying the high refractive index layer. Examples of the organic solvent include alcohols (eg, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, secondary butanol, tertiary butanol, pentanol, hexanol, cyclohexanol, benzyl alcohol, etc.), polyhydric alcohols ( For example, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexanediol, pentanediol, glycerin, hexanetriol, thiodiglycol, etc.), polyhydric alcohol ethers ( For example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene Glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, ethylene glycol monophenyl ether , Propylene glycol monophenyl ether, etc.), amines (for example, ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, morpholine, N-ethylmorpholine, ethylenediamine, diethylenediamine, trie Lentetramine, tetraethylenepentamine, polyethyleneimine, pentamethyldiethylenetriamine, tetramethylpropylenediamine, etc.), amides (eg, formamide, N, N-dimethylformamide, N, N-dimethylacetamide, etc.), heterocyclics (eg, 2-pyrrolidone, N-methyl-2-pyrrolidone, cyclohexyl pyrrolidone, 2-oxazolidone, 1,3-dimethyl-2-imidazolidinone, etc.), sulfoxides (eg dimethyl sulfoxide etc.), sulfones (eg sulfolane) Etc.), urea, acetonitrile, acetone and the like, and alcohols, polyhydric alcohols, and polyhydric alcohol ethers are particularly preferable.

  The high refractive index layer is obtained by applying the above composition to a transparent resin film or hard coat layer surface using a gravure coater, dip coater, reverse coater, wire bar coater, die coater, spray coating, ink jet coating or the like. It is applied at 1 to 100 μm, and after application, it is heated and dried, and is cured as necessary. The content described in the low refractive index layer described later can be used in the curing step.

  The dry film thickness is adjusted to the above film thickness by adjusting the solid content concentration of the coating composition.

(Low refractive index layer)
As a low refractive index layer in the antireflection film of the present invention, as low refractive particles, LiF, MgF, 3NaF.AlF or AlF (all of which have a refractive index of 1.4), or Na ₃ AlF ₆ (cryolite) In addition, low refractive index fine particles made of a low refractive material such as a refractive index of 1.33) can be used. Moreover, the particle | grains which have a space | gap inside a particle | grain can be used suitably. In the case of particles having voids inside the particles, the voids can be made to have a refractive index of air (≈1), so that the particles can have low refractive index having a very low refractive index. Specifically, low refractive index silica particles having voids inside can be used.

  The low refractive index fine particles used in the low refractive index layer of the present invention preferably have an average particle diameter of 1 nm to 100 nm. When the average particle diameter of the low refractive index fine particles exceeds 100 nm, light is remarkably reflected by Rayleigh scattering, and the low refractive index layer tends to be whitened to reduce the transparency of the antireflection film. On the other hand, when the average particle diameter of the low refractive index fine particles is less than 1 nm, problems such as non-uniformity of particles in the low refractive index layer due to particle aggregation occur.

  The binder matrix forming material for forming the low refractive index layer includes an ultraviolet curable material. As the ultraviolet curable material, an acrylic material exemplified as the ultraviolet curable material contained in the coating liquid for forming a high refractive index layer can be used.

  Further, since the ultraviolet curable material is cured by ultraviolet rays, a photopolymerization initiator is added to the coating solution for forming the low refractive index layer. As a photoinitiator, what was illustrated as a photoinitiator contained in the coating liquid for high refractive index layer formation can be used. Moreover, the addition amount of a photoinitiator is 0.1 weight part-10 weight part with respect to 100 weight part of ultraviolet curable materials, Preferably it is 1 weight part-7 weight part, More preferably, it is 1 weight part-5 weight. Part.

  Further, other additives may be added to the coating solution for forming a low refractive index layer. Examples of the additive include a defoaming agent, a leveling agent, an antioxidant, an ultraviolet absorber, a light stabilizer, and a polymerization inhibitor.

(Hard coat layer)
As the hard coat layer in the antireflection film of the present invention, the acrylic material exemplified as the ultraviolet curable material contained in the coating liquid for forming a high refractive index layer can be used.

  Moreover, since an ultraviolet curable material is hardened | cured by an ultraviolet-ray, a photoinitiator is added to the coating liquid for hard-coat layer formation. As a photoinitiator, what was illustrated as a photoinitiator contained in the coating liquid for high refractive index layer formation can be used. Moreover, the addition amount of a photoinitiator is 0.1 weight part-10 weight part with respect to 100 weight part of ultraviolet curable materials, Preferably it is 1 weight part-7 weight part, More preferably, it is 1 weight part-5 weight. Part.

