JP2001100005A - Antidazzle antireflection film, polarizing plate and image display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an antidazzle antireflection film excellent in visibility at a low cost. SOLUTION: At least one low refractive index layer 4 having microvoids and a refractive index of 1.38-1.49 is disposed on a substrate 1 by curing a coating film of a coating fluid comprising inorganic fine particles, a curable resin and an antifouling material with heat or ionizing radiation and an antidazzle layer 3 containing a binder having a refractive index of 1.57-2.00 is interposed between the substrate and the low refractive index layer to obtain the antidazzle antireflection film.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antireflection film having antiglare properties, a polarizing plate, and a liquid crystal display 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. Placed on the surface

[0003]

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 very low refractive index. For example, an anti-reflection film using triacetyl cellulose as a support and a UV-cured coating of dipentaerythritol hexaacrylate as a hard coat layer has a thickness of 450 to 650.
In order to make the average reflectance in nm less than 1.6%, the refractive index must be made less than 1.40. Materials having a refractive index of 1.40 or less satisfying the above conditions include magnesium fluoride and calcium fluoride for inorganic substances, and fluorine-containing compounds having a large fluorine content for organic substances. When used for a film disposed on the outermost surface, scratch resistance was insufficient. Further, in order to have sufficient scratch resistance, it was necessary to use a compound having a refractive index of 1.43 or more.

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 problem in that since the difference in refractive index from the support is large, color unevenness of the film occurs, and the wavelength dependence of the reflectance also has a large amplitude. Japanese Patent Application Laid-Open No. Hei 7-333404 describes an antiglare antireflection film having excellent gas barrier properties, antiglare properties, and antireflection properties. However, formation of a silicon oxide film by chemical vapor deposition (CVD) is essential. Therefore, the productivity is inferior to the wet coating method. An object of the present invention is to improve an antireflection film for forming a hard coat layer and a low refractive index layer on a support,
Provide an anti-glare anti-reflection film that is simple and inexpensive and has sufficient anti-reflection performance, scratch resistance, and anti-fouling properties with less color unevenness, a polarizing plate using the same, and a liquid crystal display device using the same. It is to be.

[0005]

The object of the present invention has been attained by the following inventions. (1) Microvoids having a refractive index of 1.3 obtained by curing a coating film of a coating solution composed of inorganic fine particles, a curable resin and an antifouling material on a substrate by heat or ionizing radiation.
At least one low refractive index layer having a refractive index of 8 to 1.49 is provided, and the refractive index between the base material and the low refractive index layer is 1.57 to 2.49.
An antiglare antireflection film, comprising an antiglare layer containing a binder of No. 00. (2) The antiglare antireflection film according to (1), wherein at least one hard coat is provided between the substrate and the antiglare layer. (3) The antiglare antireflection film according to (1) or (2), wherein in the low refractive index layer, the antifouling material is a fluorine-containing alkylalkoxysilane compound. (4) The antiglare according to (1) or (2), wherein in the low refractive index layer, the antifouling material is any one of a monomer, oligomer and polymer having a fluorine-containing alkyl group. Anti-reflective film. (5) The anti-glare layer according to (1), (2), (3) or (4), wherein the anti-glare layer is made of a binder containing a cured product of mat fine particles and a heat or ionizing radiation curable resin. Anti-glare anti-reflection film. (6) The average particle diameter of the mat fine particles is 1 μm to 10 μm
The antiglare antireflection film according to the item (5), wherein (7) In the antiglare layer, the binder having a refractive index of 1.57 to 2.00 is a heat or ionizing radiation cured product of a mixture of a high refractive index monomer and a trifunctional or higher (meth) acrylate monomer. The anti-glare anti-reflection film according to item (5). (8) In the antiglare layer, the binder having a refractive index of 1.57 to 2.00 is Al, Zr, Zn, Ti, or I.
Anti-glare reflection according to item (5), which is a heat or ionizing radiation cured product of a mixture of ultrafine particles of a metal oxide selected from n and Sn and a trifunctional or higher (meth) acrylate monomer. Prevention film. (9) The antiglare antireflection film according to any one of (1) to (8) is used for at least one of two protective films of a polarizing layer in a polarizing plate. Polarizer. (10) With the antiglare antireflection film according to any one of (1) to (8) or the polarizing plate according to (9) as the antireflection layer on the front side, the outermost layer of the display. A liquid crystal display device characterized by using:

