JP2005181834A - Antireflection film, polarizing plate and picture display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an antireflection film which has a satisfactory antireflection property and a visuality enhancing performance of display, at the same time, has an improved resistance to scuffing and, further, has an excellent productivity, and to provide a polarizing plate and a picture display device using the antireflection film. <P>SOLUTION: In the antireflection film, at least one light scattering layer is disposed on a transparent substrate and, further thereon, at least one or more thin film layer formed by supplying reactive gas under application of high frequency voltage nearly at the atmospheric pressure is disposed. In the polarizing plate, the antireflection film is used for one or the other of two sheets of protective films of a polarizer therein. In the picture display device, the antireflection film or the polarizing plate is used for the outermost surface of the display. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to an antireflection film, a polarizing plate using the antireflection film, and an image display device. More specifically, the antireflection film has antireflection properties, scattering properties, scratch resistance, and high productivity. The present invention relates to a polarizing plate and an image display device using the antireflection film.

Antireflection films generally have a function to reduce the reflectance using the principle of optical interference by laminating layers with different refractive indexes, and a function to scatter reflected light by forming irregularities on the surface to blur the reflected image. (Anti-glare function), and placed on the outermost surface of a display device such as a cathode ray tube display (CRT), plasma display (PDP), electroluminescence display (ELD) or liquid crystal display (LCD) In addition, it prevents contrast reduction and image reflection due to external light reflection on the display surface.
In general, in order to impart an antiglare function, particles are dispersed in a transparent resin to form irregularities on the surface of the layer. In addition, the anti-reflection film has light-scattering properties for the purpose of improving viewing angle characteristics, concealing display irregularities, and preventing glare in images when combining anti-glare type anti-reflection films using surface irregularities with high-definition displays. May be granted. When imparting light scattering properties, particles having a refractive index of about 0.5 to 10 μm are dispersed in the transparent resin. The particles for imparting the antiglare function and the particles for imparting the light scattering property as described above may have both functions in one kind of particle, or both functions may be imparted by two or more kinds of particles. However, since unevenness is generated on the surface, it is difficult to uniformly apply a thin optical interference layer of about 100 nm formed thereon.
As a method for forming a layer of an antireflection film, in general, the coating method is advantageous in terms of high productivity and the ability to disperse particles in the layer. However, there are problems such as difficulty in forming a uniform film thickness, poor film density, and environmental burden due to the use of a solvent. On the other hand, vacuum film-forming methods such as sputtering, vacuum deposition, and ion plating can form dense and high-precision thin films, but have problems such as low productivity, large capital investment, and high costs. There is.
From the above, from the viewpoint of performance, it is desirable to form the optical interference layer by the vacuum film-forming method after forming the antiglare function-providing scattering layer by the coating method, but the productivity and cost of the vacuum film-forming method are reduced. There is a problem that it is necessary to solve the problem and it is difficult to provide adhesion between two layers having different methods.
In recent years, there has been a problem that the surface of the antireflection film is easily scratched, and there has been a demand for the development of an antireflection film having excellent surface scratch resistance.

In short, the conventionally proposed antireflection films have not yet been proposed for antireflection films that sufficiently satisfy required performances such as antireflection properties, light scattering properties, and scratch resistance, and that are excellent in productivity. There is no current situation.
An object of the present invention is to provide a highly productive antireflection film while having antireflection properties, scattering properties, and scratch resistance. Furthermore, it is providing the polarizing plate and display apparatus using such an antireflection film.

As a result of intensive studies to solve the above-mentioned problems, the present inventors used a plasma discharge under normal pressure when forming a thin film layer after forming a light scattering layer for imparting an antiglare function by a coating method. It has been found that an antireflection film that achieves the above object can be provided by using a thin film forming method.
According to the present invention, an antireflection film, a polarizing plate and a display device having the following constitution are provided, and the above object is achieved.
(1) An antireflection film in which a light scattering layer is formed on a transparent support, and one or more thin film layers including a low refractive index layer are further formed on the light scattering layer. , At least one kind of translucent particles having an average particle diameter of 0.5 to 5 μm is dispersed in a translucent resin, and a difference in refractive index between the translucent particles and the translucent resin is 0.02. Is a layer formed by a coating method in which the light-transmitting particles are contained in an amount of 3 to 30% by mass of the total solid content of the light scattering layer, and the low refractive index layer is an atmospheric pressure. Alternatively, a refractive index of 1.30 to 1.55 is formed on the surface of the substrate disposed between the electrodes by applying a high-frequency voltage between the opposing electrodes while feeding the reaction gas under a pressure near atmospheric pressure. An antireflection film characterized by being a layer of the above.
(2) An antireflection film in which a light scattering layer is formed on a transparent support, and one or more thin film layers including a low refractive index layer are further formed on the light scattering layer,
The light scattering layer is formed by dispersing at least one kind of translucent particles having an average particle diameter of 0.5 to 5 μm in a translucent resin, and has a refractive index of the translucent particles and the translucent resin. The difference is 0.02 to 0.2, and the translucent particles are contained by 3 to 30% by mass of the total solid content of the light scattering layer.
The high-refractive index layer has at least one high refractive index layer having a higher refractive index than the light scattering layer and the low refractive index layer between the light scattering layer and the low refractive index layer. An antireflection film formed on the surface of a substrate disposed between electrodes by applying a high-frequency voltage between opposing electrodes while sending a reaction gas under atmospheric pressure or a pressure near atmospheric pressure .
(3) The translucent particles are composed of two or more types of translucent particles, and the difference in refractive index between at least two types of the two or more types of translucent particles is 0.01 to 0.2. The antireflection film as described in (1) or (2) above.
(4) The outermost surface of the antireflection film has an arithmetic average roughness Ra of 0.02 to 0.5 μm, an average interval Sm of 5 to 100 μm, and a 10-point average roughness Rz / arithmetic average roughness Ra. The antireflection film as described in any one of (1) to (3) above, which has an uneven shape of 10 or less.
(5) The antireflection according to any one of (1) to (4), wherein the low refractive index layer contains a polymer containing a silicon oxide group and / or a fluorine-containing functional group as a main component. the film.
(6) The antireflective film (7) according to any one of the above (2) to (5), wherein the high refractive index layer is composed mainly of titanium oxide and has a refractive index of 1.6 or more. The antireflection film as described in any one of (1) to (6) above, wherein the film thickness distribution of the low refractive index layer and / or the high refractive index layer is within 5% in an area of 1 m ^2. .
(8) A transparent antistatic layer having a surface resistance of 1 × 10 ¹¹ Ω / □ or less and a haze of 10% or less between the transparent support and the low refractive index layer ( The antireflection film according to any one of 1) to (7).
(9) The antifouling layer comprising a silicon compound and / or a fluorine compound and having a water contact angle of 70 ° or more is formed on the low refractive index layer. The antireflection film as described in any one of 8).
(10) The method for producing an antireflection film according to any one of (1) to (9) above, wherein the surface of the light scattering layer is subjected to a hydrophilic treatment so that the contact angle with water is 70 degrees or less. Thereafter, a method for producing an antireflection film, comprising forming a thin film layer on the surface.
(11) The above-mentioned (10), wherein the roll-like long film in which the light scattering layer is formed on the transparent support is continuously subjected to the hydrophilic treatment on the surface of the light scattering layer and the formation of the thin film layer. The manufacturing method of the antireflection film as described in 1 ..
(12) The above-mentioned (10), wherein the formation of the light scattering layer, the hydrophilic treatment on the surface of the light scattering layer, and the formation of the thin film layer are continuously performed on the roll-shaped long transparent support. ) For producing an antireflection film.
(13) A polarizing plate having the antireflection film according to any one of (1) to (9) as a protective film on one side of the polarizing plate.
(14) An image display device in which the antireflection film as described in (1) to (9) or the polarizing plate as described in (13) is installed so that the low refractive index layer is located on the viewer side.

  The antireflection film of the present invention is excellent in environmental resistance such as sufficient antireflection properties, light scattering properties, and scratch resistance, and is also excellent in productivity. Furthermore, the image display device provided with the antireflection film of the present invention and the image display device provided with a polarizing plate using the antireflection film of the present invention have little reflection of external light and background reflection, and are extremely visible. Is expensive.

A basic configuration of an antireflection film suitable as an embodiment of the present invention will be described with reference to the drawings.
Here, FIG. 1 is a cross-sectional view schematically showing one embodiment of the antireflection film of the present invention.
An antireflection film 1 shown in FIG. 1 includes a transparent support 2, a light scattering layer 3 (hard coat, with an antiglare function) formed on the transparent support 2, and a thin film layer including a low refractive index layer 7. Consists of. The thin film layer is composed of a high refractive index layer (transparent antistatic layer) 4, a low refractive index layer 5, a high refractive index layer 6, a low refractive index layer 7, and an antifouling layer 8 in this order from the light scattering layer 3 side. It is formed with the layer structure. The light scattering layer 3 is formed by dispersing light scattering particles 9 and antiglare particles 10 which are light transmitting particles in a light transmitting resin.
In the present specification, the description of “numerical value A to numerical value B” representing the range of physical property values and the like represents the meaning of “numerical value A” to “numerical value B”.
The refractive index of the translucent resin is preferably in the range of 1.50 to 2.00, the refractive index of the high refractive index layer 4 is preferably in the range of 1.6 to 2.6, and the low refractive index. The refractive index of layer 5 is in the range of 1.30 to 1.55.
In the embodiment of FIG. 1, an example using two types of light scattering particles 9 and anti-glare particles 10 has been described, but it is also possible to use one type of particles having both functions.