  Furthermore, a solvent and various additives can be added to the coating liquid for forming a hard coat layer as necessary. Solvents include aromatic hydrocarbons such as toluene, xylene, cyclohexane and cyclohexylbenzene, hydrocarbons such as n-hexane, dibutyl ether, dimethoxymethane, dimethoxyethane, diethoxyethane, propylene oxide, dioxane, dioxolane, and trioxane. , Ethers such as tetrahydrofuran, anisole and phenetole, and ketones such as methyl isobutyl ketone, methyl butyl ketone, acetone, methyl ethyl ketone, diethyl ketone, dipropyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, methylcyclohexanone, and methylcyclohexanone , Ethyl formate, propyl formate, n-pentyl formate, methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, Coating suitability among esters such as acid n-pentyl and γ-ptyrolactone, cellosolves such as methyl cellosolve, cellosolve, butyl cellosolve, cellosolve acetate, and alcohols such as methanol, ethanol, isopropyl alcohol, butanol, etc. Is selected as appropriate. In addition, a surface adjusting agent, a refractive index adjusting agent, an adhesion improver, a curing agent, and the like can be added to the coating liquid as additives.

  Moreover, you may add another additive to the coating liquid for hard-coat layer formation. Examples of the additive include a defoaming agent, a leveling agent, an antioxidant, an ultraviolet absorber, a light stabilizer, and a polymerization inhibitor.

  Examples of the coating method of the hard coat layer, the high refractive index layer and the low refractive index layer in the present invention include existing coating methods such as a spray method, a screen printing method, a doctor blade method, a gravure printing method, a die coating method, and an inkjet method. However, it is not particularly limited.

  As the transparent film substrate in the antireflection film of the present invention, polyethylene, polypropylene, etc. in consideration of optical properties such as transparency and refractive index of light, as well as various physical properties such as impact resistance, heat resistance and durability. Polyolefins such as polyesters such as polyethylene terephthalate and polyethylene naphthalate, celluloses such as triacetyl cellulose, diacetyl cellulose and cellophane, polyamides such as 6-nylon and 6,6-nylon, acrylics such as polymethyl methacrylate, An organic polymer such as polystyrene, polyvinyl chloride, polyimide, polyvinyl alcohol, polycarbonate, ethylene vinyl alcohol, or the like is used. In particular, polyethylene terephthalate, triacetyl cellulose, polycarbonate, and polymethyl methacrylate are preferable. Among these, triacetyl cellulose can be suitably used for various displays because of its low birefringence and good transparency.

  Furthermore, these organic polymers may be added with known additives such as ultraviolet absorbers, infrared absorbers, plasticizers, lubricants, colorants, antioxidants, flame retardants, etc. Can be used. Further, the transparent film substrate may be composed of one or a mixture of two or more selected from the above organic polymers, or a polymer, or may be a laminate of a plurality of layers.

  In addition, it is preferable that the thickness of a transparent film base material exists in the range of 20 micrometers or more and 200 micrometers or less, Furthermore, it is preferable to exist in the range of 20 micrometers or more and 80 micrometers or less.

  The antireflection film of the present invention can be suitably used for the display surface. Examples of the display include LCD, PDP, CRT, projection display, EL display and the like. It can also be used inside a display. The case where the antireflection film of the present invention is used as a member of a liquid crystal display is described below.

  The structure of the antireflection polarizing plate and the transmissive liquid crystal display using the antireflection film of the present invention will be described.

  In a transmissive liquid crystal display, an antireflection polarizing plate, a liquid crystal cell, and a second antireflection film provided with a low refractive index layer non-forming surface, the first polarizing plate having the antireflection film of the present invention bonded to one surface. A polarizing plate and a backlight unit are provided in this order. At this time, the antireflection film side becomes the observation side, that is, the display surface.

  It is a transmissive liquid crystal display provided with a transparent base material for the antireflection film and a transparent base material for the first polarizing plate separately.

  The backlight unit includes a light source and a light diffusing plate. The liquid crystal cell has a structure in which an electrode is provided on one transparent substrate, an electrode and a color filter are provided on the other transparent substrate, and liquid crystal is sealed between both electrodes. The first and second polarizing plates provided so as to sandwich the liquid crystal cell have a structure in which a polarizing layer is sandwiched between transparent substrates.

  In addition, an antireflection film provided with a low refractive index layer on one surface of a transparent base material, and a polarizing layer and a transparent base material are provided in this order on the non-formation surface of the antireflective film. A polarizing plate is formed, and an antireflection polarizing plate, a liquid crystal cell, a second polarizing plate, and a backlight unit are provided in this order. At this time, the low refractive index layer side of the antireflection film becomes the observation side, that is, the display surface.