[0006]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Preferred embodiments 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, which comprises a transparent support 1 made of triacetyl cellulose, a hard coat layer 2, an antiglare layer 3, and a low refractive index having microvoids. It has a layer configuration in the order of layer 4. Reference numeral 5 denotes resin mat fine particles. In the antireflection film, the low refractive index layer preferably satisfies the following formula (I).

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

Wherein m is a positive odd number (generally 1);
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 the wavelength of the light beam used. The refractive index of the low refractive index layer is preferably 1.43 to 1.4.
8 If this is too small, the film strength will be weak and the scratch resistance will be reduced, and if it is too large, the antireflection properties will be reduced.

The binder of the antiglare layer of the present invention has a refractive index of:
It is from 1.57 to 2.00, preferably from 1.57 to 1.80, and if it is too small or too large, the antireflection property is reduced. The refractive index of, for example, triacetyl cellulose used as a support is 1.48. In this binder, the high refractive index material is a monomer having two or more ethylenically unsaturated groups and titanium, aluminum, indium,
In the case of ultrafine particles having a particle diameter of 100 nm or less made of at least one oxide selected from zinc, tin, and antimony, scattering does not occur because the particle diameter of the ultrafine particles is sufficiently smaller than the wavelength of light. It is described in Japanese Patent Application Laid-Open No. H8-110401 that it exhibits a behavior as a homogeneous substance.

The anti-glare layer is not affected by optical interference in the anti-glare layer because surface scattering is caused by mat fine particles dispersed in the high refractive index material. The mat particles act on the anti-glare property. In the high refractive index hard coat layer having no matte fine particles, a large amplitude of the reflectance is seen in the wavelength dependence of the reflectance due to the optical interference due to the refractive index difference between the hard coat layer and the support. Although the prevention effect deteriorates and color unevenness occurs at the same time, these problems were solved by the antireflection film of the present invention by the scattering effect due to the surface unevenness of the antiglare layer.

In the present invention, a transparent support is used as a substrate. As the transparent support, triacetyl cellulose is preferable, but polyethylene terephthalate, polyethylene naphthalate, polycarbonate and the like can also be used. When the antiglare antireflection film of the present invention is used for a liquid crystal display device, it is disposed on the outermost surface of the display by providing an adhesive layer on one surface or the like. Since triacetyl cellulose is used for a protective film for protecting a polarizing layer of a polarizing plate, it is preferable in terms of cost to use the antiglare antireflection film of the present invention as it is for a protective film.

In the present invention, it is preferable to provide at least one hard coat between the substrate and the antiglare layer. The compound used for forming the hard coat layer is preferably a polymer having a saturated hydrocarbon or polyether as a main chain, and more preferably a polymer having a saturated hydrocarbon as a main chain. The binder polymer is preferably crosslinked. The polymer having a saturated hydrocarbon as a main chain is preferably obtained by a polymerization reaction of an ethylenically unsaturated monomer. In order to obtain a crosslinked binder polymer, it is preferable to use a monomer having two or more ethylenically unsaturated groups.

Examples of the monomer having two or more ethylenically unsaturated groups include esters of polyhydric alcohol and (meth) acrylic acid (eg, ethylene glycol di (meth) acrylate, 1,4-dichlorohexane diacrylate) Pentaerythritol tetra (meth) acrylate), pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethanetri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta ( (Meth) acrylate, dipentaerythritol 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 included.

The polymer having a polyether as a main chain is preferably synthesized by a ring-opening polymerization reaction of a polyfunctional epoxy compound. These monomers having an ethylenically unsaturated group need to be cured by a polymerization reaction by ionizing radiation or heat after coating.