  The antireflection film of the present invention has a surface roughness of 0.02 to 0.5 μm in arithmetic average roughness Ra and a ratio Rz / Ra of 10-point average roughness Rz to centerline average roughness Ra is 10 or less. In addition, it is preferable that the average interval (average mountain valley distance) Sm of the unevenness is 5 to 100 μm because uniform antiglare property is achieved.

  Note that the high refractive index, low refractive index, and medium refractive index described later refer to the relative refractive index between layers. That is, each layer has a relationship of refractive index of the high refractive index layer> refractive index of the middle refractive index layer> refractive index of the low refractive index layer.

[Light scattering layer]
First, the light scattering layer in the antireflection film of the present invention will be described.

  In the present invention, the light scattering layer is a layer formed by a coating method. As the solvent composition of the coating solution, it is preferable to use a ketone solvent, which may be either alone or mixed. When mixing, the content of the ketone solvent is 10% by mass or more of the total solvent contained in the coating composition. Preferably there is. Preferably it is 30 mass% or more, More preferably, it is 60 mass% or more.

  The coating solvent may contain a solvent other than the ketone solvent. For example, as a solvent having a boiling point of 100 ° C. or lower, hexane (boiling point 68.7 ° C., hereinafter “° C.” is omitted), heptane (98.4), cyclohexane (80.7), benzene (80.1), etc. Hydrocarbons such as dichloromethane (39.8), chloroform (61.2), carbon tetrachloride (76.8), 1,2-dichloroethane (83.5), trichloroethylene (87.2), etc. Hydrogens, diethyl ether (34.6), diisopropyl ether (68.5), dipropyl ether (90.5), ethers such as tetrahydrofuran (66), ethyl formate (54.2), methyl acetate (57. 8), esters such as ethyl acetate (77.1) and isopropyl acetate (89), acetone (56.1), 2-butanone (= methyl ethyl ketone, 9.6), alcohols such as methanol (64.5), ethanol (78.3), 2-propanol (82.4), 1-propanol (97.2), acetonitrile (81.6) ), Cyano compounds such as propionitrile (97.4), carbon disulfide (46.2), and the like. Of these, ketones and esters are preferable, and ketones are particularly preferable. Among the ketones, 2-butanone is particularly preferable.

  Examples of the solvent having a boiling point of 100 ° C. or higher include octane (125.7), toluene (110.6), xylene (138), tetrachloroethylene (121.2), chlorobenzene (131.7), and dioxane (101.3). ), Dibutyl ether (142.4), isobutyl acetate (118), cyclohexanone (155.7), 2-methyl-4-pentanone (= MIBK, 115.9), 1-butanol (117.7), N, N-dimethylformamide (153), N, N-dimethylacetamide (166), dimethyl sulfoxide (189), and the like. Cyclohexanone and 2-methyl-4-pentanone are preferable.

In the production of the antireflection film of the present invention, the coating solution for the light scattering layer is prepared by dissolving, dispersing, and diluting the solid composition constituting the layer with the solvent having the above composition. The concentration of the coating solution is preferably adjusted as appropriate in consideration of the viscosity of the coating solution and the specific gravity of the layer material, but is preferably 5 to 70% by mass, more preferably 10 to 60% by mass.
Moreover, the solvent of each functional layer and the low refractive index layer may be the same composition, and may differ.

The light-scattering layer contains a light-transmitting resin for imparting hard coat properties and light-scattering particles for imparting light-scattering properties as essential components, and preferably further anti-glare for imparting anti-glare properties. It is a layer formed by coating the transparent support with a coating liquid formed by adding particles and an inorganic filler for increasing the refractive index, preventing crosslinking shrinkage, and increasing the strength.
The translucent resin is preferably a binder polymer having a saturated hydrocarbon chain or a polyether chain as a main chain, and more preferably a binder polymer having a saturated hydrocarbon chain as a main chain. The binder polymer preferably has a crosslinked structure.
As the binder polymer having a saturated hydrocarbon chain as a main chain, a polymer of an ethylenically unsaturated monomer is preferable. As the binder polymer having a saturated hydrocarbon chain as the main chain and having a crosslinked structure, a (co) polymer of monomers having two or more ethylenically unsaturated groups is preferable.
In order to obtain a high refractive index, the monomer structure preferably contains an aromatic ring or at least one atom selected from halogen atoms other than fluorine, sulfur atoms, phosphorus atoms, and nitrogen atoms.

  Examples of the monomer having two or more ethylenically unsaturated groups include esters of polyhydric alcohol and (meth) acrylic acid, such as ethylene glycol di (meth) acrylate, 1,4-cyclohexanediacrylate, pentaerythritol tetra (Meth) acrylate], pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, Dipentaerythritol hexa (meth) acrylate, pentaerythritol hexa (meth) acrylate, 1,2,3-cyclohexanetetramethacrylate, polyurethane polyacrylate, polyester Acrylate], vinylbenzene and derivatives thereof (eg, 1,4-divinylbenzene, 4-vinylbenzoic acid-2-acryloylethyl ester, 1,4-divinylcyclohexanone), vinylsulfone (eg, divinylsulfone), acrylamide ( Examples include methylenebisacrylamide) and methacrylamide. Two or more of these monomers may be used in combination. In the present specification, “(meth) acrylate” is used to mean “acrylate or methacrylate”.

  Specific examples of the high refractive index monomer include bis (4-methacryloylthiophenyl) sulfide, vinyl naphthalene, vinyl phenyl sulfide, 4-methacryloxyphenyl-4′-methoxyphenyl thioether, and the like. Two or more of these monomers may be used in combination.

Polymerization of these monomers having an ethylenically unsaturated group can be carried out by irradiation with ionizing radiation or heating in the presence of a photo radical initiator or a thermal radical initiator.
Accordingly, a coating liquid containing a monomer having an ethylenically unsaturated group, a photo radical initiator or a thermal radical initiator, translucent particles (mat particles) and an inorganic filler is prepared, and the coating liquid is placed on the transparent support. After coating, it can be cured by a polymerization reaction with ionizing radiation or heat to form a light scattering layer of the antireflection film.

As radical photopolymerization initiators, acetophenones, benzoins, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones, azo compounds, peroxides, 2,3-dialkyldione compounds, disulfide compounds And fluoroamine compounds and aromatic sulfoniums. Examples of acetophenones include 2,2-diethoxyacetophenone, p-dimethylacetophenone, 1-hydroxydimethylphenyl ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-4-methylthio-2-morpholinopropiophenone and 2 -Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone is included. Examples of benzoins include benzoin benzene sulfonate, benzoin toluene sulfonate, benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether. Examples of benzophenones include benzophenone, 2,4-dichlorobenzophenone, 4,4-dichlorobenzophenone and p-chlorobenzophenone. Examples of phosphine oxides include 2,4,6-trimethylbenzoyldiphenylphosphine oxide.
Various examples are described in the latest UV curing technology (P.159, issuer; Kazuhiro Takasagi, publisher; Technical Information Association, Inc., published in 1991), which is useful for the present invention.
Preferable examples of commercially available photocleavable photoradical polymerization initiators include Irgacure (651, 184, 907) manufactured by Nippon Ciba-Geigy Co., Ltd.
It is preferable to use a photoinitiator in the range of 0.1-15 mass parts with respect to 100 mass parts of polyfunctional monomers, More preferably, it is the range of 1-10 mass parts.
In addition to the photopolymerization initiator, a photosensitizer may be used. Specific examples of the photosensitizer include n-butylamine, triethylamine, tri-n-butylphosphine, Michler's ketone and thioxanthone.

As the thermal radical initiator, organic or inorganic peroxides, organic azo, diazo compounds, and the like can be used.
Specifically, benzoyl peroxide, halogen benzoyl peroxide, lauroyl peroxide, acetyl peroxide, dibutyl peroxide, cumene hydroperoxide, butyl hydroperoxide as organic peroxides, hydrogen peroxide, peroxides as inorganic peroxides. Ammonium sulfate, potassium persulfate, etc., 2-azo-bis-isobutyronitrile, 2-azo-bis-propionitrile, 2-azo-bis-cyclohexanedinitrile, etc. as diazo compounds, diazoaminobenzene, p-nitrobenzenediazonium Etc.

The polymer having a polyether as the main chain is preferably a ring-opening polymer of a polyfunctional epoxy compound. The ring-opening polymerization of the polyfunctional epoxy compound can be performed by irradiation with ionizing radiation or heating in the presence of a photoacid generator or a thermal acid generator.
Accordingly, a coating liquid containing a polyfunctional epoxy compound, a photoacid generator or a thermal acid generator, matte particles and an inorganic filler is prepared, and the coating liquid is applied onto a transparent support and then subjected to a polymerization reaction by ionizing radiation or heat. It can be cured to form a light scattering layer of the antireflection film.

Instead of or in addition to a monomer having two or more ethylenically unsaturated groups, a monomer having a crosslinkable functional group is used to introduce a crosslinkable functional group into the polymer, and by reaction of this crosslinkable functional group, A crosslinked structure may be introduced into the binder polymer.
Examples of the crosslinkable functional group include an isocyanate group, an epoxy group, an aziridine group, an oxazoline group, an aldehyde group, a carbonyl group, a hydrazine group, a carboxyl group, a methylol group, and an active methylene group. Vinylsulfonic acid, acid anhydride, cyanoacrylate derivative, melamine, etherified methylol, ester and urethane, and metal alkoxide such as tetramethoxysilane can also be used as a monomer for introducing a crosslinked structure. A functional group that exhibits crosslinkability as a result of the decomposition reaction, such as a block isocyanate group, may be used. That is, in the present invention, the crosslinkable functional group may not react immediately but may exhibit reactivity as a result of decomposition.
These binder polymers having a crosslinkable functional group can form a crosslinked structure by heating after coating.