  Moreover, it is a transmissive liquid crystal display provided with an antireflection polarizing plate provided with a polarizing layer and a transparent substrate in this order as a first polarizing plate on the antireflection layer-free surface of the antireflection film.

  The backlight unit includes a light source and a light diffusing plate. The liquid crystal cell has a structure in which an electrode is provided on one transparent substrate, an electrode and a color filter are provided on the other transparent substrate, and liquid crystal is sealed between both electrodes. The first and second polarizing plates provided so as to sandwich the liquid crystal cell have a structure in which a polarizing layer is sandwiched between transparent substrates.

  Moreover, in the transmissive liquid crystal display of this invention, you may provide another functional member. Other functional members include, for example, a diffusion film, a prism sheet, a brightness enhancement film for effectively using light emitted from a backlight, and a phase difference film for compensating for a phase difference between a liquid crystal cell and a polarizing plate. However, the transmissive liquid crystal display of the present invention is not limited to these.

  As described above, a transmissive liquid crystal display using the antireflection film of the present invention is manufactured.

  EXAMPLES Hereinafter, although an Example and a comparative example further demonstrate this invention, this invention is not limited to the following Example.

<Adjustment example 1>
(Coating liquid for forming hard coat layer)
25 parts by mass of dipentaerythritol triacrylate, 25 parts by mass of pentaerythritol tetraacrylate, 50 parts by mass of urethane acrylate, 5 parts by mass of Irgacure 184 (manufactured by BASF (photopolymerization initiator)) are dissolved in methyl ethyl ketone and hardened. A coating layer forming coating solution, HC1, was prepared.

<Adjustment example 2>
(Coating liquid for high refractive index layer formation)
A mixture having a composition (mass ratio) shown in Table 1 was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to prepare coating solutions for forming a high refractive index layer of HR1 to HR8.

The specific contents of the composition in Table 1 are shown below.
・ High refractive index fine particle solution:
- ATO dispersion: 20% solids, solvent methyl isobutyl ketone, ZrO ₂ dispersion: 50% solids, solvent methyl isobutyl ketone, inorganic particle solution, SiO ₂ dispersion: 20% solids, solvent methyl isobutyl ketone-Al ₂ O ₃ dispersion: solid content 20%, solvent methyl isobutyl ketone TiO ₂ dispersion: solid content 20%, solvent methyl isobutyl ketone Photopolymerization initiator Irg 184: “Irgacure 184” manufactured by BASF
OXE01: “Irgacure OXE01” manufactured by Ciba Japan
・ Irg907: “Irgacure 907” manufactured by Ciba Japan
UV curable resin: Pentaerythritol triacrylate (PETA)
・ Solvent: Methyl isobutyl ketone (MIBK)

<Adjustment example 3>
(Coating liquid for forming low refractive index layer)
A mixture having a composition (mass ratio) shown in Table 2 was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to prepare low-refractive index layer coating liquids LR1 to LR4.

The specific contents of the composition in Table 2 are shown below.
・ Fine particle solution: Porous silica fine particle dispersion (solid content 20%, solvent: methyl isobutyl ketone)
Photopolymerization initiator: Irg 184: “Irgacure 184” manufactured by Ciba Japan
UV curable resin: Pentaerythritol triacrylate (PETA)
・ Solvent: Methyl isobutyl ketone (MIBK)

<Example 1>
(Formation of hard coat layer)
A coating liquid HC1 for forming a hard coat layer is applied to one side of a triacetyl cellulose film (manufactured by Fuji Film: film thickness 40 μm), dried in an oven at 80 ° C. for 60 seconds, and after drying, an ultraviolet irradiation device (Fusion UV System Japan, A transparent hard coat layer having a dry film thickness of 5 μm was formed by irradiating ultraviolet rays at an irradiation dose of 300 mJ / m ² using a light source H bulb. The thickness of the hard coat layer was 5 μm, and the refractive index at a wavelength of 550 nm was 1.52.

(Formation of high refractive index layer)
The coating liquid HR1 for forming a high refractive index layer was applied on the hard coat layer formed by the above method so that the film thickness after drying was 150 nm. Using a UV irradiation device (Fusion UV System Japan, light source H bulb), UV irradiation was performed at an irradiation dose of 192 mJ / m ² and cured to form a high refractive index layer. The film thickness of the high refractive index layer was 165 nm, and the refractive index at a wavelength of 550 nm was 1.58.