A compound having a crosslinkable group may be used instead of or in addition to the monomer having two or more ethylenically unsaturated groups, and a crosslinked structure may be introduced into the binder polymer by the reaction. Examples of crosslinkable functional groups include isocyanate groups, epoxy groups, aziridine groups, oxazoline groups, aldehyde groups, carbonyl groups, hydrazine groups,
Includes carboxyl, methylol and active methylene groups. 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. Further, in the present invention, the cross-linking group is not limited to the above-mentioned compound, but may be one which shows reactivity as a result of decomposition of the above-mentioned functional group. These compounds having a cross-linking group need to be cross-linked by heat or the like after coating.

The compound for forming the antiglare layer may contain, in addition to the material for forming the hard coat layer, a monomer having a high refractive index or inorganic fine particles having a high refractive index necessary for realizing the above-mentioned predetermined high refractive index. Including only. Examples of high refractive index monomers include:
Bis (4-methacryloylthiophenyl) sulfide,
Vinyl naphthalene, vinyl phenyl sulfide, 4-methacryloxyphenyl-4′-methoxyphenyl thioether and the like. Examples of the high refractive index inorganic fine particles preferably contain fine particles having a particle diameter of 100 nm or less, preferably 50 nm or less, made of at least one oxide selected from titanium, aluminum, indium, zinc, tin, and antimony. . Examples of fine particles include A
Examples include oxides of metals selected from l, Zr, Zn, Ti, In, and Sn. The addition amount of the high refractive index inorganic fine particles is preferably from 10 to 90% by weight, more preferably from 20 to 80% by weight, based on the total weight of the antiglare layer.

For the antiglare layer, matte fine particles of a resin or an inorganic compound are used for the purpose of imparting antiglare properties, preventing deterioration in reflectance due to interference of the hard coat layer, and preventing color unevenness. The average particle size is preferably from 1.0 to 10.0 μm, and from 1.5 to 5.
0 μm is more preferred. Examples of such resin or inorganic compound particles include particles of crosslinked acrylic resin, crosslinked polystyrene, melamine formaldehyde resin, aluminum oxide, silicon oxide, and the like. Further, it is preferable that the amount of the matte fine particles having a particle size smaller than the binder film thickness of the antiglare layer is less than 50% of the entire matte fine particles. The coating amount of the mat fine particles is preferably 10 to 1000 mg.
/ M ² , more preferably 30 to 100 mg / m ² . The particle size distribution can be measured by a Coulter counter method, a centrifugal sedimentation method, or the like, and the distribution is converted into a particle number distribution. The thickness of the antiglare layer is preferably 0.5 to 10 μm, more preferably 1 to 5 μm.

The coating liquid for forming the low refractive index layer contains inorganic fine particles having an average particle size of 0.5 nm to 100 nm, a curable resin and an antifouling material. Examples of the inorganic fine particles include silica fine particles and magnesium fluoride. Among them, silica fine particles are preferably used. The content of the inorganic fine particles is preferably 50 to 9 in the low refractive index layer.
0% by weight. Silica sol dispersed in various commercially available solvents can be used for the silica fine particles. For the purpose of improving the film strength, it is preferable to use a silane coupling agent having a reactive group such as (meth) acrylate or epoxy reacted on the surface of the silica fine particles, and the functional group is reactive with the functional group of the curable resin. Those having a group are more preferred. By adjusting the amount ratio between the inorganic fine particles and the binder, a microvoid (gap) is formed between the particles, and the refractive index is reduced accordingly. The low-refractive-index layer of the antiglare antireflection film of the present invention has microvoids (voids) formed between the fine particles by stacking at least two or more inorganic fine particles, and therefore has a very low refractive index. Are formed. Further, since the inorganic fine particles are adhered by the polymer, the strength of the low refractive index layer is excellent. Since the microvoids are not filled with the polymer, the function of lowering the refractive index of the microvoids is not impaired. The low refractive index layer is a porous layer. In the low refractive index layer, the average particle size is 0.
At least two or more inorganic fine particles of 5 to 200 nm are stacked. Microvoids are formed between the inorganic fine particles. The low refractive index layer further comprises a polymer in an amount of 5 to 50% by weight. The cured product of the curable resin adheres the inorganic fine particles but does not completely fill the microvoids. The microvoid content (ie, porosity) is preferably 5 to 30%, more preferably 10 to 20%. As the curable resin, a polyfunctional acrylate monomer or the like used for the hard coat layer is preferably used.

