JP2001343503A - Antidazzle antireflection film, polarizing plate and liquid crystal display - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an antidazzle antireflection film which can easily be produced at a low cost only by forming an antidazzle hard coat layer and a low refractive index layer on a base, has superior antireflection performance and flaw resistance, further has good stain-proofing property and is nearly free from tints and irregular color and to provide a polarizing plate which prevents the reflection of outside light and is excellent in antifouling property and flaw resistance and a liquid crystal display. SOLUTION: The antidazzle antireflection film is obtained by disposing an antidazzle layer and at least one low refractive index layer in this order on a transparent base and has <=1.2% mean value of specular reflectance in 5 deg. incidence in the wavelength range of 450-650 nm. The polarizing plate uses the antireflection film as a protective film. The liquid crystal display uses the antireflection film or the antireflection layer of the polarizing plate as the top layer of the display.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an antireflection film having antiglare properties, a polarizing plate, and a liquid crystal display device using the same.

[0002]

2. Description of the Related Art Antireflection films are generally used for cathode ray tube displays (CRT), plasma display panels (PD).
P) and image display devices such as liquid crystal display devices (LCDs), in order to prevent a reduction in contrast and reflection of an image due to reflection of external light, a display that reduces reflectance using the principle of optical interference. It is located on the surface.

However, in an antireflection film having only a hard coat layer and a low refractive index layer on a transparent support,
In order to reduce the reflectance, the low-refractive-index layer must have a sufficiently low refractive index. For example, in order to reduce the average reflectance in the range of 450 nm to 650 nm to 1.6% or less in an antireflection film using triacetyl cellulose as a support and a UV cured coating of dipentaerythritol hexaacrylate as a hard coat layer, The refractive index must be less than 1.40. Examples of the material having a refractive index of 1.40 or less include a fluorine-containing compound such as magnesium fluoride and calcium fluoride as an inorganic substance, and a fluorine-containing compound having a large fluorine content as an organic substance. As a result, the film placed on the outermost surface of the display lacked scratch resistance. Therefore, in order to have sufficient scratch resistance, a compound having a refractive index of 1.43 or more was required.

Japanese Patent Application Laid-Open No. 7-287102 describes that the reflectance is reduced by increasing the refractive index of the hard coat layer. However, such a high-refractive-index hard coat layer has a large difference in refractive index from the support, so that color unevenness of the film occurs, and the wavelength dependence of the reflectivity also has a large amplitude.

Japanese Patent Application Laid-Open No. 7-333404 discloses that
Although an anti-glare anti-reflection film having excellent gas barrier properties, anti-glare properties, and anti-reflection properties is described, a silicon oxide film formed by a CVD method is indispensable. Therefore, a wet coating method in which a coating solution is applied to form a film. It is inferior in productivity as compared with. Further, the antireflection properties of the antiglare antireflection film thus obtained were not satisfactory.

[0006]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a simple and inexpensive production method simply by forming an antiglare layer and a low-refractive-index layer on a support. An object of the present invention is to provide an anti-glare anti-reflection film having scratch resistance, and further, anti-fouling properties, and in addition, having less color and uneven color.
Another object of the present invention is to provide a polarizing plate and a liquid crystal display device in which reflection of external light is sufficiently prevented, and which is excellent in stain resistance and scratch resistance.

[0007]

According to the present invention, an antiglare antireflection film, a polarizing plate and a liquid crystal display having the following constitutions are provided, and the above object is achieved. 1. An antiglare layer and at least one low-refractive-index layer are provided in this order on a transparent support, and the average value of the specular reflectance at a 5-degree incidence in the wavelength region from 450 nm to 650 nm is 1. An antiglare antireflection film, wherein the content is 2% or less. 2. Triacetyl cellulose produced by dissolving triacetyl cellulose in a solvent and dispersing the triacetyl cellulose dope in a single-layer casting method or a multi-layer co-casting method. 2. The antiglare antireflection film according to 1, wherein the antireflection film is a cellulose film. 3. 3. The triacetyl cellulose dope according to 2, wherein the triacetyl cellulose dope is a triacetyl cellulose dope prepared by dissolving triacetyl cellulose in a solvent substantially free of dichloromethane by a low-temperature dissolution method or a high-temperature dissolution method. Anti-glare anti-reflection film. From 450 nm of the integrated reflectance at 4.5 degree incidence, 65
4. The antiglare antireflection film according to any one of 1 to 3, wherein an average value in a wavelength region up to 0 nm is 2.5% or less. 5. CI in the wavelength range from 380 nm to 780 nm
The color of the specularly reflected light with respect to the 5-degree incident light of the E standard light source D65 is L *, a *, in the CIE1976L * a * b * color space.
b * value is L * ≦ 10, 0 ≦ a * ≦ 2, −5 ≦ b
5. The antiglare antireflection film according to any one of 1 to 4, wherein the antiglare film has a color satisfying * ≦ 2. 6. The antiglare antireflection film according to any one of 1 to 5, wherein a haze value is in a range of 5 to 15%. 7. The low refractive index layer is made of a cured product of a thermosetting or ionizing radiation-curable fluorine-containing resin.
7. The antiglare antireflection film according to any one of items 1 to 6. 8. The low refractive index layer made of a cured product of the above fluororesin has a dynamic friction coefficient in a range of 0.03 to 0.15 and a contact angle with water in a range of 90 to 120 degrees. The antiglare antireflection film according to the above. 9. A polarizing plate, wherein the antiglare antireflection film according to any one of 9.1 to 8 is used as at least one of two protective films of a polarizing layer in the polarizing plate. 10. A liquid crystal display device comprising the antiglare antireflection film according to any one of 1 to 8 or the antireflection layer of the antiglare antireflection polarizing plate according to 9 as the outermost layer of a display. .

[0008]

DESCRIPTION OF THE PREFERRED EMBODIMENTS First, the basic structure of the antiglare antireflection film of the present invention will be described with reference to the drawings.
The embodiment shown in FIG. 1 is an example of the antiglare antireflection film of the present invention. In this case, the antiglare antireflection film 1 is prepared by dissolving triacetylcellulose dope prepared by dissolving triacetylcellulose in a solvent by a single-layer casting method or a multi-layer co-casting method. The transparent support 2 made of a triacetylcellulose film, the hard coat layer 3, the antiglare layer 4, and the low refractive index layer 5 have the following layer structure. The resin mat particles 6 are dispersed in the antiglare layer 4.

In the antiglare antireflection film of the present invention, the average value of the specular reflectance at an incidence angle of 5 degrees in a wavelength region from 450 nm to 650 nm is 1.2% or less, preferably 1.1% or less. Further, the average value of the integrated reflectance in the wavelength region from 450 nm to 650 nm at 5 degrees incidence is preferably 2.5% or less, more preferably 2.3% or less.

