JP2001100004A - Antidazzle antireflection film and image display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To easily provide an antidazzle antireflection film having satisfactory antireflection performance, scuffing resistance and antifouling property and nearly free from irregular color at a low cost and also provide a polarizing plate using the film as a constituent member and a liquid crystal display device. SOLUTION: At least one low refractive index layer containing a fluororesin having a refractive index of 1.38-1.49 is disposed on a substrate and an antidazzle layer 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. This antireflection film is used as at least one of two protective films for a polarizing film in a polarizing plate to obtain the objective polarizing plate. The objective liquid crystal display device uses the antireflection film or the polarizing plate as the top layer of the display.

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 excellent antiglare properties, a polarizing plate using the same as a constituent member, and a liquid crystal display device.

[0002]

2. Description of the Related Art In general, an antireflection film is used in an image display device such as a cathode ray tube display device, a plasma display panel, and a liquid crystal display device in order to prevent a decrease in contrast and reflection of an image due to reflection of external light. It is placed on the outermost surface of the display, which reduces reflectance using the principle of interference.

[0003]

However, in an antireflection film having only a hard coat layer and a low refractive index layer on a transparent support, the low refractive index layer must have a sufficiently low refractive index to reduce the reflectance. 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 of the low refractive index layer must be made less than 1.40. Materials having a refractive index of 1.40 or less include magnesium fluoride and calcium fluoride for inorganic substances, and fluorine-containing compounds having a large fluorine content for organic substances. These fluorine compounds have no cohesive force and are arranged on the outermost surface of the display. The resulting film had insufficient scratch resistance. Therefore, it has been conventionally necessary to use a compound having a refractive index of 1.43 or more in order to have sufficient scratch resistance.

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. Also, JP-A-7-3
No. 33404 describes an antiglare antireflection film having excellent gas barrier properties, antiglare properties, and antireflection properties.
Since a silicon oxide film formed by chemical vapor deposition (CVD) is essential, productivity is inferior to wet coating. Accordingly, the present invention provides a simple and inexpensive anti-reflection film having sufficient anti-reflection performance, scratch resistance, and anti-fouling properties with less color unevenness, a polarizing plate and a liquid crystal using this film as a constituent member. It is an object to provide a display device.

[0005]

The object of the present invention has been attained as follows. (1) At least one layer having a refractive index of 1.38 on a substrate.
An antiglare antireflection film provided with a low refractive index layer containing a fluorine-containing resin having a refractive index of 1.49 or less, wherein the refractive index between the base material and the low refractive index layer is 1.57 to 2. An anti-glare anti-reflection film, comprising an anti-glare layer containing a binder of No. 00. (2) The antiglare antireflection film according to the above (1), wherein at least one hard coat layer is provided between the substrate and the antiglare layer. (3) The antiglare antireflection film according to (1) or (2), wherein the fluorine-containing resin is a resin cured by heat or ionizing radiation. (4) The anti-glare layer according to (1), (2) or (3), wherein the anti-glare layer comprises anti-glare particles and a binder containing a compound cured by ionizing radiation. Anti-glare anti-reflection film. (5) The difference in refractive index between the antiglare particles and the binder is 0.0
The anti-glare anti-reflection film according to item (4), wherein the number is less than 5. (6) The antiglare antireflection film according to the above (4), wherein the average particle size of the antiglare particles is 1 to 10 μm. (7) The binder of the anti-glare layer comprises a compound obtained by curing a mixture of a high refractive index monomer and a (meth) acrylate monomer having at least three functional groups by heat or ionizing radiation. (1)-(6)
The antiglare antireflection film according to any one of the above items. (8) The binder of the anti-glare layer is Al, Zr, Zn, T
a compound obtained by curing a mixture of at least one metal oxide ultrafine particle selected from i, In, and Sn and a (meth) acrylate monomer having at least three functional groups by heat or ionizing radiation. The antiglare antireflection film according to any one of the above items (1) to (6). (9) The low refractive index layer has a dynamic friction coefficient of 0.03 to 0.1.
5. The antiglare antireflection film according to any one of (1) to (8), wherein a contact angle with water is 90 to 120 °. (10) The antiglare antireflection film according to any one of (1) to (9) is used as at least one of two protective films of a polarizing layer in a polarizing plate. Polarizer. (11) A liquid crystal display using the antiglare antireflection film according to any one of (1) to (9) or the polarizing plate according to (10) as the outermost layer of a display. apparatus.

[0006]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The basic structure of an antiglare antireflection film suitable as one embodiment of the present invention will be described with reference to the drawings.