The translucent particles used in the light scattering layer are used for the purpose of imparting light scattering properties and antiglare properties, and have an average particle size of 0.5 to 5 μm, preferably 1 to 4 μm. When the average particle size is less than 0.5 μm or more than 5 μm, good light scattering properties cannot be obtained. The light scattering layer may further contain inorganic filler particles having a particle size of 100 nm or less.
Specific examples of the translucent particles include particles of inorganic compounds such as silica particles and TiO ₂ particles; acrylic particles, crosslinked acrylic particles, methacrylic particles, crosslinked methacrylic particles, polystyrene particles, crosslinked styrene particles, melamine resin particles, Preferred examples include resin particles such as benzoguanamine resin particles. Of these, crosslinked styrene particles, crosslinked acrylic particles, crosslinked acrylic styrene particles, and silica particles are preferable.
The translucent particles can be either spherical or indefinite.

Moreover, you may use together and use 2 or more types of translucent particle | grains from which a particle diameter differs. It is possible to impart an antiglare property with a light-transmitting particle having a larger particle size and to impart another optical characteristic with a light-transmitting particle having a smaller particle size. For example, when an antireflection film is attached to a high-definition display of 133 ppi or higher, it is required that there is no problem in optical performance called glare as described above. Glare is derived from the fact that the unevenness of the film surface (which contributes to antiglare properties) causes the pixels to be enlarged or reduced and loses brightness uniformity, but is smaller than the light-transmitting particles that impart antiglare properties. The diameter can be greatly improved by using translucent particles different from the refractive index of the binder.
Thus, when using 2 or more types of translucent particle | grains, the difference of the refractive index of the translucent particle to be used (difference of particles with the highest refractive index and particles with the lowest refractive index) is 0.01-0. 2 is preferable in terms of both antiglare properties and imparting light scattering properties, and more preferably 0.02 to 0.18. That is, in the present invention, it is preferable that the translucent particles are composed of at least two kinds of translucent particles and the difference in refractive index of the translucent particles is not in the above range.

  Further, the particle size distribution of the translucent particles is most preferably monodispersed, and the particle size of each particle is preferably as close as possible. For example, when particles having a particle size of 20% or more than the average particle size are defined as coarse particles, the proportion of coarse particles is preferably 1% or less of the total number of particles, more preferably 0.1%. Or less, more preferably 0.01% or less. The translucent particles having such a particle size distribution are obtained by classification after a normal synthesis reaction, and a more preferable distribution can be obtained by increasing the number of classifications or increasing the degree thereof.

The translucent particles are blended in the formed light scattering layer so as to be contained in an amount of 3 to 30% by mass in the total solid content of the light scattering layer. Preferably it is 5-25 mass%. If it is less than 3% by mass, the light scattering effect is lowered, and if it exceeds 30% by mass, the light transmittance is lowered.
The density of the translucent particles is preferably 10 to 1000 mg / m ² , more preferably 100 to 700 mg / m ² .
The particle size distribution of the translucent particles is measured by a Coulter counter method, and the measured distribution is converted into a particle number distribution.

In addition to translucent particles, the light scattering layer preferably contains the inorganic filler in order to increase the refractive index of the layer. The inorganic filler is made of an oxide of at least one metal selected from titanium, zirconium, aluminum, indium, zinc, tin, and antimony, and has an average particle size of 0.2 μm or less, preferably 0.1 μm or less. Preferably it is 0.06 micrometer or less.
Conversely, in order to increase the difference in refractive index between the translucent particles and the translucent resin, in the light scattering layer using the high refractive index translucent particles, in order to keep the refractive index of the layer low. It is also preferable to use an oxide of silicon. The preferred particle size is the same as that of the aforementioned inorganic filler.
Specific examples of the inorganic filler used in the light scattering layer include TiO ₂ , ZrO ₂ , Al ₂ O ₃ , In ₂ O ₃ , ZnO, SnO ₂ , Sb ₂ O ₃ , ITO and SiO ₂ . TiO ₂ and ZrO ₂ are particularly preferable in terms of increasing the refractive index. The surface of the inorganic filler is preferably subjected to a silane coupling treatment or a titanium coupling treatment, and a surface treatment agent having a functional group capable of reacting with a binder species on the filler surface is preferably used.
When using these inorganic fillers, the addition amount is preferably 10 to 90% of the total mass of the light scattering layer, more preferably 20 to 80%, and particularly preferably 30 to 75%.
Such an inorganic filler does not scatter because its particle size is sufficiently smaller than the wavelength of light, and a dispersion in which the filler is dispersed in a binder polymer behaves as an optically uniform substance.

  The bulk refractive index of the mixture of binder and inorganic filler in the light scattering layer of the present invention is preferably 1.48 to 2.00, more preferably 1.50 to 1.80. In order to make the refractive index within the above range, the kind and amount ratio of the binder and the inorganic filler may be appropriately selected. How to select can be easily known experimentally in advance.

  The film thickness of the light scattering layer is preferably 1 to 10 μm, more preferably 1.2 to 6 μm.

In addition, the present inventors have confirmed that the intensity distribution of scattered light measured with a goniophotometer correlates with the viewing angle improvement effect. That is, the more the light emitted from the backlight is scattered by the light scattering film installed on the polarizing plate surface on the viewing side, the better the viewing angle characteristics. However, if the light is scattered too much, back scattering increases and the front brightness decreases, or the scattering is too large and the image clarity deteriorates. Therefore, it is necessary to control the scattered light intensity distribution within a certain range. Therefore, as a result of intensive studies, in order to achieve the desired visual characteristics, the scattered light intensity at 30 °, which correlates particularly with the visual angle improvement effect, is 0.01 with respect to the light intensity at the output angle 0 ° of the scattered light profile. % To 0.2% is preferable, 0.02% to 0.15% is more preferable, and 0.03% to 0.1% is particularly preferable.
The scattered light profile can be measured using the automatic variable angle photometer GP-5 manufactured by Murakami Color Research Laboratory Co., Ltd. for the created light scattering film.

  The light scattering layer in the antireflection film of the present invention has a surface modification of either fluorine or silicone, particularly in order to ensure surface uniformity without application unevenness, drying unevenness, point defects, etc., at high speed application. An agent or both of them can also be contained in the coating composition for forming the functional layer. In particular, a fluorine-based surface modifier is preferably used because an effect of improving surface defects such as coating unevenness, drying unevenness, and point defects of the antireflection film appears with a smaller addition amount.

The light scattering layer of the antireflection film of the present invention can be formed by the following method, but is not limited to this method.
First, a coating solution containing components for forming a layer is prepared. Next, the coating solution is prepared by a dip coating method, an air knife coating method, a curtain coating method, a roller coating method, a wire bar coating method, a gravure coating method, a die coating method or an extrusion coating method (see US Pat. No. 2,681,294). It is coated on a transparent support, heated and dried, and a die coating method, a wire bar coating method, and a micro gravure coating method are particularly preferable. Thereafter, the monomer for forming the layer is polymerized and cured by light irradiation or heating. Thereby, a light scattering layer is formed.

  The microgravure coating method used in the present invention is a gravure roll having a diameter of about 10 to 200 mm, preferably about 20 to 120 mm, and engraved with a gravure pattern on the entire circumference, below the support and in the transport direction of the support The gravure roll is rotated in reverse with respect to the gravure roll, the excess coating liquid is scraped off from the surface of the gravure roll by a doctor blade, and a fixed amount of the coating liquid is removed from the support in a position where the upper surface of the support is in a free state. The coating method is characterized in that the coating liquid is transferred onto the lower surface for coating. A roll-shaped transparent support is continuously unwound, and a hard coat layer, a light scattering layer, a fluoropolymer-containing low refractive index layer, etc. are coated on one side of the unwound support by a microgravure coating method. can do.

  As coating conditions by the micro gravure coating method, the number of gravure patterns engraved on the gravure roll is preferably 50 to 800 / inch, more preferably 100 to 300 / inch, and the depth of the gravure pattern is 1 to 600 μm. Is preferable, 5 to 200 μm is more preferable, the rotation speed of the gravure roll is preferably 3 to 800 rpm, more preferably 5 to 200 rpm, and the conveyance speed of the support is 0.5 to 100 m / min. It is preferably 1 to 50 m / min.