A description will be given of the specular reflectance at the 5 degree incidence and the 5 degree incidence. The specular reflectance at 5 ° incidence is the ratio of the intensity of light reflected in the normal direction −5 ° with respect to the incident light from the normal direction + 5 ° of the sample, and is a measure of reflection due to specular reflection of the background. When applied to an antiglare antireflection film, the intensity of light reflected at -5 degrees in the normal direction becomes weaker by the amount of scattered light caused by surface irregularities provided for imparting antiglare properties. Therefore,
It can be said that the specular reflectance is a measurement method that reflects the contribution of both the antiglare property and the antireflection property. On the other hand, the integrated reflectance at 5 degrees incidence is the ratio of the integrated value of the intensity of light reflected in all directions with respect to light incident from the normal direction of the sample +5 degrees. When applied to an anti-glare anti-reflection film, the reflected light does not decrease due to the anti-glare property, so that measurement reflecting only the anti-reflective property is possible. Therefore, the average values of the above two reflectances in the wavelength region from 450 nm to 650 nm are respectively 1.2% or less (specular reflectance) and 2.5%.
% Or less (integral reflectance) makes it possible to simultaneously satisfy the antiglare property and the antireflection property.

When the average value of the specular reflectivity of the antiglare antireflection film at 5 degrees incidence in the wavelength region from 450 nm to 650 nm exceeds 1.2%, the reflection of the background is anxious, and the display device has a problem. The visibility when applied to the surface film is reduced. On the other hand, if the average value of the integrated reflectance of the antiglare antireflection film at a 5 degree incidence in the wavelength region from 450 nm to 650 nm exceeds 2.5%, the effect of improving the contrast of the display device is reduced, and the antiglare property is reduced. The display screen is whitened by scattered light caused by surface irregularities for application,
The display quality of the display device is reduced.

The antiglare antireflection film of the present invention has a CI
The color of the specularly reflected light with respect to the 5-degree incident light of the E standard light source D65 is L *, a *, in the CIE1976L * a * b * color space.
When quantified by b * value, L * ≦ 10, 0 ≦
It is preferable that it is designed to fall within the ranges of a * ≦ 2 and −5 ≦ b * ≦ 2. The color of the specular light that satisfies this is a neutral color. The tint of the specularly reflected light with respect to the 5-degree incident light of the CIE standard light source D65 is calculated by calculating the product of the specular reflectance in the wavelength range of 380 nm to 780 nm at the 5-degree incidence and the spectral distribution at each wavelength of the light source D65. From the obtained spectral reflection spectrum, CIE
It can be quantified by calculating the L * value, a * value, and b * value of the 1976 L * a * b * color space, respectively. L
* If the value is larger than 10, the antireflection property is not sufficient. a
* If the value is greater than 2, the red spot color of the reflected light is strong and 0
On the other hand, if it is less than 10, the green color is undesirably strong. Also, b *
If the value is less than -5, the bluish color is strong, and if it is more than 2, the yellow color is strong, which is not preferable.

The anti-glare anti-reflection film having such a neutral-colored reflected light and having a low reflectance has a balance between the refractive index of the low-refractive-index layer and the refractive index of the binder material of the anti-glare layer. Is obtained by optimizing. In general, an antireflection film made of an optical thin film formed by vapor deposition or sputtering of three or more layers can reduce the average value of specular reflectance to 0.3% or less, and thus can reduce the L * value to 3 or less. Is 10 or more and the b * value is less than -10, and the tint of the reflected light is very strong. In the antiglare antireflection film of the present invention, the tint of the reflected light is low. It has been greatly improved.

The antiglare antireflection film of the present invention preferably has a haze value of 5 to 15%, more preferably 7 to 13. Although the antiglare property and the haze value do not always correspond linearly, if the haze value is less than 5%, an antiglare film having sufficient antiglare property cannot be obtained. On the other hand, when the haze value is larger than 15%, scattering on the surface and inside is too strong, which causes problems such as deterioration of image clarity and whitening, which is not preferable.

The layers constituting the antiglare antireflection film of the present invention having such characteristics will be described below. The antiglare antireflection film of the present invention has an antiglare layer on a transparent support, and further has at least one low-refractive-index layer thereon. Can be provided with a smooth hard coat layer.

As the transparent support of the antiglare antireflection film of the present invention, a plastic film is preferably used. Examples of the polymer forming the plastic film include cellulose ester (eg, triacetyl cellulose, diacetyl cellulose), polyamide, polycarbonate, polyester (eg, polyethylene terephthalate, polyethylene naphthalate), polystyrene, polyolefin, ARTON (trade name, JSR Corporation) ), Substance name: norbornene-based polyolefin), ZEONEX (trade name, manufactured by Nippon Zeon Co., Ltd., substance name: norbornene-based polyolefin). Among them, triacetyl cellulose, polyethylene terephthalate, polyethylene naphthalate, ARTON and ZEONEX are preferred, and triacetyl cellulose is particularly preferred. Triacetyl cellulose has a refractive index of 1.48.

As the transparent support of the antiglare antireflection film of the present invention, triacetylcellulose dope prepared by dissolving triacetylcellulose in a solvent may be either a single-layer cast or a multi-layer co-cast. It is preferable to use a triacetylcellulose film produced by casting by the casting method described above. In particular, from the viewpoint of environmental protection, a triacetyl cellulose film prepared using a triacetyl cellulose dope prepared by dissolving triacetyl cellulose in a solvent substantially free of dichloromethane by a low-temperature dissolution method or a high-temperature dissolution method. Is preferred. Single-layer triacetylcellulose is prepared by drum casting or band casting disclosed in Japanese Patent Application Laid-Open No. 7-11055 or the like. JP-A-61-94725, JP-B-62-438
46 and the like. It is created by the so-called co-casting method. That is, the raw material flakes are converted into halogenated hydrocarbons (dichloromethane, etc., alcohols (methanol, ethanol, butanol, etc.), esters (methyl formate,
Dissolve in solvents such as methyl acetate) and ethers (dioxane, dioxolan, diethyl ether, etc.), and add various additives such as plasticizers, ultraviolet absorbers, anti-deterioration agents, slip agents, and peeling accelerators as necessary. When a solution (referred to as a dope) to which an additive is added is cast by a dope supply means (referred to as a die) onto a support made of a horizontal endless metal belt or a rotating drum, a single layer A single dope is cast in a single layer, and if there are multiple layers, a low-concentration dope is co-cast on both sides of a high-concentration cellulose ester dope. It is a method comprising removing the solvent by peeling it off from the body and then passing it through a drying section by various transporting means.

As a solvent for dissolving triacetyl cellulose as described above, dichloromethane is typical. However, technically, a halogenated hydrocarbon such as dichloromethane can be used without any problem. However, from the viewpoint of the global environment and working environment, it is preferable that the solvent does not substantially contain a halogenated hydrocarbon such as dichloromethane.
“Substantially free” means that the proportion of halogenated hydrocarbon in the organic solvent is less than 5% by mass (preferably less than 2% by mass). When a dope of triacetyl cellulose is prepared using a solvent substantially free of dichloromethane or the like, a special dissolution method as described below is essential.