As the antifouling material contained in the low refractive index layer, a fluorine-containing resin is preferably used. Specifically, a fluorinated alkylalkoxysilane compound, a fluorinated alkyl group-containing monomer, oligomer, polymer, or the like is preferable, and it is particularly preferable to have a functional group capable of crosslinking with the curable resin. It is preferable that the amount of the antifouling material added is a minimum amount required to exhibit the antifouling property. The effect is that the fluorine-containing alkyl group in the antifouling material contained in the low-refractive-index coating liquid is selectively oriented to the hydrophobic air-coating liquid interface during the drying process, and is cured as it is. Accordingly, it is considered that antifouling properties are generally imparted to a low refractive index layer composed of silica fine particles having poor antifouling properties and a binder resin. In the present invention, the thickness of the low refractive index layer and the hard coat layer is preferably 0.08 to 0.15 μm in the former,
The latter is preferably from 1 to 10 μm.

Each layer of the antireflection film is formed by a dip coating method, an air knife coating method, a curtain coating method, a roller coating method, a wire bar coating method, a gravure coating method or an extrusion coating method (US Pat. No. 26812).
No. 94) can be formed by coating. Two or more layers may be applied simultaneously. The method of simultaneous coating is described in U.S. Pat.
Nos. 898, 3508947 and 3526528, and Yuji Harazaki, Coating Engineering, 253
Page, Asakura Shoten (1973), and can be carried out according to the methods described in these pages. The antiglare antireflection film is preferably fixed to at least one of the protective films on both sides of the polarizing plate by adhesion or the like.

The antireflection film is a liquid crystal display (LC)
D), an image display device such as a plasma display panel (PDP), an electroluminescence display (ELD), and a cathode ray tube display (CRT). When the antireflection film has a transparent support, the transparent support side is adhered to the image display surface of the image display device.

[0023]

EXAMPLES The present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

(Preparation of Coating Solution A for Antiglare Layer) 125 g of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (trade name: DPHA, manufactured by Nippon Kayaku Co., Ltd.), bis (4-methacryloylthiophenyl) ) 125 g of sulfide (trade name: MPSMA, manufactured by Sumitomo Seika Co., Ltd.) was dissolved in 439 g of a mixed solvent of methyl ethyl ketone / cyclohexanone = 50/50 wt%. A photopolymerization initiator (trade name:
A solution of 5.0 g of Irgacure 907, manufactured by Ciba-Geigy Corporation and 3.0 g of a photosensitizer (trade name: Kayacure DETX, manufactured by Nippon Kayaku Co., Ltd.) in 49 g of methyl ethyl ketone was added. The refractive index of the coating film obtained by applying this solution and curing with ultraviolet light was 1.60. Further, 10 g of crosslinked polystyrene particles having an average particle size of 2 μm (trade name: SX-200H, manufactured by Soken Kagaku Co., Ltd.) was added to the solution, and the mixture was stirred at 5000 rpm for 1 hour with a high-speed disperser.
After dispersion, 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 (zirconium oxide 3) was added to a mixed solvent of 104.1 g of cyclohexanone and 61.3 g of methyl ethyl ketone while stirring with an air disper.
8% by weight, trade name: KZ-7886A, JSR
217.0 g). The refractive index of the coating film obtained by applying this solution and curing with ultraviolet light was 1.61. Further, crosslinked polystyrene particles having an average particle size of 2 μm (trade name: SX-200H, Soken Chemical Co., Ltd.)
5g) and 5000 rpm at high speed disper
After stirring and dispersion 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 C for Antiglare Layer) Hard coat coating solution containing zirconium oxide dispersion (containing 71% by weight of zirconium oxide, trade name: KZ-7991, JSR
Co., Ltd.) was applied and cured by ultraviolet light, and the coating film obtained had a refractive index of 1.70. To this solution, 5 g of crosslinked polystyrene particles (trade name: SX-200H, manufactured by Soken Chemical Co., Ltd.) having an average particle size of 2 μm was added, and 500
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 D for Hard Coat Layer) 250 g of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.) was mixed with 439 g of methyl ethyl ketone / cyclohexanone = 50/50. It dissolved in the mixed solvent of weight%. 4. 7.5 g of a photopolymerization initiator (Irgacure 907, manufactured by Ciba Geigy) and a photosensitizer (Kayacure DETX, manufactured by Nippon Kayaku Co., Ltd.)
A solution of 0 g in 49 g of methyl ethyl ketone was added. The refractive index of the coating film obtained by applying this solution and curing with ultraviolet light was 1.53. Further, the solution was added to a pore size of 30.
The solution was filtered through a μm polypropylene filter to prepare a coating solution for the hard coat layer.