[Hydrophilic treatment]
The surface of the light scattering layer is hydrophilized before the thin film layer is provided thereon, and the contact angle of water is set to 70 degrees or less, because the adhesion with the thin film layer is improved. preferable.
As a hydrophilic treatment method, there are a method of treating in a vacuum and a method of treating near atmospheric pressure. As a method of processing in a vacuum, there is a method of generating a plasma by introducing a gas into a vacuum and applying a direct current or a high frequency voltage to an electrode, and processing the surface of the substrate with the plasma. Moreover, as a method of processing near atmospheric pressure, there are UV irradiation processing, corona discharge processing, and glow discharge processing. The hydrophilicity of the surface of the light scattering layer that has been subjected to hydrophilic treatment can be measured by the contact angle of water. As described above, the contact angle of water is desirably 70 degrees or less, more desirably 50 degrees or less, and particularly desirably 40 degrees or less. As long as the contact angle of water can be reduced, any method of hydrophilic treatment can be selected. However, considering productivity and treatment cost, treatment near atmospheric pressure is desirable, and corona discharge treatment and glow discharge treatment are particularly desirable. . By these treatments, the surface of the substrate is preferably removed from 1 nm to 150 nm, and more preferably from 3 nm to 80 nm.
In order to increase the effect of the surface treatment, it is desirable to have an ester bond in the material for forming the light scattering layer. When it has an ester bond, the ester bond is cleaved by corona discharge treatment and atmospheric pressure plasma discharge treatment, and a carboxylic acid group is generated on the surface, so that the adhesion to the thin film layer formed thereon can be improved. . In order to have an ester bond in the light-scattering layer, it is desirable to have the above-mentioned monomer having two or more ethylenically unsaturated groups as the binder polymer, desirably 10% or more of the monomer component, % Or more is more desirable, and 50% or more is particularly desirable.
In addition, when an inorganic component is contained in the light scattering layer, a hydrophilic group such as —COOH and —Si (Y) ₂ OH is formed by corroding the surface of the light scattering layer by corona discharge treatment and glow discharge treatment. It can expose and can improve adhesiveness with a thin film layer. Y represents a group bonded to Si by O, N, C or the like.

[Thin film layer]
The antireflection film of the present invention is produced by forming a light scattering layer on a transparent support composed of a roll-like long film and then forming an entire thin film layer.
In the present invention, the transparent support preferably has a long film shape, and is used in a roll shape when used. Thereby, manufacture of an antireflection film can be performed continuously.
And a light-scattering layer can be formed by coating continuously the coating liquid for light scattering layer formation mentioned above, sending out a transparent support body.
Furthermore, the hydrophilic treatment on the surface of the light scattering layer can be performed continuously with the coating of the light scattering layer. Furthermore, the coating of the light scattering layer, the hydrophilic treatment on the surface thereof, and the formation of the thin film layer can be performed continuously.
The thin film layer is formed by applying a high-frequency voltage between the opposing electrodes while sending a reaction gas onto the light-scattering layer in the transparent support on which the light-scattering layer is formed, under atmospheric pressure or a pressure near atmospheric pressure. , Formed continuously. Thereby, an antireflection film can be obtained with industrially good productivity.
In the present embodiment, as described above, the low refractive index of the high refractive index layer (transparent antistatic layer), the low refractive index layer, the high refractive index layer, the low refractive index layer, and the antifouling layer is used as the thin film layer. One or more layers are provided.
In the method for forming a thin film layer used in the present invention, a high frequency voltage of 30 KHz or more is applied between opposing electrodes to excite reactive gas to generate plasma. As for the high frequency voltage applied between electrodes, it is especially desirable that the high frequency voltage applied between electrodes for plasma discharge treatment is a frequency of 50 kHz to 150 MHz. If the frequency applied for the plasma discharge treatment is less than 30 kHz, the formed film tends to be porous, and the film becomes weak. If it exceeds 150 MHz, it is difficult to obtain a stable discharge space, and it is particularly preferably 150 MHz or less. As a result, a more uniform and strong film can be formed uniformly.
The above-described discharge plasma treatment is performed at or near atmospheric pressure. Here, “near atmospheric pressure” represents a pressure of 20 kPa to 200 kPa. In order to preferably obtain the effects described in the present invention, 90 kPa to 110 kPa. Is preferred.

  Moreover, in the plasma discharge processing apparatus according to the surface treatment method of the present invention, the maximum height (Rmax) of the surface roughness defined by JIS B 0601 in the electrodes facing each other and the electrodes in contact with the substrate. Is preferably 10 μm or less, more preferably the maximum value of the surface roughness is 8 μm or less, and particularly preferably 7 μm or less.

  The arithmetic average roughness (Ra) defined by JIS B 0601 is preferably 0.5 μm or less, and more preferably 0.1 μm or less.

  Next, the mixed gas according to the surface treatment method of the present invention will be described. In order to form a thin film according to the present invention, a mixed gas containing an organometallic compound or an organic substance in a rare gas is preferably used. By changing the reaction gas, a thin film (layer) having various functions such as a high refractive index layer, a low refractive index layer, a transparent antistatic layer, and an antifouling layer can be formed.

  In order to produce the antireflection film by the surface treatment method of the present invention, it is preferable to adjust the refractive index, film thickness, etc. of the thin film formed on the base material to a desired value, and from this point of view, the present invention As such a mixed gas, a gas containing at least an organic gas containing a rare gas and an organic fluorine compound, a silicon compound or a titanium compound, particularly an organic metal compound such as organic silicon or a titanium compound is used. Here, the mixed gas may contain compounds other than those described above as other components.

  As the film thickness of the thin film obtained by the above surface treatment method, a thin film in the range of 1 nm to 1000 nm is obtained.

  Examples of the rare gas described above include Group 18 elements of the periodic table, specifically helium, neon, argon, krypton, xenon, radon, etc. In order to obtain the effects described in the present invention, Helium and argon are preferably used.

As the organic fluorine compound, a fluorocarbon gas, a fluorinated hydrocarbon gas, or the like is preferably used. For example, tetrafluoromethane (CF ₄ ), hexafluoroethane (C ₂ F ₆ ), tetrafluoroethylene (CF ₂ CF ₂ ), hexafluoropropylene (CF ₃ CFCF ₂ ), octafluorocyclobutane (C Fluorocarbon compounds such as ₄ F ₈ ); fluorinated methane (CH ₂ F ₂ ), fluorinated ethane (CFH ₂ CF ₃ ), fluorinated propylene (CF ₃ CH ₂ CH ₂ F), trifluoropropylene (CH ₂ CHCF ₃₎ fluorinated hydrocarbon compounds such as, further, 1 chloride trifluoride methane (CClF _3), 1 2 tetrafluoromethane chloride (CHClF _2), 2 chloride tetrafluoride cyclobutane (C ₄ H ₂ Cl ₂ F ₄ ) and the like, and halogenated fluoride compounds, and fluorine-substituted products of organic compounds such as alcohols, acids, and ketones. These may be used alone or in combination.

  Examples of the silicon compound include organic metal compounds such as dimethylsilane and tetramethylsilane, metal hydrogen compounds such as monosilane and disilane, metal halogen compounds such as silane dichloride and silane trichloride, tetramethoxysilane, tetraethoxysilane, Examples thereof include alkoxysilanes such as dimethyldiethoxysilane and tetraisopropoxysilane, and organosilicon compounds such as organosilane. The use of organosilicon compounds is particularly preferred, but the invention is not limited thereto. Moreover, these can be used in combination as appropriate. Moreover, these compounds may have an ethylenically unsaturated group in the molecule.

  The above compounds may be used alone or in combination. When the organic fluorine compound described above is used in the mixed gas, the content of the organic fluorine compound in the mixed gas is 0.01 to 10% by volume from the viewpoint of forming a uniform thin film on the substrate by discharge plasma treatment. Although it is preferable, it is 0.1-5 volume% more preferably.

  Further, when the organic fluorine compound is a gas at normal temperature and pressure, it can be used as it is as a component of the mixed gas, so that the method of the present invention can be performed most easily. However, when the organic fluorine compound is liquid or solid at normal temperature and normal pressure, it may be used after being vaporized or sublimated by a method such as heating or decompression, or may be used after being dissolved in an appropriate solvent. .

  When using the above-mentioned silicon compound in the mixed gas, the content of the silicon compound in the mixed gas is 0.1 to 10% by volume from the viewpoint of forming a uniform thin film on the substrate by discharge plasma treatment. However, it is more preferably 0.1 to 5% by volume.

  When a titanium compound is used as the organometallic compound described above, an organometallic compound such as tetradimethylaminotitanium, a metal hydrogen compound such as monotitanium or dititanium, a metal halogen compound such as titanium dichloride, titanium trichloride, or titanium tetrachloride It is preferable to use organic titanium compounds such as metal alkoxides such as tetraethoxytitanium, tetraisopropoxytitanium, and tetrabutoxytitanium, but it is not limited thereto.

  When using the titanium compound described above in the mixed gas, the content of the titanium compound in the mixed gas is 0.1 to 10% by volume from the viewpoint of forming a uniform thin film on the substrate by discharge plasma treatment. However, it is more preferably 0.1 to 5% by volume.

  As the organometallic compounds such as silicon compounds and titanium compounds described above, organometallic compounds such as metal alkoxides are preferable from the viewpoint of handling, because there is no corrosiveness, generation of harmful gases, and there is little contamination in the process. Are preferably used.

  In addition, it is possible to form a conductive layer or an antistatic layer made of these metals by using an organic substance containing a compound containing a metal selected from the group consisting of indium, zinc and tin as the reactive gas. .

  Moreover, the hardness of a thin film can be remarkably improved by containing 0.1-10 volume% of hydrogen gas in the said mixed gas.

  Furthermore, a nonmetallic gas selected from the group consisting of oxygen, carbon monoxide, carbon dioxide, nitrogen monoxide, nitrogen dioxide, hydrogen peroxide and ozone can also be contained.

  In order to introduce the organometallic compound such as the silicon compound and the titanium compound described above into the discharge space, both of them may be in a gas, liquid, or solid state at normal temperature and pressure. In the case of gas, it can be introduced into the discharge space as it is, but in the case of liquid or solid, it is used after being vaporized by means such as heating, decompression or ultrasonic irradiation. When a silicon compound or a titanium compound is vaporized by heating, a metal alkoxide having a liquid boiling point of 200 ° C. or less, such as tetraethoxysilane or tetraisopropoxytitanium, is suitable for a method for producing a low reflection laminate or the like. Used. The metal alkoxide may be used after being diluted with a solvent. As the solvent, an organic solvent such as methanol, ethanol, n-hexane, or a mixed solvent thereof can be used. Since these diluted solvents are decomposed into molecular and atomic forms during the plasma discharge treatment, the influence on the formation of the thin film on the substrate, the composition of the thin film, etc. can be ignored.