The first melting method is called a cooling melting method and will be described below. First, the temperature around room temperature (-10 to 40 ° C)
While dissolving, triacetyl cellulose is gradually added with stirring. Next, the mixture is -100 to -10C (preferably -80 to -10C, more preferably -50 to-
(20 ° C., most preferably −50 to −30 ° C.). Cooling is performed, for example, in a dry ice / methanol bath (−
75 ° C) or a cooled diethylene glycol solution (-30
-20 ° C). When cooled in this way,
The mixture of triacetyl cellulose and solvent solidifies. Furthermore, this is 0-200 ° C (preferably 0-150 ° C,
More preferably 0-120 ° C, most preferably 0-5.
(0 ° C.), the solution becomes a solution in which triacetyl cellulose flows in the solvent. The temperature may be raised only at room temperature or heated in a warm bath.

The second method is called a high-temperature melting method and will be described below. First, triacetyl cellulose is gradually added to a solvent at a temperature near room temperature (-10 to 40 ° C.) with stirring. Triacetyl cellulose solution of the present invention,
It is preferable to add triacetyl cellulose to a mixed solvent containing various solvents and to swell in advance. In the present method, the dissolution concentration of triacetyl cellulose is preferably 30% by mass or less, but from the viewpoint of drying efficiency during film formation,
Preferably, the concentration is as high as possible. Next, the organic solvent mixed solution is subjected to a pressure of 70 to 24 under a pressure of 0.2 MPa to 30 MPa.
0 ° C. (preferably 80-220 ° C., more preferably 100-200 ° C., most preferably 100-1 ° C.)
90 ° C). Next, since these heated solutions cannot be applied as they are, it is necessary to cool the solution below the lowest boiling point of the solution used. In that case, it is common to cool to −10 to 50 ° C. and return to normal pressure. For cooling, the high-pressure high-temperature vessel or line containing the triacetylcellulose solution may be left alone at room temperature, and more preferably, the apparatus may be cooled using a coolant such as cooling water.

Since triacetyl cellulose is usually used as a protective film for protecting a polarizing layer of a polarizing plate of a liquid crystal display device, the transparent support of the antiglare antireflection film is formed of the above triacetyl cellulose film. When there is, the antiglare antireflection film can be used as it is for the protective film, which is preferable. In this case, the anti-glare anti-reflection film can be disposed as a protective film on the outermost surface of the display of the liquid crystal display by means such as providing an adhesive layer on one surface of the anti-glare anti-reflection film.

In the antiglare layer, it is preferable that mat particles having a particle size of 1 to 10 μm and fine particles of metal oxide having a particle size of 100 nm or less are dispersed in a binder polymer.
The refractive index of a component excluding the matting particles forming the antiglare layer, that is, a binder polymer or a dispersion in which a fine particle component of a metal oxide having a particle size of 100 nm or less is dispersed therein is 1.
The refractive index is preferably from 57 to 2.00, more preferably from 1.60 to 1.80. If this value is too small, the antireflection performance will be small, and if it is too large, the tint may be too large.

In such an anti-glare layer, matte particles having a particle diameter of 1 to 10 μm dispersed in a high refractive index binder polymer cause internal scattering of light, so that the influence of optical interference in the anti-glare layer is obtained. Does not occur. In the high-refractive-index antiglare layer having no matte particles having the above particle diameter, a large amplitude of the reflectance in the wavelength dependence of the reflectance due to the optical interference due to the refractive index difference between the antiglare layer and the support. As a result, the antireflection effect deteriorates, and at the same time, color unevenness occurs.

The binder polymer is preferably a polymer having a saturated hydrocarbon chain or a polyether chain as a main chain, and more preferably a polymer having a saturated hydrocarbon chain as a main chain. Further, 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 a main chain and having a crosslinked structure, a (co) polymer of a monomer having two or more ethylenically unsaturated groups is preferable. In order to obtain a high refractive index, it is preferable that the structure of the monomer contains an aromatic ring and at least one atom selected from a halogen atom other than fluorine, a sulfur atom, a phosphorus atom, and a nitrogen atom.

Examples of the monomer having two or more ethylenically unsaturated groups include esters of a polyhydric alcohol and (meth) acrylic acid (eg, ethylene glycol di (meth) acrylate, 1,4-dichlorohexane diacrylate, Pentaerythritol tetra (meth) acrylate), pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethanetri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) A) acrylate, pentaerythritol hexa (meth) acrylate, 1,2,3-cyclohexanetetramethacrylate, polyurethane polyacrylate, polyester polyacrylate), vinylbenzene and (Eg, 1,4-divinylbenzene, 4-vinylbenzoic acid-2-acryloylethyl ester, 1,4-divinylcyclohexanone), vinylsulfone (eg, divinylsulfone), acrylamide (eg, methylenebisacrylamide) and Methacrylamide is mentioned.

Specific examples of the high refractive index monomer include bis (4-methacryloylthiophenyl) sulfide, vinylnaphthalene, vinylphenylsulfide, 4-methacryloxyphenyl-4'-methoxyphenylthioether and the like.

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 photoradical initiator or a thermal radical initiator. Therefore, a coating solution containing a monomer having an ethylenically unsaturated group, fine particles, and a photo-radical initiator or a thermal radical initiator is prepared, and after applying the coating solution on a transparent support, a polymerization reaction by ionizing radiation or heat is performed. To form an antiglare layer.

The polymer having a polyether as a main chain is preferably a ring-opened polymer of a polyfunctional epoxy compound.
The ring-opening polymerization of the polyfunctional epoxy compound can be performed by irradiation with ionizing radiation or heating in the presence of a photoacid generator or a thermal acid generator. Therefore, a coating solution containing a polyfunctional epoxy compound, fine particles, and a photoacid generator or a thermal acid generator is prepared, and the coating solution is applied on a transparent support and then cured by a polymerization reaction using ionizing radiation or heat. An anti-glare layer can be formed.

Instead of or in addition to a monomer having two or more ethylenically unsaturated groups, a crosslinkable functional group is introduced into a polymer using a monomer having a crosslinkable functional group, The reaction may introduce a crosslinked structure 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. Vinyl sulfonic 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 a decomposition reaction, such as a block isocyanate group, may be used. That is, the crosslinkable functional group is not limited to the above-mentioned functional group, but may be one that shows reactivity as a result of decomposition of the functional group. These binder polymers having a crosslinkable functional group can form a crosslinked structure by heating after application.