(Preparation of Coating Solution A for Low Refractive Index Layer) (Preparation of Coating Solution for Low Refractive Index Layer) 200 g of a methanol dispersion of silica fine particles having a particle diameter of 15 nm (methanol silica sol, manufactured by Nissan Chemical Co., Ltd.) was added to a silane cup. Ring agent (brand name: KBM-503, manufactured by Shin-Etsu Silicone Co., Ltd.) 10 g
Then, 2 g of 0.1N hydrochloric acid was added, and the mixture was stirred at room temperature for 5 hours and then left at room temperature for 4 days to prepare a dispersion of silane-coupled silica fine particles (silica fine particle content: 30% by weight). To 149 g of the dispersion, 789 g of isopropyl alcohol and 450 g of methanol were added.
3.21 g of a photopolymerization initiator (Irgacure 907, manufactured by Ciba Geigy) and a photosensitizer (Kayacure DET)
X, Nippon Kayaku Co., Ltd.) in a solution of 1.61 g in 31.62 g of isopropyl alcohol.
Mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPH
A, a solution prepared by dissolving 21.7 g of Nippon Kayaku Co., Ltd. in 78.3 g of isopropyl alcohol. Further, what added 1.47 g of trifluoropropyltrimethoxysilane as an antifouling material was stirred at room temperature for 20 minutes,
The solution was filtered through a 1 μm mesh filter to prepare a coating solution A for a low refractive index layer. The refractive index of the coating film obtained by applying this solution and curing with ultraviolet light was 1.41.

(Preparation of Coating Solution B for Low Refractive Index Layer) A fluorine-containing oligomer (trade name: Megafac F-1) was used as an antifouling material.
Coating solution B for low refractive index layer was prepared in the same manner as coating solution A for low refractive index layer, except that 76 PF (manufactured by Dainippon Ink and Chemicals, Inc.) was used. The refractive index of the coating film obtained by applying this solution and curing with ultraviolet light was 1.41.

(Preparation of Coating Solution C for Low Refractive Index Layer) The antifouling material is cured with a curable fluoropolymer (trade name: JN-722).
5, a low refractive index layer coating liquid C was prepared in the same manner as the low refractive index layer coating liquid A except that the coating liquid was replaced with JSR Co., Ltd.). The refractive index of the coating film obtained by applying this solution and curing with ultraviolet light was 1.41.

Example 1 Triaceti having a thickness of 80 μm
Luccellulose film (trade name: TAC-TD80U,
Fuji Photo Film Co., Ltd.)
Coating solution D using a bar coater, and at 120 ° C.
After drying, 160W / cm air-cooled metal halide lamp
(I-Graphics Co., Ltd.) using an illuminance of 400
mW / cm ², Irradiation dose 300mJ / cm²Illuminate the UV
4 μm thick hard coat layer
Was formed. Then, the coating solution A for the antiglare layer was
And apply the same conditions as the above hard coat layer.
And dried and cured with UV light to form an anti-glare layer
Formed. On top of this, apply the coating liquid A for a low refractive index layer to a bar.
Coating using a coater, drying at 80 ° C., illuminance 50
0mW / cm², Irradiation amount 750mJ / cm²UV light
Irradiate to cure the coating layer and form a 0.096 μm thick
A low refractive index layer having clovoids was formed.