  In the surface treatment method according to the present invention, a mixed (reaction) gas containing a rare gas selected from helium, argon, and neon and an organometallic compound such as an organosilicon compound such as alkoxysilane or an organotitanium compound such as alkoxytitanium. It is preferable to use 90 to 99.99% of the rare gas and 0.01 to 10% of the organometallic compound. Using this, it is preferable to form a thin film having the main component of silicon oxide or titanium oxide. Here, “having as a main component” represents a case where the content in the formed thin film is 50 mass% or more.

In order to effectively exhibit the object of the present invention, the refractive index of the low refractive index layer is 1.30 to 1.55, and preferably 1.35 to 1.5. The film thickness distribution of the low refractive index layer is preferably within 5% in an area of 1 m ² .
The high refractive index layer preferably has a refractive index of 1.6 or more, more preferably 1.75 or more. The film thickness distribution of the high refractive index layer is preferably within 5% in an area of 1 m ² .
The transparent antistatic layer is a layer provided between the transparent support and the low refractive index layer, having a surface resistance of 1 × 10 ¹¹ Ω / □ or less and a haze of 10% or less. It is preferable in terms of antistatic properties and translucency, and it is more preferable that the surface resistance is 1 × 10 ¹⁰ Ω / □ or less and the haze is 5% or less.
The material for forming the transparent antistatic layer may be the same as the material for forming the transparent antistatic layer usually used for this type of antireflection film, but a thin film using plasma discharge as in the case of the low refractive index layer as described later. When the layer is formed by the forming method, it is preferably formed of the following materials.

In the case of producing using plasma discharge, the transparent antistatic layer is composed of indium, zinc, tin as well as the organic fluorine compound and / or the silicon compound, and the titanium compound as a reactive gas described later. It is formed by using an organic substance or an organometallic compound containing a compound containing a metal selected from the group.
The refractive index of the transparent antistatic layer is preferably 1.70 to 2.20, more preferably 1.80 to 2.00.

[Anti-fouling layer]
Next, the antifouling layer will be described.
The antifouling layer is a layer provided on the low refractive index layer, and is composed of a silicon compound and / or a fluorine compound, and has a water contact angle of 70 degrees or more, more preferably 90 degrees or more. This is preferable in terms of easy removal of dirt.

In the present invention, a medium refractive index layer having a refractive index lower than that of the high refractive index layer and higher than that of the low refractive index layer may be provided.
As the material for forming the medium refractive index layer, the same material as the material for forming the low refractive index layer or the material for forming the high refractive index layer can be used.

(Transparent support)
As the transparent support of the antireflection film of the present invention, a plastic film is preferably used. Examples of the polymer forming the plastic film include cellulose esters (eg, triacetyl cellulose, diacetyl cellulose, typically TAC-TD80U, TD80UF, etc. manufactured by Fuji Photo Film), polyamide, polycarbonate, polyester (eg, polyethylene terephthalate, polyethylene). Naphthalate), polystyrene, polyolefin, norbornene-based resin (Arton: trade name, manufactured by JSR Corporation), amorphous polyolefin (ZEONEX: trade name, manufactured by Nippon Zeon Corporation), and the like. Of these, triacetyl cellulose, polyethylene terephthalate, and polyethylene naphthalate are preferable, and triacetyl cellulose is particularly preferable. The method for producing triacetylcellulose is described in Japanese Society for Invention and Innovation technique 2001-1745.

  When the antireflection film of the present invention is used in a liquid crystal display device, it is disposed on the outermost surface of the display by providing an adhesive layer on one side. When the transparent support is triacetylcellulose, triacetylcellulose is used as a protective film for protecting the polarizing layer of the polarizing plate. Therefore, it is preferable in terms of cost to use the antireflection film of the present invention as it is for the protective film.

When the antireflection film of the present invention is disposed on the outermost surface of the display by providing an adhesive layer on one side, or when used as it is as a protective film for a polarizing plate, on the transparent support in order to sufficiently adhere It is preferable to carry out a saponification treatment after forming the outermost layer mainly composed of a fluoropolymer. The saponification treatment is performed by a known method, for example, by immersing the film in an alkali solution for an appropriate time. After being immersed in the alkali solution, it is preferable to sufficiently wash with water or neutralize the alkali component by immersing in a dilute acid so that the alkali component does not remain in the film.
By the saponification treatment, the surface of the transparent support opposite to the side having the outermost layer is hydrophilized.
The hydrophilized surface is particularly effective for improving the adhesion with a deflection film containing polyvinyl alcohol as a main component. In addition, the hydrophilic surface makes it difficult for dust in the air to adhere to it, so it is difficult for dust to enter between the deflection film and the antireflection film when bonded to the deflection film, thus preventing point defects due to dust. It is valid.
The saponification treatment is preferably carried out so that the contact angle of water on the surface of the transparent support opposite to the side having the outermost layer is 40 ° or less. More preferably, it is 30 ° or less, particularly preferably 20 ° or less.

Specific means for the alkali saponification treatment can be selected from the following two means (1) and (2). (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, an alkaline solution is applied to the surface of the antireflection film opposite to the surface on which the antireflection film is formed, followed by heating, washing with water and / or medium. By summing, only the back surface of the film is saponified.
The antireflection film of the present invention thus formed has a haze value of 3 to 70%, preferably 4 to 60%, and an average reflectance of 450 nm to 650 nm is preferably 3.0% or less, preferably Is 2.5% or less.
When the antireflection film of the present invention has a haze value and an average reflectance in the above range, good antiglare properties and antireflection properties can be obtained without causing deterioration of the transmitted image.

〔Polarizer〕
Next, the polarizing plate of the present invention will be described.
The polarizing plate is mainly composed of two protective films that sandwich the polarizing film from both sides. And the above-mentioned antireflection film of the present invention is used for at least one of the two protective films sandwiching the polarizing plate and polarizing film of the present invention from both sides. Since the antireflection film of the present invention also serves as a protective film, the production cost of the polarizing plate can be reduced. Further, by using the antireflection film of the present invention as the outermost layer, reflection of external light and the like can be prevented, and a polarizing plate having excellent scratch resistance, antifouling property and the like can be obtained.

As the polarizing film, a known polarizing film or a polarizing film cut out from a long polarizing film whose absorption axis is neither parallel nor perpendicular to the longitudinal direction may be used. A long polarizing film whose absorption axis is neither parallel nor perpendicular to the longitudinal direction is produced by the following method.
That is, with a polarizing film stretched by applying tension while holding both ends of a continuously supplied polymer film by a holding means, stretched at least 1.1 to 20.0 times in the film width direction, The progress of the film is such that the difference between the moving speeds in the longitudinal direction of the holding device is within 3%, and the angle formed between the moving direction of the film at the exit of the process of holding both ends of the film and the substantial stretching direction of the film is inclined by 20 to 70 °. It can be produced by a stretching method in which the direction is bent while holding both ends of the film. In particular, those inclined by 45 ° are preferably used from the viewpoint of productivity.

  The method for stretching the polymer film is described in detail in paragraphs 0020 to 0030 of JP-A-2002-86554.

(Image display device)
The image display device of the present invention is formed by installing the above-described antireflection film of the present invention or the polarizing plate of the present invention so that the low refractive index layer is positioned on the viewer side.
In short, the antireflection film of the present invention can be applied to an image display device such as a liquid crystal display device (LCD), a plasma display panel (PDP), an electroluminescence display (ELD), or a cathode ray tube display device (CRT). . And since the antireflection film of this invention has a transparent support body, it adheres and uses the transparent support body side for the image display surface of an image display apparatus.

  In addition, when the antireflection film of the present invention is used as one side of the surface protective film of the polarizing film, twisted nematic (TN), super twisted nematic (STN), vertical alignment (VA), in-plane switching (IPS) Further, it can be preferably used for a transmissive, reflective, or transflective liquid crystal display device in a mode such as an optically compensated bend cell (OCB).

  The VA mode liquid crystal cell includes (1) a narrowly defined VA mode liquid crystal cell in which rod-like liquid crystalline molecules are aligned substantially vertically when no voltage is applied, and substantially horizontally when a voltage is applied (Japanese Patent Laid-Open No. Hei 2-). (2) In addition to (2) Liquid crystal cell (SID97, Digest of tech. Papers (Preliminary Collection) 28 (1997) 845 in which the VA mode is converted into a multi-domain (MVA mode) for viewing angle expansion ), (3) A liquid crystal cell in a mode (n-ASM mode) in which rod-like liquid crystalline molecules are substantially vertically aligned when no voltage is applied and twisted multi-domain alignment is applied when a voltage is applied (Preliminary collections 58-59 of the Japan Liquid Crystal Society) (1998)) and (4) SURVAVAL mode liquid crystal cells (announced at LCD International 98).

  The OCB mode liquid crystal cell is a liquid crystal display device using a bend alignment mode liquid crystal cell in which rod-like liquid crystalline molecules are aligned in a substantially opposite direction (symmetrically) between the upper part and the lower part of the liquid crystal cell. It is disclosed in the specifications of Japanese Patent Nos. 45882525 and 5410422. Since the rod-like liquid crystal molecules are symmetrically aligned at the upper and lower portions of the liquid crystal cell, the bend alignment mode liquid crystal cell has a self-optical compensation function. Therefore, this liquid crystal mode is also called an OCB (Optically Compensatory Bend) liquid crystal mode. The bend alignment mode liquid crystal display device has an advantage of high response speed.