The embodiment shown in FIG. 1 is an example of the anti-glare anti-reflection film of the present invention. The anti-glare anti-reflection film comprises a transparent support 1 made of triacetyl cellulose, a hard coat layer 2, an anti-glare layer 3, and a low refractive index layer 4. It has an orderly layer configuration. Reference numeral 5 denotes anti-glare particles, and the protruding portions of the anti-glare layer are also covered with the low refractive index layer 4. The binder of the anti-glare layer has a refractive index of 1.57-1.
80, and the low refractive index layer has a refractive index of 1.43 to 1.48.
It is.

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)

Where 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.

In the present invention, the refractive index of the material (binder portion) for forming the antiglare layer is preferably 1.57 to 2.2.
00, and more preferably 1.60 to 1.80. Triacetylcellulose, which is preferably used as a substrate, has a refractive index of 1.48. The binder forming the antiglare layer used in the present invention has a refractive index of 1.57 to 2.00.
However, if it is too small or too large, the antireflection property will be reduced. The high-refractive-index material is composed of a monomer having two or more ethylenically unsaturated groups and at least one oxide selected from the group consisting of titanium, aluminum, indium, zinc, tin, antimony and zirconium.
In the case of fine particles having a diameter of 0 nm or less, the fine particles have a sufficiently small particle size smaller than the wavelength of light, so that scattering does not occur and the fine particles behave as an optically uniform substance. This is disclosed in JP-A-8-1.
No. 10401 and the like.

In the present invention, the anti-glare layer is not affected by optical interference in the anti-glare layer because the anti-glare particles dispersed in the high refractive index material cause surface scattering. In the high refractive index hard coat layer without anti-glare particles, due to optical interference due to the refractive index difference between the hard coat layer and the substrate,
A large amplitude of the reflectance is seen in the wavelength dependence of the reflectance, and as a result, the anti-glare anti-reflection effect is deteriorated, and color unevenness occurs at the same time. These problems were solved by the scattering effect due to surface irregularities.

As the substrate used in the present invention, a preferable substrate is selected depending on its use, and specifically, a transparent support is used. It is preferable to use a plastic film as the transparent support. 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, and the like. Of these, triacetyl cellulose is preferred. 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.

The compound used in 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-cyclohexane 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 the like. Derivatives (eg, 1,4-divinylbenzene, 4-vinylbenzoic acid-2-acryloylethyl ester, 1,4-divinylcyclohexanone), vinylsulfone (eg, divinylsulfone), acrylamide (eg, methylenebisacrylamide) and methacryl Amides are 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 using ionizing radiation, heat or the like after coating. This is necessary,
It can be carried out by a known method using a photopolymerization initiator, a photosensitizer and the like.

Instead of or in addition to the monomer having two or more ethylenically unsaturated groups, a crosslinked structure may be introduced into the binder polymer by a reaction of a crosslinkable group.
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,
Metal alkoxides such as etherified methylols, esters and urethanes, tetramethoxysilane can also be used as monomers 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.

In the present invention, the anti-glare layer can be formed by using a high-refractive-index monomer or high-refractive-index inorganic ultrafine particles in addition to the material for forming the hard coat layer in the formation of the binder. Such a high refractive index monomer preferably contains at least one selected from the group consisting of an aromatic ring, a halogen atom other than a fluorine atom, a sulfur atom, a phosphorus atom, and a nitrogen atom in the structure of the monomer. Examples of such a high refractive index monomer include bis (4-methacryloylthiophenyl) sulfide, vinylnaphthalene, vinylphenylsulfide, 4-methacryloxyphenyl-4′-methoxyphenylthioether and the like. In the present invention, the amount of the high refractive index monomer used is adjusted so that the binder has a desired film refractive index. The high-refractive-index inorganic ultrafine particles preferably contain ultrafine particles having a particle diameter of 100 nm or less made of at least one oxide selected from titanium, aluminum, indium, zinc, tin, antimony and zirconium, and 50 nm or less. More preferably, the particles are ultrafine particles of Examples of such ultrafine particles include TiO ₂ ,
Al ₂ O ₃ , In ₂ O ₃ , ZnO, SnO ₂ , Sb ₂ O
₃ , ITO, ZrO _{2 and the} like. The content of the inorganic ultrafine particles in the binder is 10 to 90% of the total weight of the antiglare layer.
%, More preferably 20 to 80% by weight.

In the antiglare layer, antiglare particles of a resin or an inorganic compound are used for the purpose of imparting antiglare properties, preventing deterioration of 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.
μm is more preferred. Further, it is preferable that the weight of the anti-glare particles having a particle size smaller than the binder film thickness of the anti-glare layer is less than 50% of the whole anti-glare particles. The coating amount of the anti-glare 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. In addition, it is preferable that the difference in refractive index between the binder of the antiglare layer and the antiglare particles is less than 0.05 from the viewpoint of reducing internal scattering in the antiglare layer.