(Formation of a low refractive index layer)
The coating solution LR1 for forming a low refractive index layer was applied on the high refractive index layer formed by the above method so that the film thickness after drying was 110 nm. Using a UV irradiation device (Fusion UV System Japan, light source H bulb), UV irradiation was performed at an irradiation dose of 192 mJ / m ² and cured to form a low refractive index layer, thereby preparing an antireflection film. The film thickness of the low reflection layer was 105 nm, and the refractive index at a wavelength of 550 nm was 1.27.

  In Examples 2 to 6 and Comparative Examples 1 to 5, antireflection films were prepared by combining the hard coat layer, the high refractive index layer, and the low refractive index layer shown in Table 3. The refractive index of each layer at a wavelength of 550 nm is shown in Table 3.

<Example 2>
This is an example in which an antireflection film was produced in the same manner as in Example 1 except that HR2 was used for the high refractive index layer.

<Example 3>
This is an example in which an antireflection film was produced in the same manner as in Example 1 except that HR3 was used for the high refractive index layer.

<Example 4>
This is an example in which an antireflection film was produced in the same manner as in Example 1 except that HR4 was used for the high refractive index layer.

<Example 5>
This is an example in which an antireflection film was produced in the same manner as in Example 1 except that HR5 was used for the high refractive index layer.

<Example 6>
This is an example in which an antireflection film was produced in the same manner as in Example 1 except that LR2 was used for the low refractive index layer.

<Comparative Example 1>
This is an example in which an antireflection film was produced in the same manner as in Example 1 except that HR6 was used for the high refractive index layer.

<Comparative example 2>
This is an example in which an antireflection film was produced in the same manner as in Example 1 except that HR7 was used for the high refractive index layer.

<Comparative Example 3>
This is an example in which an antireflection film was produced in the same manner as in Example 1 except that HR8 was used for the high refractive index layer.

<Comparative example 4>
This is an example in which an antireflection film was produced in the same manner as in Example 1 except that LR3 was used for the low refractive index layer.

<Comparative Example 5>
This is an example in which an antireflection film was produced in the same manner as in Example 1 except that LR4 was used for the low refractive index layer.

  Matters that are not particularly described in Examples 2 to 6 and Comparative Examples 1 to 5 conform to the operations and processing in Example 1.

  Next, the antireflection films obtained in Examples 1 to 6 and Comparative Examples 1 to 5 were evaluated by the following methods.

(Coating unevenness)
The in-plane uniformity of the coating film was evaluated for the produced antireflection film. The in-plane uniformity of the coating film was evaluated by visual inspection after applying a matte black paint on the surface of the prepared antireflection film where the low refractive index layer was not formed and performing antireflection treatment. Judgment criteria are shown below.
○: Unevenness ×: Unevenness

(Mechanical strength)
The mechanical strength of the coating film was determined by rubbing the surface of the low refractive index layer 10 times at 200 g / cm ² with steel wool [Bonster # 0000: manufactured by Nippon Steel Wool Co., Ltd.] and visually evaluating the presence or absence of scratches (steel wool test). . Judgment criteria are shown below.
○: No scratch ×: Scratch

(Reflective hue)
About the surface of the low-refractive-index layer of the obtained antireflection film, front and diagonal hues of 45 ° were performed by sensory evaluation. Judgment is
◯: The degree of understanding that the hue change of 45 ° from the front can be understood by careful evaluation under bright illumination. X: The degree of the hue change of 45 ° from the front. In the evaluation, a matte black paint was applied to the surface of the triacetylcellulose film, which is a transparent film substrate, on which the low refractive index layer was not formed, and antireflection treatment was performed.

(Average luminous reflectance)
About the surface of the low refractive index layer of the obtained antireflection film, the spectral reflectance at an incident angle of 5 ° was measured using an automatic spectrophotometer (manufactured by Hitachi, Ltd., U-4100). The average luminous reflectance was determined from the obtained spectral reflectance curve according to JIS R3106. In the measurement, a matte black paint was applied to the surface of the triacetyl cellulose film, which is a transparent film substrate, on which the low refractive index layer was not formed, and antireflection treatment was performed.

(Comprehensive evaluation)
The characteristics as a low reflection film were comprehensively determined by combining the coating unevenness and mechanical strength evaluation results as the film characteristic evaluation with the reflection hue and the average luminous reflectance evaluation result as the optical evaluation.
○: Excellent properties as an antireflection film.
X: The property is not excellent as an antireflection film.

  Table 4 shows the evaluation results.