  In an ECB mode liquid crystal cell, rod-like liquid crystal molecules are substantially horizontally aligned when no voltage is applied, and is most frequently used as a color TFT liquid crystal display device, and is described in many documents. For example, it is described in “EL, PDP, LCD display” published by Toray Research Center (2001).

  Particularly for TN mode and IPS mode liquid crystal display devices, as described in JP-A-2001-100043, an optical compensation film having an effect of widening the viewing angle is used as a protective film on the back and front surfaces of the polarizing film. By using it on the surface opposite to the antireflection film of the present invention, a polarizing plate having an antireflection effect and a viewing angle expansion effect can be obtained with the thickness of one polarizing plate, which is particularly preferable.

[Example]
In order to describe the present invention in detail, examples will be described below, but the present invention is not limited thereto. Unless otherwise specified, “part” and “%” are based on mass.

(Perfluoroolefin copolymer (1) Synthesis of FP1A)

A 40 ml stainless steel autoclave with a stirrer was charged with 40 ml of ethyl acetate, 14.8 g of hydroxyethyl vinyl ether and 0.56 g of dilauroyl peroxide, and the system was degassed and replaced with nitrogen gas. Further, 25 g of hexafluoropropylene (HFP) was introduced into the autoclave and the temperature was raised to 65.5 ° C. The pressure when the temperature in the autoclave reached 65 ° C. was 5.4 kg / cm ² . The reaction was continued for 8 hours while maintaining the temperature, and when the pressure reached 3.3 kg / cm ² , the heating was stopped and the mixture was allowed to cool. When the internal temperature dropped to room temperature, unreacted monomers were driven out, the autoclave was opened, and the reaction solution was taken out. The obtained reaction solution was poured into a large excess of hexane, and the polymer was precipitated by removing the solvent by decantation. Further, this polymer was dissolved in a small amount of ethyl acetate and reprecipitated twice from hexane to completely remove the residual monomer. After drying, 28 g of polymer was obtained. Next, 20 g of the polymer was dissolved in 100 ml of N, N-dimethylacetamide, and 11.6 g of acrylic acid chloride was added dropwise under ice cooling, followed by stirring at room temperature for 10 hours. Ethyl acetate was added to the reaction solution, washed with water, the organic layer was extracted and concentrated, and the resulting polymer was reprecipitated with hexane to obtain 19 g of perfluoroolefin copolymer (1) FP1A. The obtained polymer had a refractive index of 1.425.

(Preparation of sol solution a)
A stirrer, a reactor equipped with a reflux condenser, 120 parts of methyl ethyl ketone, 100 parts of acryloxypropyltrimethoxysilane (KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.), 3 parts of diisopropoxyaluminum ethyl acetoacetate were added and mixed. Thereafter, 30 parts of ion-exchanged water was added and reacted at 60 ° C. for 4 hours, and then cooled to room temperature to obtain sol solution a. The mass average molecular weight was 1600, and among the components higher than the oligomer component, the component having a molecular weight of 1000 to 20000 was 100%. Further, from the gas chromatography analysis, no acryloxypropyltrimethoxysilane as a raw material remained.

(Preparation of coating solution A for light scattering layer)
52 g of a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (PETA, Nippon Kayaku Co., Ltd.) was diluted with 38.8 g of toluene. Furthermore, 2 g of a polymerization initiator (Irgacure 184, manufactured by Ciba Specialty Chemicals Co., Ltd.) was added and mixed and stirred. The refractive index of the coating film obtained by applying this solution and curing with ultraviolet rays was 1.51.
Further, a 30% toluene dispersion of crosslinked polystyrene particles having an average particle size of 3.5 μm (refractive index: 1.60, SX-350, manufactured by Soken Chemical Co., Ltd.) dispersed in this solution for 20 minutes at 10,000 rpm with a polytron disperser. Add 13.3 g of 30% toluene dispersion of crosslinked acrylic-styrene particles (refractive index 1.55, manufactured by Soken Chemical Co., Ltd.) having 1.7 g and an average particle size of 3.5 μm, and finally, fluorine-based surface modification 0.77 g of agent (FP-1) and 10 g of silane coupling agent (KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.) were added to obtain a finished solution.
The mixture solution was filtered through a polypropylene filter having a pore diameter of 30 μm to prepare a coating solution A for light scattering layer.

(Preparation of coating solution B for light scattering layer)
287 g of commercially available zirconia-containing UV curable hard coat solution (Desolite Z7404, manufactured by JSR Corporation, solid content concentration of about 61%, ZrO ₂ content of solid content of about 70%, polymerizable monomer, polymerization initiator included), dipenta 86 g of a mixture of erythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.) was mixed, and further diluted with 60 g of methyl isobutyl ketone and 17 g of methyl ethyl ketone. Furthermore, 28 g of a silane coupling agent (KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.) was mixed and stirred. The refractive index of the coating film obtained by applying this solution and curing with ultraviolet rays was 1.61.
Further, a 30% methyl isobutyl ketone dispersion of classified strengthened crosslinked PMMA particles having an average particle diameter of 3.0 μm (refractive index 1.49, MXS-300, manufactured by Soken Chemical Co., Ltd.) was added to this solution at 10,000 rpm with a Polytron disperser. 35 g of a dispersion dispersed for 20 minutes was added, and then a 30% methyl ethyl ketone dispersion of silica particles having an average particle diameter of 1.5 μm (refractive index 1.46, Seahosta KE-P150, manufactured by Nippon Shokubai Co., Ltd.) 90 g of a dispersion dispersed at 10,000 rpm for 30 minutes was added, and finally 0.12 g of a fluorine-based surface modifier (FP-1) was mixed and stirred to obtain a finished solution.
The mixture solution was filtered through a polypropylene filter having a pore size of 30 μm to prepare a coating solution B for a light scattering layer.

(Preparation of coating solution C for light scattering layer)
In the light scattering layer coating solution B, instead of silica particles having an average particle diameter of 1.5 μm, classified reinforcing highly crosslinked PMMA particles having an average particle diameter of 1.5 μm (MXS-150H, a crosslinking agent ethylene glycol dimethacrylate, an amount of crosslinking agent of 30 %, A coating solution C for a light scattering layer was prepared in the same manner as the coating liquid A, including the amount added, except that 130 g of 30% methyl ethyl ketone dispersion liquid manufactured by Soken Chemical Co., Ltd., refractive index 1.49) was used. .

(Preparation of antireflection film sample)
1) Coating of light scattering layer A triacetylcellulose film (TAC-TD80U, manufactured by Fuji Photo Film Co., Ltd.) having a thickness of 80 μm is unrolled in a roll form, and the above functional layer (antiglare hard coat layer) The coating liquid for coating was applied under the conditions of a gravure roll rotation speed of 30 rpm and a conveyance speed of 30 m / min using a micro gravure roll having a diameter of 180 lines / inch and a gravure pattern with a depth of 40 μm and a doctor blade, and a temperature of 60 ° C. After drying for 150 seconds, the sample was further irradiated with ultraviolet rays having an illuminance of 400 mW / cm ² and an irradiation amount of 250 mJ / cm ² using a 160 W / cm air-cooled metal halide lamp (made by Eye Graphics Co., Ltd.) under a nitrogen purge. The coating layer was cured to form a functional layer having a thickness of 6 μm and wound up.

2) Hydrophilization treatment (corona discharge treatment)
The hydrophilic treatment was performed by either of the following.
The surface of the light scattering layer was subjected to corona discharge five times at 1.0 kW and 10 m / min. After the treatment, the contact angle of water on the surface was measured.
(Glow discharge treatment)
The said base material with a light-scattering layer is conveyed between a pair of electrodes which oppose. A voltage of 5 kHz was applied between the electrodes, and an atmosphere of atmospheric pressure was formed between the electrodes with a mixed gas of 86/8/7 of argon, carbon dioxide and nitrogen. After the treatment, the contact angle of water on the surface was measured.

3) Formation of thin film layer (formation of thin film layer A)
One low refractive index layer was formed on the light scattering layer of the base material by applying a high frequency voltage between the opposing electrodes while feeding the reaction gas under a pressure near atmospheric pressure. The electrode on one side of the opposing electrode rotates in a roll shape (roll electrode) and is electrically grounded. The substrate is conveyed on its surface in contact with the light scattering layer on the outside. The other electrode (counter electrode) facing each other is disposed so as to face the roll electrode, and both the roll electrode and the counter electrode are covered with a dielectric. The gap between both electrodes was 1 mm. A gas having the following composition was introduced between both electrodes, and plasma discharge treatment was performed at 13.56 MHz at 20 W / cm ² to produce a thin film. The produced low refractive index layer had a refractive index of 1.44 and a film thickness of 95 nm.
Gas mixture for low refractive index layer formation (vol%)
Argon: hydrogen: tetramethoxysilane = 98.5: 1.2: 0.3

(Formation of thin film layer B)
High-refractive index layer 1 / low-refractive index layer 1 / high-refractive layer on the light-scattering layer of the base material by applying a high-frequency voltage between the opposing electrodes while sending the reaction gas under pressure near atmospheric pressure Four thin film layers were successively formed in the order of index layer 2 / low refractive index layer 2. The low refractive index layer was produced by the same method as in the case of the thin film layer A. The high refractive index layer was also formed as a thin film by the same method as the low refractive layer formation except that the following mixed gas was used as the reactive gas. The refractive index of the obtained high refractive index layer and low refractive index layer is 2.35 and 1.44, respectively, and high refractive index layer 1 / low refractive index layer 1 / high refractive index layer 2 / low refractive index layer 2 The film thickness was 12 nm / 38 nm / 120 nm / 92 nm.