The anti-glare layer has an average particle size as a mat particle for the purpose of imparting anti-glare properties, preventing deterioration of reflectance due to interference of a hard coat layer provided below the anti-glare layer, and preventing color unevenness. Particles of 1 to 10 μm, preferably 1.5 to 5 μm, for example, inorganic compound particles or resin particles are contained. Specific examples of the above particles include silica particles and TiO ₂
Particles of inorganic compounds such as particles; preferably, resin particles such as crosslinked acrylic particles, crosslinked styrene particles, melamine resin particles, and benzoguanamine resin particles. Among them, the above resin particles are preferable. The shape of the particles can be either a true sphere or an irregular shape. Further, two or more different kinds of particles may be used in combination. Further, it is preferable that the mat particles having a particle diameter smaller than the binder film thickness of the antiglare layer account for less than 50% of the entire mat particles. The particle size distribution can be measured by the Coulter counter method, but the distribution is converted to a particle number distribution. The particles are contained in the anti-glare layer such that the amount of particles in the formed anti-glare layer is preferably 10 to 1000 mg / m ² , more preferably 30 to 100 mg / m ² .

The antiglare layer is used to increase the refractive index of the layer.
In addition to the matte particles, titanium, zirconium, aluminum, indium, zinc, tin, consisting of an oxide of at least one metal selected from antimony,
It is preferable to contain inorganic fine particles having a particle size of 100 nm or less, preferably 50 nm or less. Specific examples of the inorganic fine particles include TiO ₂ , ZrO ₂ , Al ₂ O ₃ , In ₂ O ₃ , Z
Fine particles such as nO, SnO ₂ , Sb ₂ O ₃ , and ITO can be used. The addition amount of these inorganic fine particles is preferably 10 to 90%, more preferably 20 to 80% of the total mass of the antiglare layer. In addition, since such fine particles have a particle size sufficiently smaller than the wavelength of light, haze does not increase, and a dispersion in which the fine particles are dispersed in a binder polymer behaves as an optically uniform substance.

As described above, the refraction of the component excluding the mat particles dispersed in the antiglare layer, that is, the binder polymer or the dispersion in which the above-described fine particle component of the metal oxide having a particle size of 100 nm or less is dispersed. The rate is 1.57 ~
2.00, and more preferably 1.6.
0 to 1.80. In order to set the refractive index in the above range, the types and the proportions of the binder polymer and the fine particles of the metal oxide may be appropriately selected. How to choose is
It can be easily known experimentally in advance.

The thickness of the antiglare layer is preferably 0.5 to 10 μm, more preferably 1 to 5 μm.

In the antiglare antireflection film of the present invention, a smooth hard coat layer may be provided between the transparent support and the antiglare layer, if necessary, for the purpose of improving the film strength. The thickness of the smooth hard coat layer is preferably from 1 to 10 μm, more preferably from 1.2 to 6 μm. The components used for the smooth hard coat layer are the same as those described for the antiglare layer except that no matte particles are used.

As described above, the refractive index of the low refractive index layer of the antiglare antireflection film of the present invention is preferably in the range of 1.38 to 1.49. When the refractive index is in the above range, sufficient antireflection properties and scratch resistance can be compatible,
Good results are obtained. Further, it is preferable that (B) the low refractive index layer satisfies the following formula (I) from the viewpoint of antireflection properties.

(Mλ / 4) × 0.7 <n ₁ d ₁ <(mλ / 4) × 1.3 (Equation (I))

In the formula, m is a positive odd number, n ₁ is the refractive index of the low refractive index layer, and d ₁ is the thickness (nm) of the low refractive index layer. Λ is a wavelength, and is 500 to 55
It is a value in the range of 0 (nm). Satisfying the formula (I) means that m (a positive odd number, usually 1) that satisfies the formula (I) exists in the wavelength range.

The low refractive index layer is preferably made of a cured product of a thermosetting or ionizing radiation curable fluororesin. The cured product of the fluororesin has a dynamic friction coefficient of 0.03 to
0.15, the contact angle to water is preferably in the range of 90 to 120 degrees. Perfluoroalkyl group-containing silane compounds (for example, (heptadecafluoro-1,1,2,2-tetradecyl) triethoxysilane and the like), a fluorine-containing vinyl monomer, and a crosslinkable group Preferred are fluorine-containing copolymers formed from monomers for application. When the fluorinated copolymer has a thermally crosslinkable functional group, it is a thermosetting type,
When it has an ionizing radiation crosslinkable functional group, it is an ionizing radiation curing type.

Specific examples of the above-mentioned fluorine-containing vinyl monomer include, for example, fluoroolefins (for example, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, hexafluoroethylene, hexafluoropropylene, perfluoro-2,2-dimethyl- 1,3-dioxole, etc.), partially or fully fluorinated alkyl ester derivatives of (meth) acrylic acid (for example, Biscoat 6F
M (manufactured by Osaka Organic Chemicals) and M-2020 (manufactured by Daikin)
Etc.), fully or partially fluorinated vinyl ethers and the like. As the monomer for providing the crosslinkable group,
In addition to (meth) acrylate monomers having a crosslinkable functional group in the molecule in advance such as glycidyl methacrylate, (meth) acrylate monomers having a carboxyl group, a hydroxyl group, an amino group, a sulfonic acid group, etc. (for example, (meth) acrylic acid , Methylol (meth) acrylate, hydroxyalkyl (meth) acrylate, allyl acrylate, etc.). The latter, after copolymerization,
JP-A-10-25388 and JP-A-10-147739 describe that a crosslinked structure can be introduced.

Further, in addition to the above monomers, a fluorine-containing copolymer formed by using a fluorine-containing vinyl monomer and a monomer other than a monomer for providing a crosslinkable group in combination with a fluorine-containing copolymer before curing. You may use as a fluororesin. There are no particular limitations on the monomers that can be used in combination, and for example, olefins (ethylene, propylene, isoprene, vinyl chloride, vinylidene chloride, etc.), acrylates (methyl acrylate, methyl acrylate, ethyl acrylate, acrylic acid) 2-ethylhexyl), methacrylates (methyl methacrylate,
Ethyl methacrylate, butyl methacrylate, ethylene glycol dimethacrylate, etc.), styrene derivatives (styrene, divinylbenzene, vinyl toluene, α-methylstyrene, etc.), vinyl ethers (methyl vinyl ether, etc.), vinyl esters (vinyl acetate, propionic acid) Vinyl, vinyl cinnamate, etc.), acrylamides (Nt
tert-butylacrylamide, N-cyclohexylacrylamide, etc.), methacrylamides, acrylonitrile derivatives and the like.

The proportion of each of the above-mentioned monomers used to form the fluorine-containing copolymer before curing is preferably 20 to 80% by mass of a fluorine-containing vinyl monomer, The amount of the monomer is preferably 1 to 30% by mass, and the amount of other monomers used in combination is preferably 0 to 70% by mass.

Inorganic fine particles can be added to the low refractive index layer of the antiglare antireflection film of the present invention. Thereby, the volume shrinkage at the time of curing is reduced, the adhesion is improved, and the scratch resistance is prevented from lowering. Further, the hardness of the inorganic fine particles improves the film strength and the scratch resistance.