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. . On top of that, the coating liquid A for the low refractive index layer
Is applied using a bar coater, dried at 80 ° C., and then irradiated with ultraviolet light having an illuminance of 500 mW / cm ² and an irradiation amount of 750 mJ / cm ² to cure the applied layer, and to have a thickness of 0.096 μm.
A low refractive index layer having microvoids was formed.

Example 3 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 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. . On top of that, the coating solution B for the low refractive index layer
Is applied using a bar coater, dried at 80 ° C., and then irradiated with ultraviolet light having an illuminance of 500 mW / cm ² and an irradiation amount of 750 mJ / cm ² to cure the applied layer, and to have a thickness of 0.096 μm.
A low refractive index layer having microvoids was formed.

Example 4 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 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. . On top of that, the coating liquid C for the low refractive index layer
Is applied using a bar coater, dried at 80 ° C., and then irradiated with ultraviolet light having an illuminance of 500 mW / cm ² and an irradiation amount of 750 mJ / cm ² to cure the applied layer, and to have a thickness of 0.096 μm.
A low refractive index layer having microvoids was formed.

[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 anti-glare layer having a thickness of about 1.5 μm. This antiglare layer had a refractive index of 1.51. The coating liquid A 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 microvoided low refractive index layer having a thickness of 0.096 μm.

Comparative Example 2 A triacetylcellulose film (TAC-TD80U, manufactured by Fuji Photo Film Co., Ltd.) having a thickness of 80 μm
A μm hard coat layer was formed. 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. . A silica sol (methanol silica sol, manufactured by Nissan Chemical Co., Ltd.) and a coating solution for a low refractive index layer composed of a hydrolyzate of tetraethoxysilane are applied thereon using a bar coater, and dried at 80 ° C.
Further heat-crosslinking at 120 ° C for 10 minutes, thickness 0.096μ
m, a low refractive index layer having a microvoid and a refractive index of 1.43 was formed.

(Evaluation of Antireflection Film) The following items were evaluated for the obtained film. (1) Porosity of Low Refractive Index Layer The refractive index of the film is defined as the average value of the volume fraction of the refractive index of the material contained in the low refractive index layer and the volume fraction (porosity) of air (refractive index = 1.00). Since the refractive index was observed, the porosity was calculated from the refractive index of the film calculated from the reflectance by the spectrophotometer and the refractive index of the used material. (2) Average reflectance 380-7 using a spectrophotometer (manufactured by JASCO Corporation)
The spectral reflectance at an incident angle of 5 ° was measured in a wavelength region of 80 nm. The average reflectance of 450 to 650 nm was used for the results. (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
After humidity control for 2 hours at% RH, scratching was performed at a load of 1 kg using a 3H test pencil specified in JIS S6006, and the occurrence of scratches was evaluated according to the following criteria. No scratches were observed in the evaluation of n = 5: ○ 1 or 2 scratches in the evaluation of n = 5: Δ 3 or more scratches in the evaluation of n = 5: × (5) Contact angle, fingerprint adhesion Evaluation As an index of the contamination resistance of the surface, the optical material was heated at a temperature of 25 ° C.
After adjusting the humidity at 60% RH for 2 hours, the contact angle to water was measured. After attaching a fingerprint to the sample surface, the sample was wiped off with a cleaning cloth to observe the state, and the fingerprint adhesion was evaluated as follows. Fingerprints can be completely wiped off: ○ Fingerprints can be seen slightly: △ Fingerprints can hardly be wiped off: ×

(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 for 2 hours at 25 ° C and 60% relative humidity.
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 ²) And the reflection image is blurred
The degree was evaluated based on 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 hardly blurs: × (8) Glare evaluation Light diffuser with louver on conductive film
And the glare on the surface was evaluated according to the following criteria. There is almost no glare: ○ There is slight glare: △ There is glare of a size that can be identified by eyes: ×

Table 1 shows the results of Examples and Comparative Examples.
Both Examples 1 and 2 were excellent in antireflection performance, and all performances required for antiglare antireflection films such as pencil hardness, fingerprint adhesion, antiglare properties, and glare were good. Comparative Example 1
No sufficient antireflection performance was obtained due to the low refractive index of the antiglare layer. In Comparative Example 2, the contact angle of the low refractive index layer was small, and the fingerprint adhesion was poor.