(Formation of thin film layer C)
High-refractive index layer 1 / low-refractive index layer 1 / high-refractive layer on the light-scattering layer of the base material by applying a high-frequency voltage between the opposing electrodes while sending the reaction gas under pressure near atmospheric pressure Four thin film layers were successively formed in the order of index layer 2 / low refractive index layer 2. The same method as thin film layer B, except that a mixed gas in which tetrabutyltin bubbled with argon and triethylindium bubbled with argon were mixed 1: 1 as the reactive gas of high refractive index layer 1 was diluted with argon. A thin film was prepared. The refractive index of the obtained high refractive index layer 1 is 1.9, and the refractive indexes of the high refractive index layer 2 and the low refractive index layer are 2.35 and 1.44, respectively. The film thickness of the refractive index layer 1 / the high refractive index layer 2 / the low refractive index layer 2 was 18 nm / 37 nm / 120 nm / 92 nm. Further, the surface resistance after the formation of the high refractive index layer 1 was 10 ⁴ Ω / □, and the haze was 1% or less. That is, the high refractive index layer 1 is a transparent antistatic layer.

(Formation of thin film layer D)
High-refractive index layer 1 / low-refractive index layer 1 / high-refractive layer on the light-scattering layer of the base material by applying a high-frequency voltage between the opposing electrodes while sending the reaction gas under pressure near atmospheric pressure Four thin film layers were successively formed in the order of index layer 2 / low refractive index layer 2. A thin film was produced in the same manner as the thin film layer B, except that a mixed gas of 99.7 vol% argon and 0.3 vol% propylene hexafluoride was used as the reactive gas for the low refractive index layer 2. The obtained low refractive index layer 2 has a refractive index of 1.35, and the high refractive index layer and the low refractive index layer 1 have refractive indexes of 2.35 and 1.44, respectively. The film thickness of the refractive index layer 2 / the high refractive index layer 1 / the low refractive index layer 2 was 25 nm / 36 nm / 125 nm / 102 nm. The contact angle of water on the surface was 95 degrees, and it could be wiped clean even with a fingerprint. That is, the low refractive index layer 2 is an antifouling layer.

(Formation of thin film layer E)

(Preparation of coating solution E-1 for medium refractive index layer)
<Preparation of titanium dioxide fine particle dispersion>
As the titanium dioxide fine particles, titanium dioxide fine particles (MPT-129, manufactured by Ishihara Sangyo Co., Ltd.) containing cobalt and surface-treated with aluminum hydroxide and zirconium hydroxide were used.
The following dispersant (38.8 g) and cyclohexanone (704.8 g) were added to 257.5 g of the particles and dispersed by dynomill to prepare a titanium dioxide dispersion having a mass average diameter of 72 nm.

<Preparation of medium refractive index layer coating solution E-1>
To 89.0 g of the above titanium dioxide dispersion, 58.7 g of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA), 3.1 g of a photopolymerization initiator (Irgacure 907), a photosensitizer (Kayacure DETX) 1.1 g of Nippon Kayaku Co., Ltd.), 482.4 g of methyl ethyl ketone and 1869.8 g of cyclohexanone were added and stirred. The solution was filtered through a polypropylene filter having a pore diameter of 0.4 μm to prepare an intermediate refractive index layer coating solution E-1.

(Preparation of coating solution E-2 for high refractive index layer)
To 587.0 g of the above titanium dioxide dispersion, 48.0 g of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.), a photopolymerization initiator (Irgacure 907, Nippon Ciba Geigy ( 4.0 g), photosensitizer (Kayacure-DETX, Nippon Kayaku Co., Ltd.) 1.3 g, methyl ethyl ketone 455.8 g, and cyclohexanone 1427.8 g were added and stirred. The solution was filtered through a polypropylene filter having a pore diameter of 0.4 μm to prepare a coating solution E-2 for a high refractive index layer.

(Preparation of coating solution E-3 for low refractive index layer)
15.5 g of the perfluoroolefin copolymer (1), 1.45 g of silica sol (silica, MEK-ST with different particle size, average particle size 45 nm, solid content concentration 30%, manufactured by Nissan Chemical Co., Ltd.), reactive silicone X-22-164C (trade name; manufactured by Shin-Etsu Chemical Co., Ltd.) 0.3 g, sol solution a 7.3 g, photopolymerization initiator (Irgacure 907 (trade name), manufactured by Ciba Geigy) 0.76 g, methyl ethyl ketone 301 g, cyclohexanone After adding 9.0 g and stirring, it was filtered through a polypropylene filter having a pore size of 5 μm to prepare a coating solution E-3 for a low refractive index layer.

(Preparation of antireflection film)
The medium refractive index layer coating solution E-1 was applied on the light scattering layer that had not been subjected to the hydrophilization treatment using a gravure coater. After drying at 100 ° C., an illuminance of 550 mW / cm using an air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) of 240 W / cm while purging with nitrogen so that the atmosphere has an oxygen concentration of 1.0% by volume or less. ^{2. The} coating layer was cured by irradiating with an ultraviolet ray having an irradiation amount of 600 mJ / cm ² to form a thin film layer E, that is, a medium refractive index layer (refractive index 1.66, film thickness 67 nm).
On the medium refractive index layer, a coating solution E-2 for a high refractive index layer was applied using a gravure coater. After drying at 100 ° C., an illuminance of 550 mW / cm using an air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) of 240 W / cm while purging with nitrogen so that the atmosphere has an oxygen concentration of 1.0% by volume or less. ^2. An ultraviolet ray with an irradiation amount of 600 mJ / cm ² was irradiated to cure the coating layer to form a high refractive index layer (refractive index 1.92, film thickness 106 nm).

On the high refractive index layer, the low refractive index layer coating solution E-3 was applied using a gravure coater. After drying at 80 ° C. and using a 160 W / cm air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) while purging with nitrogen so that the oxygen concentration becomes 1.0 vol% or less, the illuminance is 550 mW / cm ^2, an irradiation dose of 600 mJ / cm ^2, to form a low refractive index layer (refractive index 1.43, film thickness 85 nm).

(Evaluation of antireflection film)
About the obtained antireflection film, the following items were evaluated. The results are shown in Table 1.

(1) Average reflectance Using a spectrophotometer (manufactured by JASCO Corporation), the spectral reflectance at an incident angle of 5 ° was measured in a wavelength region of 380 to 780 nm. For the results, an integrating sphere average reflectance of 450 to 650 nm was used.

(2) Steel wool scratch resistance evaluation A rubbing test was performed under the following conditions using a rubbing tester.
Evaluation environmental conditions: 25 ° C., 60% RH
Rub material: Steel wool (manufactured by Nippon Steel Wool Co., Ltd., Gelade No. 0000) was wound around the rubbing tip (1 cm × 1 cm) of a tester that was in contact with the sample, and the band was fixed so as not to move.
Moving distance (one way): 13 cm, rubbing speed: 13 cm / sec, load: 500 g / cm ² , tip contact area: 1 cm × 1 cm, rubbing frequency: 10 reciprocations.
An oil-based black ink was applied to the back side of the rubbed sample and visually observed with reflected light, and scratches on the rubbed portion were evaluated according to the following criteria.
A: Even when viewed very carefully, no scratches are visible.
○: Slightly weak scratches are visible when viewed very carefully.
○ △: Weak scratches are visible.
Δ: Moderate scratches are visible.
Δ × ˜ ×: There is a scratch that can be seen at first glance.

(3) Evaluation of resistance to rubbing with a cotton swab A cotton swab is fixed to the rubbing tip of a rubbing tester, and the upper and lower sides of the sample are fixed with clips in a smooth dish, and the sample and the swab are immersed in water at 25 ° C at room temperature 25 ° C. A rubbing test was performed by applying a load of 500 g and changing the number of rubbing. The rubbing conditions are as follows.
Rubbing distance (one way): 1 cm, rubbing speed: about 2 reciprocations / second The sample after rubbing was observed, and the rubbing resistance was evaluated as follows according to the number of film peeling.
0-10 round trip film peeling ×
Film peeling after 10 to 30 round trips
30-50 reciprocating film peeling
50-100 reciprocating film peeling
100-150 round trip film peeling ○
No film peeling even after 150 reciprocations ◎

(4) Effect of scattered light profile Using an automatic goniophotometer GP-5 (manufactured by Murakami Color Research Laboratory Co., Ltd.), the film is placed perpendicular to the incident light and scattered in all directions. The light profile was measured. From this profile, the scattered light intensity at 30 ° C. with respect to an emission angle of 0 ° was obtained.

[Example 1 Samples 1 to 9, Comparative Example 1 Samples 10 and 11]
Table 1 shows configurations and evaluation results of Examples 1 to 1 and Comparative Example 1 and Samples 10 and 11. Moreover, the film thickness distribution of each layer of the thin film layer of the example produced this time is within 5% at the maximum, and it can be seen that the thin film layer is uniformly formed on the light scattering layer having surface irregularities. The thickness of the light scattering layer after drying was 3.4 μm.

From the results shown in Table 1, the following is clear.
In the antireflection film of the present invention, the antireflection film produced by atmospheric pressure plasma treatment has scattering properties, and does not use a solvent for the attachment of the thin film layer, has high film thickness uniformity, and has a high reflectance. Can be reduced. Further, it is possible to impart reflectance, conductivity, and antifouling properties. In addition, an antireflection film having excellent performance in adhesion and scratch resistance can be obtained with high productivity.