As the inorganic fine particles to be used in the low refractive index layer, amorphous fine particles are preferably used.
It is preferably made of a nitride, a sulfide or a halide, and particularly preferably a metal oxide. As the metal atom, Na, K, Mg, Ca, Ba, Al, Zn, F
e, Cu, Ti, Sn, In, W, Y, Sb, Mn, G
a, V, Nb, Ta, Ag, Si, B, Bi, Mo, C
e, Cd, Be, Pb and Ni are preferred, and Mg, C
a, B and Si are more preferred. Inorganic fine particles containing two or more metals may be used. Particularly preferred inorganic fine particles are silicon dioxide fine particles, that is, silica fine particles. The average particle size of the inorganic fine particles is preferably from 0.001 to 0.2 μm, more preferably from 0.005 to 0.05 μm. The particle diameter of the fine particles is preferably as uniform (monodispersed) as possible. When the particle size of the inorganic fine particles is too large, the film becomes opaque, and when the particle size is too small, the film is easily aggregated and the synthesis and handling are difficult.

The amount of the inorganic fine particles is preferably 3 to 90% by mass, more preferably 5 to 70% by mass, and particularly preferably 7 to 50% by mass of the total mass of the low refractive index layer.
% By mass. If the addition amount of the inorganic fine particles is too large, a continuous layer of the fluorine-containing copolymer component as a binder cannot be formed, resulting in brittleness. If the addition amount is too small, the effect of adding the fine particles cannot be obtained.

The inorganic fine particles are preferably subjected to a surface treatment before use. As the surface treatment method, there are a physical surface treatment such as a plasma discharge treatment and a corona discharge treatment and a chemical surface treatment using a coupling agent, but the use of a coupling agent is preferred. As the coupling agent, an organoalkoxy metal compound (eg, a titanium coupling agent, a silane coupling agent, etc.) is preferably used. When the inorganic fine particles are silica, treatment with a silane coupling agent is particularly effective.

Curing is performed by applying a coating liquid, drying and then heating or irradiating with ionizing radiation (ultraviolet rays, electron beams, etc.) to form a low refractive index layer.

The thickness of the low refractive index layer of the antiglare antireflection film is preferably 0.05 to 0.2 μm, more preferably 0.08 to 0.12 μm.

The adjustment of the refractive index of the low refractive index layer to the above specified range and further satisfying the above formula (I) are performed by adjusting the solid content concentration of the coating solution and the wet coating amount.

The layers constituting the antiglare antireflection film of the present invention have been described above. As already described, the anti-glare antireflection film of the present invention has (a) an average value of specular reflectance at a 5-degree incidence in a wavelength region from 450 nm to 650 nm of 1.2% or less; Preferably, the integrated reflectivity at 450 degrees from 5 nm is 450 nm to 65 nm.
The average value in the wavelength region up to 0 nm is 2.5% or less, and (c) preferably, the wavelength is from 380 nm to 780 nm.
When the color of specularly reflected light with respect to the incident light of 5 degrees of the CIE standard light source D65 in the region of No. is measured by L *, a *, and b * values in the CIE1976 L * a * b * color space, L * ≦ 10 each. , 0 ≦ a * ≦ 2, −5 ≦ b * ≦ 2, and (d) preferably a haze value of 5-1
It is in the range of 5%.

Each layer of the antiglare antireflection film of the present invention may be formed by a dip coating method, an air knife coating method, a curtain coating method, a roller coating method, a wire bar coating method, a gravure coating method or an extrusion coating method (US Pat. No. 2,681,294). According to the specification, a coating liquid for forming each layer can be applied, and if necessary, can be formed by irradiation or heating. Two or more layers may be applied simultaneously. Regarding the method of simultaneous coating, U.S. Pat. Nos. 2,761,791 and 2,918,898,
Nos. 3,508,947 and 3,526,528, and in Yuji Harazaki, Coating Engineering, page 253, Asakura Shoten (1973).

The antiglare antireflection film of the present invention can be used for a liquid crystal display (LCD), a plasma display panel (P
DP), electroluminescent display (EL)
D) or an image display device such as a cathode ray tube display device (CRT). The anti-glare anti-reflection film of the present invention is applied by adhering the transparent support side to the image display surface of the image display device. When applied to the surface or the inner surface of the LCD, it protects the polarizing layer of the polarizing plate. More preferably, it is used as it is as a film on one side of the two protective films.

[0052]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the invention in any way.

(Preparation of Coating Solution A for Antiglare Layer) 125 g of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.), bis (4-methacryloylthiophenyl) sulfide ( MPSMA, manufactured by Sumitomo Seika Co., Ltd.)
125 g was dissolved in 439 g of a mixed solvent of methyl ethyl ketone / cyclohexanone = 50/50% by mass. A solution prepared by dissolving 5.0 g of a photopolymerization initiator (Irgacure 907, manufactured by Ciba Geigy) and 3.0 g of a photosensitizer (Kayacure DETX, manufactured by Nippon Kayaku Co., Ltd.) in 49 g of methyl ethyl ketone was added to the obtained solution. added. The refractive index of the coating film obtained by applying this solution and curing with ultraviolet light is 1.60.
Met. Further, 10 g of crosslinked polystyrene particles having an average particle size of 2 μm (trade name: SX-200H, manufactured by Soken Chemical Co., Ltd.) was added to this solution, and 500 g of high-speed disperser was used.
After stirring and dispersing at 0 rpm for 1 hour, the mixture was filtered through a polypropylene filter having a pore size of 30 μm to prepare a coating solution for the antiglare layer.

(Preparation of Coating Solution B for Antiglare Layer) A hard coat coating solution containing a zirconium oxide dispersion (Desolite KZ-7) was mixed with a mixed solvent of 104.1 g of cyclohexanone and 61.3 g of methyl ethyl ketone while stirring with an air disper.
886A (manufactured by JSR Corporation) 217.0 g. The refractive index of the coating film obtained by applying this solution and curing with ultraviolet light was 1.61. In addition, the average particle size
μm crosslinked polystyrene particles (trade name: SX-200)
H, manufactured by Soken Chemical Co., Ltd.), and the mixture was stirred and dispersed at 5000 rpm for 1 hour with a high-speed disperser.
The solution was filtered through a 0 μm polypropylene filter to prepare a coating solution for the antiglare layer.