  From the results of Table 4, the antireflection films of Examples 1 to 6 showed good performance in both film properties and optical properties. On the other hand, in the antireflection film of Comparative Example 1, since the size of the inorganic particles in the coating liquid for forming the high refractive index layer is too large, the average luminous reflection is accompanied by coating unevenness and a decrease in the refractive index of the high refractive index layer. The rate has risen. In addition, in the antireflection film of Comparative Example 2, the amount of inorganic particles added in the coating solution for forming a high refractive index layer is too large, so that coating unevenness, a decrease in scratch resistance, and a decrease in the refractive index of the high refractive index layer are achieved. Increased average luminous reflectance was observed. Moreover, in the antireflection film of Comparative Example 3, the scratch resistance was lowered because there was no addition of inorganic particles in the coating solution for forming a high refractive index layer. In the antireflection film of Comparative Example 4, since the addition amount of the low refractive index fine particles in the low refractive index layer forming coating liquid was small, the average luminous reflectance was 0.5% or more. In the antireflection film of Comparative Example 5, since the amount of the low refractive index fine particles added in the coating solution for forming a low refractive index layer was too large, coating unevenness and a significant decrease in scratch resistance occurred.

<Example 7>
(Preparation of polarizing plate with antireflection film)
A polarizing film was prepared by adsorbing iodine to a stretched polyvinyl alcohol film. The antireflective film of Example 1 of the present invention that has been saponified is attached to one side of the polarizing film using a polyvinyl alcohol adhesive so that the transparent film side (triacetylcellulose) of the antireflective film is the polarizing film side. I attached. A viewing angle widening film (Wi-View film SA12B, manufactured by Fuji Photo Film Co., Ltd.) having an optical compensation layer was saponified and attached to the other side of the polarizing film using a polyvinyl alcohol adhesive. In this way, a polarizing plate was produced. As a result of evaluation in accordance with (Reflection Hue Evaluation) in this polarizing plate state, it was found that the polarizing plate using the antireflection film of Example 1 had no poor appearance and had low reflectance. .

<Example 8>
Furthermore, when the sample of 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. Furthermore, as a result of performing an evaluation according to (reflection hue evaluation) for these display devices, the display device equipped with the antireflection film of the present invention is compared with the display device equipped with the antireflection film of the comparative example. As a result, it was found that the reflectance was kept low without an appearance defect.

<Example 9>
When the sample of Example 1 was bonded to the surface of the organic EL display device and the glass plate on the touch panel surface via an adhesive, and further bonded to the side of the sample via the adhesive, Reflection was suppressed and a highly visible touch panel was obtained. Furthermore, as a result of evaluating these touch panels in accordance with (Reflection Hue Evaluation), it was found that the touch panel equipped with the antireflection film of the present invention had a low reflectance and no poor appearance. .

  The present invention can be applied to an image display device such as a liquid crystal display, a plasma display, a CRT, a projection display, and an EL display, an image display device equipped with a touch panel, and the like.

DESCRIPTION OF SYMBOLS 10 ... Antireflection film 11 ... Transparent film base material 12 ... Hard-coat layer 13 ... High refractive index layer 14 ... Low refractive index layer

Claims (7)

In the antireflection film having a hard coat layer, a high refractive index layer having a refractive index higher than that of the hard coat layer, and a low refractive index layer having a refractive index lower than that of the hard coat layer on the transparent film substrate,
The high refractive index layer is formed of high refractive index fine particles, inorganic particles, and a first ultraviolet curable material,
The average particle diameter of the inorganic particles is at 3nm or 20nm or less, the added amount of the inorganic particles on the solid content of the high refractive index layer-forming composition state, and are less than 20 parts by weight or more and 3 parts by weight,
The low refractive index layer is formed of low refractive index fine particles and a second ultraviolet curable material;
The antireflection film amount of the low refractive index fine particles on the solid content of the low refractive index layer-forming composition, characterized by der Rukoto below 91 parts by weight or more 83 parts by weight.   The antireflection film according to claim 1, wherein an average luminous reflectance on the surface of the antireflection film is 0.5% or less.   The antireflective film according to claim 1 or 2, wherein the high refractive index layer contains the high refractive index fine particles in a solid content of 50 parts by weight or more and 80 parts by weight or less.   The high refractive index layer has a refractive index in the range of 1.55 to 1.75, and the low refractive index layer has a refractive index in the range of 1.25 to 1.35. The antireflection film according to any one of claims 1 to 3.   The antireflection film of any one of Claims 1-4 is used, The polarizing plate characterized by the above-mentioned. The touchscreen board | substrate characterized by using the antireflection film of any one of Claims 1-4 . An image display device using the antireflection film according to any one of claims 1 to 4 .

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