[Example 2]
(Saponification treatment of antireflection film)
The antireflection film of Example 1 was subjected to the following saponification treatment.
A 1.5 mol / l aqueous sodium hydroxide solution was prepared and kept at 55 ° C. A 0.01 mol / l dilute sulfuric acid aqueous solution was prepared and kept at 35 ° C. After protecting the surface of the antireflection film on which the thin film layer was formed with a laminate film, the surface was immersed in the aqueous sodium hydroxide solution for 2 minutes, and then immersed in water to sufficiently wash away the aqueous sodium hydroxide solution. Subsequently, after being immersed in the above-mentioned dilute sulfuric acid aqueous solution for 1 minute, it was immersed in water to sufficiently wash away the dilute sulfuric acid aqueous solution. Finally, the sample was thoroughly dried at 120 ° C.
In this way, a saponified antireflection film was produced.
The PVA film was immersed in an aqueous solution of 2.0 g / l iodine and 4.0 g / l potassium iodide at 25 ° C. for 240 seconds, and further immersed in an aqueous solution of boric acid 10 g / l at 25 ° C. for 60 seconds. It introduced into the tenter drawing machine of the form of FIG. 2 described in 2002-86554 gazette, it extended | stretched 5.3 time, the tenter was bent with respect to the extending | stretching direction, and the width | variety was kept constant hereafter. After drying in an atmosphere of 80 ° C., it was detached from 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 46 °. Here, | L1-L2 | is 0.7 m, W is 0.7 m, and | L1-L2 | = W. The substantial stretching direction Ax-Cx at the tenter outlet was inclined by 45 ° with respect to the center line 22 of the film sent to the next process. Wrinkles and film deformation at the tenter exit were not observed.
Furthermore, it was bonded to Fuji Photo Film Co., Ltd. Fujitac (cellulose triacetate, retardation value 3.0 nm), which was saponified with an aqueous solution of PVA (Pura-117H, Kuraray Co., Ltd.) 3%, and further 80 ° C. And dried to obtain a polarizing plate having an effective width of 650 mm. The absorption axis direction of the obtained polarizing plate was inclined 45 ° with respect to the longitudinal direction. The polarizing plate had a transmittance at 550 nm of 43.7% and a polarization degree of 99.97%. Further, when the substrate was cut into a size of 310 × 233 mm, a polarizing plate having a 45 ° absorption axis inclined with respect to the side with an area efficiency of 91.5% was obtained.
Next, the saponified films of Examples 1 to 9 and Comparative Example 1 Sample 1 were bonded to the above polarizing plate to produce a polarizing plate with antiglare and antireflection. Using this polarizing plate, a liquid crystal display device having an antireflection layer disposed on the outermost layer was produced. As a result, in Examples 1 to 9, excellent contrast was obtained because there was no reflection of external light, and antiglare was obtained. The reflection image was not conspicuous due to the property, and the visibility was excellent.

[Example 3]
An 80 μm-thick triacetylcellulose film (TAC-TD80U, manufactured by Fuji Photo Film Co., Ltd.), immersed in a 1.5 mol / l, 55 ° C. NaOH aqueous solution for 2 minutes, neutralized and washed with water, and Examples Polarizers were prepared by adhering and protecting both sides of a polarizer prepared by adsorbing iodine on polyvinyl alcohol on the backside saponified triacetylcellulose films of Samples 1 to 9 and Comparative Example 1 Sample 1. A liquid crystal display device of a notebook personal computer equipped with a transmissive TN liquid crystal display device (Sumitomo 3M Co., Ltd., which is a polarization separation film having a polarization selection layer) so that the anti-reflection film side is the outermost surface. In Example 1 samples 1 to 9, when the D-BEF made of D-BEF was replaced with the polarizing plate on the viewing side, the background reflection was very small, and the display quality was very high. A high display device was obtained.

[Example 4]
Example 1 Protective film on the liquid crystal cell side of the polarizing plate on the viewing side of the transmissive TN liquid crystal cell to which the samples of Samples 1 to 9 and Comparative Example 1 Sample 1 were attached, and the liquid crystal cell side of the polarizing plate on the backlight side As the protective film, the disc surface of the discotic structural unit 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 is 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.) having a changing optical compensation layer is used, the contrast in a bright room is excellent, and the viewing angles in the vertical and horizontal directions are extremely high. In addition, a liquid crystal display device having a wide display and excellent visibility and high display quality was obtained. In addition, in Examples 1 and 2 (anti-glare hard coat liquids B and C), the scattered light intensity at 30 ° with respect to the emission angle of 0 ° is 0.06%. The viewing angle was improved, and the yellow color in the left-right direction was improved. For comparison, the film produced in the same manner as Sample 1 in Example 1 except that the cross-linked PMMA particles and silica particles were removed from the antiglare hard coat solution B, and the scattered light intensity of 30 ° with respect to an output angle of 0 ° was substantially zero. It was 0%, and the downward viewing angle was increased, and the yellowness improving effect was not obtained at all.

[Example 5]
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.

[Example 6]
Using the sample of Example 1, a polarizing plate with a single-sided antireflection film was prepared, and a λ / 4 plate was bonded to the opposite side of the polarizing plate having the antireflection film, and the surface of the organic EL display device was When affixed to a glass plate, the surface reflection and the reflection from the inside of the surface glass were cut, and a display with extremely high visibility was obtained.

FIG. 1 is a cross-sectional view schematically showing one embodiment of the antireflection film of the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Antireflection film 2 Transparent support 3 Light scattering layer 4 High refractive index layer 5 Low refractive index layer 6 High refractive index layer 7 Low refractive index layer 8 Antifouling layer 9 Light scattering particle 10 Anti-glare imparting particle

Claims (14)

An antireflection film in which a light scattering layer is formed on a transparent support, and one or more thin film layers including a low refractive index layer are further formed on the light scattering layer,
The light scattering layer is formed by dispersing at least one kind of translucent particles having an average particle diameter of 0.5 to 5 μm in a translucent resin, and has a refractive index of the translucent particles and the translucent resin. The difference is 0.02 to 0.2, and the translucent particles are contained by 3 to 30% by mass of the total solid content of the light scattering layer.
The low refractive index layer is formed on the surface of the substrate disposed between the electrodes by applying a high frequency voltage between the opposing electrodes while sending the reaction gas under atmospheric pressure or a pressure near atmospheric pressure. An antireflection film, which is a layer having a refractive index of 1.30 to 1.55. An antireflection film in which a light scattering layer is formed on a transparent support, and one or more thin film layers including a low refractive index layer are further formed on the light scattering layer,
The light scattering layer is formed by dispersing at least one kind of translucent particles having an average particle diameter of 0.5 to 5 μm in a translucent resin, and has a refractive index of the translucent particles and the translucent resin. The difference is 0.02 to 0.2, and the translucent particles are contained by 3 to 30% by mass of the total solid content of the light scattering layer.
The high-refractive index layer has at least one high refractive index layer having a higher refractive index than the light scattering layer and the low refractive index layer between the light scattering layer and the low refractive index layer. An antireflection film formed on the surface of a substrate disposed between electrodes by applying a high-frequency voltage between opposing electrodes while sending a reaction gas under atmospheric pressure or a pressure near atmospheric pressure .   The translucent particles are composed of two or more kinds of translucent particles, and the difference in refractive index between at least two kinds of the two or more kinds of translucent particles is 0.01 to 0.2. The antireflection film according to claim 1 or 2.   The outermost surface of the antireflection film has an arithmetic average roughness Ra of 0.02 to 0.5 μm, an average interval Sm of unevenness of 5 to 100 μm, and a 10-point average roughness Rz / arithmetic average roughness Ra of 10 or less. It has a certain uneven | corrugated shape, The antireflection film of Claims 1-3 characterized by the above-mentioned.   The antireflection film according to any one of claims 1 to 4, wherein the low refractive index layer contains a polymer containing silicon oxide and / or a fluorine compound as a main component.   The antireflective film according to claim 2, wherein the high refractive index layer contains titanium oxide as a main component and has a refractive index of 1.6 or more. The antireflection film according to claim 1, wherein a film thickness distribution of the low refractive index layer and / or the high refractive index layer is within 5% in an area of 1 m ² . A transparent antistatic layer having a surface resistance of 1 × 10 ¹¹ Ω / □ or less and a haze of 10% or less is provided between the transparent support and the low refractive index layer. 8. The antireflection film as described in any one of 7 above.   9. The antifouling layer comprising a silicon compound and / or a fluorine compound and having a water contact angle of 70 degrees or more is formed on the low refractive index layer. The antireflection film as described in 1.   It is a manufacturing method of the antireflection film in any one of Claims 1-9, Comprising: After hydrophilizing the surface of a light-scattering layer so that a contact angle with water may be 70 degrees or less, on this surface A method for producing an antireflection film, comprising forming a thin film layer.   11. The roll-like long film in which a light scattering layer is formed on a transparent support, the hydrophilic treatment on the surface of the light scattering layer and the formation of a thin film layer are successively performed. Manufacturing method of antireflection film.   The light-scattering layer is formed on the roll-like long transparent support, the surface of the light-scattering layer is hydrophilized, and the thin film layer is continuously formed. A method for producing an antireflection film.   A polarizing plate comprising the antireflection film according to claim 1 as a protective film on one side of the polarizing plate.   An image display device comprising the antireflection film according to claim 1 or the polarizing plate according to claim 13 installed such that the low refractive index layer is located on the viewer side.

Images