(Preparation of Coating Solution C for Antiglare Layer) 91 g of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.), a hard coat coating solution containing a zirconium oxide dispersion ( Desolite KZ-7115, JSR
199 g) and a hard coat coating solution containing zirconium oxide dispersion (Desolite KZ-7161, J
19 g of SR (manufactured by SR Corporation) was dissolved in 52 g of a mixed solvent of methyl ethyl ketone / cyclohexanone = 54/46% by mass. To the resulting solution was added 10 g of a photopolymerization initiator (Irgacure 907, manufactured by Ciba Geigy). The refractive index of the coating film obtained by applying this solution and curing with ultraviolet light is 1.6.
It was one. Further, 20 g of crosslinked polystyrene particles having an average particle diameter of 2 μm (trade name: SX-200H, manufactured by Soken Chemical Co., Ltd.) was added to this solution in 80 g of a mixed solvent of methyl ethyl ketone / cyclohexanone = 54/46% by mass at 5,000 rpm by a high-speed disper. Dispersion liquid 2 with stirring and dispersion for 1 hour
After adding 9 g and stirring, the mixture was filtered through a polypropylene filter having a pore size of 30 μm to prepare a coating solution for the antiglare layer.

(Preparation of Coating Solution D for Hard Coat Layer) An ultraviolet-curable hard coat composition (Desolite KZ-768)
A solution prepared by dissolving 250 g of 9,72% by mass (manufactured by JSR Corporation) in 62 g of methyl ethyl ketone and 88 g of cyclohexanone was added. The refractive index of the coating film obtained by applying this solution and curing with ultraviolet light was 1.53. This solution was further filtered through a polypropylene filter having a pore size of 30 μm to prepare a coating solution for the hard coat layer.

(Preparation of Coating Solution for Low Refractive Index Layer) Refractive index
42 heat-crosslinkable fluoropolymers (TN-049, JS
MEK-ST (average particle size: 10 to 2)
MEK of SiO2 sol with 0 nm and solid content concentration of 30% by mass
8 g of the dispersion, manufactured by Nissan Chemical Co., Ltd.) and 100 g of methyl ethyl ketone were added, and after stirring, the mixture was filtered through a polypropylene filter having a pore size of 1 μm to prepare a coating solution for a low refractive index layer.

Example 1 The above coating solution D for a hard coat layer was applied to a triacetyl cellulose film (TAC-TD80U, manufactured by Fuji Photo Film Co., Ltd.) having a thickness of 80 μm using a bar coater. After drying at 120 ° C., an illuminance of 400 mW / cm was applied using an air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) of 160 W / cm.
cm ^2, and an irradiation dose of 300 mJ / cm ² to cure the coating layer, to form a hard coat layer having a thickness of 2.5 [mu] m. The anti-glare layer coating solution A was applied thereon using a bar coater, dried and cured under the same conditions as the hard coat layer to form an anti-glare layer having a thickness of about 1.5 μm. . The coating liquid for a low refractive index layer was applied thereon using a bar coater, dried at 80 ° C, and further dried at 120 ° C.
For 10 minutes to form a low refractive index layer having a thickness of 0.096 μm.

Example 2 A hard coat layer was formed on a triacetyl cellulose film (TAC-TD80U, manufactured by Fuji Photo Film Co., Ltd.) having a thickness of 80 μm in the same manner as in Example 1. The anti-glare layer coating solution B was applied thereon using a bar coater, dried and cured under the same conditions as the hard coat layer to form an anti-glare layer having a thickness of about 1.5 μm. . The low refractive index layer coating solution is applied thereon using a bar coater, dried at 80 ° C., and thermally crosslinked at 120 ° C. for 10 minutes to form a low refractive index layer having a thickness of 0.096 μm. did.

Example 3 A hard coat layer was formed in the same manner as in Example 1 on a triacetyl cellulose film (TAC-TD80U, manufactured by Fuji Photo Film Co., Ltd.) having a thickness of 80 μm. The anti-glare layer coating solution C was applied thereon using a bar coater, dried and cured under the same conditions as the hard coat layer to form an anti-glare layer having a thickness of about 1.5 μm. . The low refractive index layer coating solution is applied thereon using a bar coater, dried at 80 ° C., and thermally crosslinked at 120 ° C. for 10 minutes to form a low refractive index layer having a thickness of 0.096 μm. did.

[Comparative Example 1] The above coating solution D for a hard coat layer was coated on a triacetyl cellulose film (TAC-TD80U, manufactured by Fuji Photo Film Co., Ltd.) having a thickness of 80 μm using a bar coater. After drying at 120 ° C., an illuminance of 400 mW / cm was applied using an air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) of 160 W / cm.
cm ^2, and an irradiation dose of 300 mJ / cm ² to cure the coating layer, to form a hard coat layer having a thickness of 4 [mu] m. On top of that, the same anti-glare layer coating liquid as the anti-glare layer coating liquid A was applied using a bar coater except that all of the MPSMA was replaced with DPHA, and dried under the same conditions as the hard coat layer. UV curing was performed to form an antiglare layer having a thickness of about 1.5 μm and a refractive index of 1.51. The above-mentioned coating solution for a low refractive index layer was applied thereon using a bar coater.
, And then thermally crosslinked at 120 ° C. for 10 minutes to form a low refractive index layer having a thickness of 0.096 μm.

(Evaluation of antireflection film) The following items were evaluated for the obtained film. (1) Specular reflectivity and tint An adapter ARV-474 was attached to a spectrophotometer V-550 (manufactured by JASCO Corporation), and an emission angle of -5 at an incident angle of 5 ° in a wavelength range of 380 to 780 nm. The specular reflectivity was measured, the average reflectivity at 450 to 650 nm was calculated, and the antireflection property was evaluated. Further, from the measured reflection spectrum, CIE1976L * a representing the color of specularly reflected light with respect to the incident light of 5 degrees of the CIE standard light source D65 from the CIE standard light source D65.
The L * value, a * value, and b * value of the * b * color space were calculated, and the tint of the reflected light was evaluated. (2) Integrated reflectance The adapter ILV-471 was attached to a spectrophotometer V-550 (manufactured by JASCO Corporation), and the integrated reflectance at an incident angle of 5 ° was measured in a wavelength range of 380 to 780 nm. The average reflectance from 450 to 650 nm was calculated. (3) Haze The haze of the obtained film was measured using a haze meter MODEL.
It measured using 1001DP (made by Nippon Denshoku Industries Co., Ltd.). (4) Pencil hardness evaluation A pencil hardness evaluation described in JIS K 5400 was performed as an index of scratch resistance. Antireflection film at a temperature of 25 ° C and a humidity of 60
% RH for 2 hours, using a 3H test pencil specified in JIS S 6006, with a load of 1 kg, and no scratches are observed in the evaluation of n = 5: ○ In the evaluation of n = 5 1 or 2 flaws: Δ 3 or more flaws in evaluation of n = 5: × (5) Contact angle measurement As an index of surface contamination resistance (fingerprint adhesion), an optical material was subjected to a temperature of 25 ° C. and a humidity of 60. After conditioning for 2 hours at% RH, the contact angle to water was measured.