[0040]

[Table 1]

Next, an antiglare antireflection polarizing plate was prepared using the film of Example 4. When a liquid crystal display device in which an antireflection layer was disposed on the outermost layer using this polarizing plate was prepared, excellent contrast was obtained because there was no reflection of external light, color unevenness did not occur, and anti-glare properties were obtained. The reflected image was inconspicuous, had excellent visibility, and had good fingerprints.

[0042]

The anti-glare anti-reflection film of the present invention is excellent in that it can be produced simply and at low cost, has sufficient anti-glare properties, anti-reflection performance, scratch resistance and stain resistance, and has less color unevenness. It has a function and effect. Therefore, in a polarizing plate using the same and an image display device using the anti-glare anti-reflection film on the front surface of the display device, the anti-glare property has excellent visibility without a decrease in contrast and reflection of an image due to reflection of external light. With no color unevenness of the image, scratch resistance of the display surface,
It has an excellent effect of having high antifouling properties.

[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 Transparent support made of triacetyl cellulose 2 Hard coat layer 3 Antiglare layer 4 Low refractive index layer 5 Matt fine particles

 ────────────────────────────────────────────────── ─── front page of continued F-term (reference) 2H049 BB17 BB33 BB65 BC22 BC24 2H091 FA08X FA37X FB03 FB12 FB13 FC01 FC23 GA16 KA01 2K009 AA15 BB28 CC09 CC24 CC26 CC42 DD02 DD05 EE00 EE05 4F100 AA19C AA19H AA21C AA21H AA25C AA25H AA27C AA27H AA28C AA28H AH05B AH06B AJ06 AK12 AK25C AR00C AT00A BA04 BA07 BA10C CA02 CA23B CA23H CC00D CC01B CC02B CC02C CC03B CC03C DE01 DE04C DE04H DJ01B EJ54 GB41 JK12D JL06 JN06 JN18B JN18C JN30 YY00

Claims (10)

[Claims] 1. A microvoided refractive index of 1.38, obtained by curing a coating film of a coating solution comprising inorganic fine particles, a curable resin and an antifouling material on a substrate by heat or ionizing radiation. And at least one low-refractive-index layer having a refractive index of 1.57 between the substrate and the low-refractive-index layer.
An antiglare antireflection film, comprising an antiglare layer containing a binder having a thickness of from 2.00 to 2.00. 2. The antiglare antireflection film according to claim 1, further comprising at least one hard coat between the base material and the antiglare layer. 3. The antiglare antireflection film according to claim 1, wherein the antifouling material in the low refractive index layer is a fluorine-containing alkylalkoxysilane compound. 4. The antiglare property according to claim 1, wherein the antifouling material in the low refractive index layer is any one of a monomer, an oligomer and a polymer having a fluorinated alkyl group. Anti-reflection film. 5. The anti-glare anti-reflection according to claim 1, wherein the anti-glare layer is made of a binder containing matte fine particles and a cured product of a heat or ionizing radiation curable resin. the film. 6. An average particle size of the mat fine particles is 1 μm or more.
The antiglare antireflection film according to claim 5, wherein the thickness is 10 µm. 7. The anti-glare layer, wherein the anti-glare layer has a thickness of 1.57 to 1.57.
The anti-glare property according to claim 5, wherein the binder having a refractive index of 2.00 is a heat or ionizing radiation cured product of a mixture of a high refractive index monomer and a tri- or higher functional (meth) acrylate monomer. Anti-reflection film. 8. The anti-glare layer, wherein the anti-glare layer has a thickness of 1.57 to 1.57.
The binder having a refractive index of 2.00 is Al, Zr, Z
6. A heat- or ionizing radiation-cured product of a mixture of ultrafine particles of a metal selected from n, Ti, In, and Sn and a trifunctional or higher functional (meth) acrylate monomer. Dazzling anti-reflection film. 9. Polarized light, 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. Board. 10. The antiglare antireflection film according to any one of claims 1 to 8, or the polarizing plate according to claim 9 used as an outermost layer of a display with the antireflection layer as a front side. A liquid crystal display device characterized by the above-mentioned.