(6) Measurement of dynamic friction coefficient The dynamic friction coefficient was evaluated as an index of the surface slip property. Motion
The coefficient of friction was adjusted at 25 ° C and 60% relative humidity for 2 hours.
5mmφ with HEIDON-14 dynamic friction measuring machine
Stainless steel ball, load 100g, speed 60cm / min
The value measured in was used. (7) Evaluation of antiglare property Exposed fluorescence without louver on the prepared antiglare film
Light (8000 cd / m ^Two) And the reflection image is blurred
The degree was evaluated according to the following criteria. The outline of the fluorescent lamp is not known at all: ◎ The outline of the fluorescent lamp is slightly recognized: ○ The fluorescent lamp is blurred, but the outline can be identified: △ The fluorescent lamp is hardly blurred: ×

Table 1 shows the results of Examples and Comparative Examples.
The following is clear from the results shown in Table 1. Any of the anti-glare anti-reflection films of Examples 1, 2, and 3,
The antiglare property and the antireflection property were excellent, the color was weak, and the evaluation results reflecting the film properties such as pencil hardness, fingerprint adhesion and dynamic friction coefficient were also good. On the other hand, in Comparative Example 1, sufficient antireflection properties could not be obtained because the refractive index of the antiglare layer was low.

[0065]

[Table 1]

Next, an antiglare antireflection polarizing plate was prepared using the film of Example 3. When a liquid crystal display device in which an antireflection layer was disposed on the outermost layer was prepared using this polarizing plate, an excellent contrast was obtained because there was no reflection of external light, and a reflection image was inconspicuous due to antiglare properties. It had visibility and fingerprints were good.

(Preparation of Triacetyl Cellulose Dope A) 17.4 parts by mass of triacetyl cellulose, 2.6 parts by mass of triphenyl phosphate, 66 parts by mass of dichloromethane
A raw material consisting of parts by mass, 5.8 parts by mass of methanol, and 8.2 parts by mass of normal butanol was mixed with stirring and dissolved to prepare triacetyl cellulose dope A.

(Preparation of triacetyl cellulose dope B) 24 parts by weight of triacetyl cellulose, 4 parts by weight of triphenyl phosphate, 66 parts by weight of dichloromethane,
A raw material consisting of 6 parts by mass of methanol was mixed and dissolved with stirring to prepare triacetyl cellulose dope B.

(Preparation of Triacetyl Cellulose Dope C) Triacetyl cellulose 20 parts by mass, methyl acetate 4
8 parts by mass, cyclohexanone 20 parts by mass, methanol 5
Parts by mass, ethanol 5 parts by mass, triphenyl phosphate / biphenyl diphenyl phosphate (1/2) 2 parts by mass, silica (particle size: 20 nm) 0.1 part by mass, 2,4-
Bis- (n-octylthio) -6- (4-hydroxy-
After adding 0.2 parts by mass of 3,5-di-tert-butylanilino) -1,3,5-triazine and stirring, the resulting non-uniform gel-like solution was cooled at -70 ° C for 6 hours. , 50
The mixture was heated to ℃ and stirred to prepare dope C.

(Preparation of Triacetyl Cellulose Dope D) The heterogeneous gel solution obtained in the same manner as in the above triacetyl cellulose dope C was heated at 180 ° C. and 1 MPa in a stainless steel closed vessel for 5 minutes. The whole container was put into a water bath at 50 ° C. and cooled to prepare triacetylcellulose dope D.

(Preparation of Coating Solution A 'for Antiglare Layer) A mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, Nippon Kayaku
91 g, zirconium oxide dispersion-containing hard coat coating solution (Desolite Z-7401, manufactured by JSR Corporation)
218 g was dissolved in 52 g of a mixed solvent of methyl ethyl ketone / cyclohexanone = 54/46% by mass. To the resulting solution was added 10 g of a photopolymerization initiator (Irgacure 907, manufactured by Ciba Geigy). The refractive index of the coating film obtained by applying this solution and curing with ultraviolet light was 1.61.
Further, 20 g of crosslinked polystyrene particles having an average particle size of 2 μm (trade name: SX-200H, manufactured by Soken Chemical Co., Ltd.) were added to this solution.
To 80 g of methyl ethyl ketone / cyclohexanone = 5
5000 in a mixed solvent of 4/46 mass% by high-speed disperser
After adding and stirring 29 g of the dispersion liquid stirred and dispersed at 1 rpm for 1 hour, the mixture was filtered through a polypropylene filter having a pore diameter of 30 μm to prepare a coating liquid A for the antiglare layer.

(Preparation of Coating Solution B 'for Antiglare Layer) A mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, Nippon Kayaku
250 g) was dissolved in 439 g of a mixed solvent of methyl ethyl ketone / cyclohexanone = 50/50% by mass. To the obtained solution, 5.0 g of a photopolymerization initiator (Irgacure 907, manufactured by Ciba Geigy) and 3.0 g of a photosensitizer (Kayacure DETX, manufactured by Nippon Kayaku Co., Ltd.)
Was dissolved in 49 g of methyl ethyl ketone. The coating film obtained by applying this solution and curing with ultraviolet light had a refractive index of 1.51. In addition, the average particle size
μm crosslinked polystyrene particles (trade name: SX-200)
H, manufactured by Soken Chemical Co., Ltd.) and stirred and dispersed at 5,000 rpm for 1 hour with a high-speed disperser.
The solution was filtered through a μm polypropylene filter to prepare a coating solution B ′ for the antiglare layer.

(Preparation of Coating Solution C 'for Hard Coat Layer) An ultraviolet-curable hard coat composition (Desolite Z-752)
A solution prepared by dissolving 250 g of 6, 72% by mass (manufactured by JSR Corporation) in 62 g of methyl ethyl ketone and 88 g of cyclohexanone was added. The refractive index of the coating film obtained by applying this solution and curing with ultraviolet light was 1.53. The solution was further filtered through a polypropylene filter having a pore size of 30 μm to prepare a coating solution C ′ for the hard coat layer.

(Preparation of Coating Solution D 'for Low Refractive Index Layer) The refractive index was 1.42, and 6% by mass of the thermally crosslinkable fluoropolymer.
Of methyl ethyl ketone (JN-7228, JSR
MEK-ST (average particle size: 10 to 20 n) in 93 g
m, 8 g of a methyl ethyl ketone dispersion of a SiO ₂ sol having a solid concentration of 30% by mass (manufactured by Nissan Chemical Co., Ltd.), 94 g of methyl ethyl ketone, and 6 g of cyclohexanone. After stirring, a polypropylene filter having a pore diameter of 1 μm (P
The mixture was filtered through PE-01) to prepare a coating liquid D 'for the low refractive index layer.

Example 4 According to JP-A-11-254594 and the like, a three-layer co-casting die was used, and a dope A was arranged on both sides of a dope B so as to be co-cast and discharged simultaneously onto a metal drum. After the multilayer casting, the casting film was peeled off from the drum, dried, and 10 μm, 60 μm,
A 10 μm three-layer co-cast triacetyl cellulose film was prepared. In this film, no clear interface was formed between the layers. The triacetyl cellulose film is coated with the coating solution C ′ for a hard coat layer using a bar coater, and dried at 120 ° C. for 5 minutes.
Illuminance of 400 mW / c using a 160 W / cm air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.)
The coating layer was cured by irradiating ultraviolet rays with m ² and an irradiation amount of 300 mJ / cm ² to form a hard coat layer having a thickness of 2.5 μm. The antiglare layer coating solution A 'was applied thereon using a bar coater, and dried and cured with ultraviolet light under the same conditions as the hard coat layer except that the oxygen concentration in the atmosphere was reduced to 6% by nitrogen purge. Thus, an anti-glare layer having a thickness of about 1.5 μm was formed. The coating solution D 'for a low refractive index layer was applied thereon using a bar coater, dried at 80 ° C, and further dried at 12 ° C.
Thermal crosslinking was performed at 0 ° C. for 8 minutes to form a low refractive index layer having a thickness of 0.096 μm.

Example 5 In accordance with JP-A-7-11055, the above triacetylcellulose dope C was cast in a single-layer drum to form a triacetylcellulose film having a thickness of 80 μm. Thus, a hard coat layer, an antiglare layer, and a low refractive index layer were formed.

Example 6 According to JP-A-7-11055, the above-mentioned triacetylcellulose dope D was cast in a single-layer drum to form a triacetylcellulose film having a thickness of 80 μm. Thus, a hard coat layer, an antiglare layer, and a low refractive index layer were formed.

Comparative Example 2 The above coating solution D ′ for a hard coat layer was coated on a triacetyl cellulose film (TAC-TD80U, manufactured by Fuji Photo Film Co., Ltd.) having a thickness of 80 μm using a bar coater. After drying at 120 ° C., the illuminance was 400 mW / c using an air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) of 160 W / cm.
The coating layer was cured by irradiating ultraviolet rays having an irradiation amount of 300 mJ / cm ² with m ² , and a hard coat layer having a thickness of 4 μm was formed. An anti-glare layer coating solution B ′ was applied thereon using a bar coater, dried and cured under the same conditions as for the hard coat layer, to a thickness of about 1.5 μm and a refractive index of 1.51. An antiglare layer was formed. The coating liquid D ′ for a low refractive index layer was applied thereon using a bar coater, dried at 80 ° C., and further thermally crosslinked at 120 ° C. for 10 minutes, to a thickness of 0.09.
A 6 μm low refractive index layer was formed.

Table 2 shows the results of Examples 4 to 6 and Comparative Example 2. The evaluation method is as described above. The following is clear from the results shown in Table 2. Each of the anti-glare and anti-reflection films of Examples 4, 5, and 6 has excellent anti-glare properties and anti-reflection properties, has low tint, and reflects film properties such as pencil hardness, fingerprint adhesion, and dynamic friction coefficient. The result of the evaluation was also good. On the other hand, in Comparative Example 2, sufficient antireflection properties could not be obtained because the refractive index of the antiglare layer was low.

[0080]

[Table 2]

Next, an antiglare antireflection polarizing plate was prepared using the film of Example 6. When a liquid crystal display device in which an antireflection layer was disposed on the outermost layer was prepared using this polarizing plate, an excellent contrast was obtained because there was no reflection of external light, and a reflection image was inconspicuous due to antiglare properties. It had visibility and had good fingerprints.

[0082]

The anti-glare anti-reflection film of the present invention can be manufactured simply and inexpensively simply by forming an anti-glare layer and a low refractive index layer on a support, and has sufficient anti-reflection performance and scratch resistance. Properties and antifouling properties, as well as little color and uneven color. Further, the polarizing plate and the liquid crystal display device of the present invention can obtain excellent contrast because the reflection of external light is sufficiently prevented, and are excellent in stain resistance and scratch resistance.

[Brief description of the drawings]

FIG. 1 is a schematic sectional view showing a layer configuration of an antiglare antireflection film.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Anti-glare antireflection film 2 Transparent support made of triacetyl cellulose 3 Hard coat layer 4 Anti-glare layer 5 Low refractive index layer 6 Resin mat particles

 ──────────────────────────────────────────────────続 き Continuing on the front page F term (reference) 2H049 BA02 BB33 BB63 BB65 BC22 2H091 FA08X FA37X FB02 FC01 FD06 FD15 GA16 KA01 LA02 LA03 LA07 2K009 AA04 BB14 CC26 CC42 DD02 4F100 AA27 AJ06A AK12 AK17C00 AR25 BA03 EH46 EH90 EJ54 GB41 JB06C JB13C JB14C JK16C JN01A JN06 JN08 JN18C JN28 JN30B YY00C 5G435 AA00 AA02 AA04 AA17 BB12 FF02 FF05 HH02 HH03 KK07

Claims (10)

[Claims] An antiglare layer and at least one antiglare layer are provided on a transparent support.
And a low-refractive-index layer in this order, and the average value of the specular reflectance at a 5-degree incidence in a wavelength region from 450 nm to 650 nm is 1.2% or less. Anti-reflective film. 2. A transparent support, wherein triacetyl cellulose dope prepared by dissolving triacetyl cellulose in a solvent is cast by a single-layer casting method or a multi-layer co-casting method. The anti-glare anti-reflection film according to claim 1, which is a prepared triacetyl cellulose film. 3. The triacetyl cellulose dope,
The anti-glare antireflection according to claim 2, wherein the dope is prepared by dissolving triacetyl cellulose in a solvent substantially free of dichloromethane by a low-temperature dissolution method or a high-temperature dissolution method. the film. 4. An integrated reflectance of 450n at 5 degrees incidence.
The average value in the wavelength region from m to 650 nm is 2.5%
The anti-glare anti-reflection film according to claim 1, wherein: 5. The color of specularly reflected light with respect to 5 degrees incident light of the CIE standard light source D65 in the wavelength range of 380 nm to 780 nm is L in the CIE1976L * a * b * color space.
*, A *, and b * values are L * ≦ 10, 0 ≦ a * ≦
The anti-glare anti-reflection film according to claim 1, wherein the anti-glare film has a color satisfying −5 ≦ b * ≦ 2. 6. The antiglare antireflection film according to claim 1, wherein the haze value is in the range of 5 to 15%. 7. The antiglare antireflection according to claim 1, wherein the low refractive index layer is made of a cured product of a thermosetting or ionizing radiation curable fluororesin. the film. 8. The low refractive index layer comprising a cured product of the above-mentioned fluororesin, wherein the coefficient of dynamic friction is in the range of 0.03 to 0.15 and the contact angle with water is in the range of 90 to 120 degrees. The anti-glare anti-reflection film according to claim 7, characterized in that: 9. A polarizing plate, wherein the antiglare antireflection film according to claim 1 is used for at least one of two protective films of a polarizing layer in a polarizing plate. 10. The antiglare antireflection film according to claim 1 or the antireflection layer of the antiglare antireflection polarizing plate according to claim 9 is used as the outermost layer of a display. A liquid crystal display device characterized by the above-mentioned.