A fluorine-containing resin is used for the low refractive index layer,
Fluorine-containing compounds (resins) that are crosslinked by heat or ionizing radiation are preferably used. The refractive index of the low refractive index layer is 1.
When the value is too low, the film strength decreases, and when the value is too high, the antireflection property deteriorates. The dynamic friction coefficient of this layer is preferably 0.03 to 0.15, more preferably 0.07 to 0.10. If the dynamic friction coefficient is too small, slipping of the handling film becomes a problem, and if it is too large, the scratch resistance deteriorates. The contact angle of the low refractive index layer with water is preferably 90 to 120 °, more preferably 100 to 120 °. If the contact angle is too small, the antifouling property is poor.

As the crosslinkable fluoropolymer compound constituting such a resin, a perfluoroalkyl group-containing silane compound (for example, (heptadecafluoro-1,1,2,2,3)
In addition to 2-tetradecyl) triethoxysilane) and the like, a fluorinated copolymer containing a fluorinated monomer component and a monomer component for providing a crosslinkable group as constituent components is exemplified. Specific examples of the fluorine-containing monomer component 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 6FM (manufactured by Osaka Organic Chemicals) and M-2020 (manufactured by Daikin)), and fully or partially fluorinated vinyl ethers. As a monomer component for providing a crosslinkable group, in addition to a (meth) acrylate monomer having a crosslinkable functional group in the molecule in advance, such as glycidyl methacrylate, it has a carboxyl group, a hydroxyl group, an amino group, a sulfonic acid group, and the like ( (Meth) acrylate monomers (for example, (meth) acrylic acid, methylol (meth) acrylate, hydroxyalkyl (meth) acrylate, allyl acrylate, etc.). The latter can introduce a crosslinked structure after copolymerization, as disclosed in JP-A-10-25388 and JP-A-10-14.
7739.

In addition to the polymer having the above-mentioned fluorine-containing monomer as a constitutional unit, a copolymer with a monomer containing no fluorine atom may be used. There is no particular limitation on the monomer units that can be used in combination. For example, olefins (ethylene, propylene, isoprene, vinyl chloride, vinylidene chloride, etc.), acrylates (methyl acrylate,
Ethyl acrylate, 2-ethylhexyl acrylate),
Methacrylates (methyl methacrylate, ethyl methacrylate, butyl methacrylate, ethylene glycol dimethacrylate, etc.), styrene derivatives (styrene,
Divinylbenzene, vinyltoluene, α-methylstyrene, etc.), vinyl ethers (methylvinyl ether, etc.), vinyl esters (vinyl acetate, vinyl propionate, vinyl cinnamate, etc.), acrylamides (N-te
rt butyl acrylamide, N-cyclohexyl acrylamide, etc.), methacrylamides, acrylonitrile derivatives and the like.

Each layer of the antireflection film is formed by a dip coating method,
It can be formed by coating by 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). Two or more layers may be applied simultaneously. The method of simultaneous coating is described in 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). In the present invention, the thickness of the substrate is completely different depending on the use. The anti-glare layer is as described above, and the low refractive index layer is preferably 0.08 to 0.15 μm.
m, more preferably 0.09 to 0.12 μm, and the thickness of the hard coat layer is preferably 1 to 10 μm, more preferably 3 to 6 μm.

The antiglare antireflection film of the present invention may be constituted by sequentially providing the antiglare layer and the low refractive index layer on the base material.
Two or more low refractive index layers having different refractive indices having the refractive index defined in the present invention may be provided. In the present invention, it is preferable to further provide the hard coat layer between the substrate and the antiglare layer.
More than one layer may be provided.

The anti-reflection film includes a liquid crystal display (LCD),
The present invention is applied to 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. An image display device to which the antiglare reflective film of the present invention can be applied is disclosed in
287102 (for example, paragraphs (0059) to (00)
61) and FIGS. 14 and 15), JP-A-7-333404 (for example, paragraphs (0078) to (0079) and FIG.
9, 20)).

[0026]

EXAMPLES The present invention will be described in detail with reference to the following 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. In addition, the refractive index of the coating film obtained by applying this solution and curing with ultraviolet light was 1.60. 10 g of crosslinked polystyrene particles (trade name: SX-200H, manufactured by Soken Chemical Co., Ltd.) having an average particle size of 2 μm were added to this solution.
Was added thereto, and the mixture was stirred and dispersed at 5000 rpm for 1 hour using a high-speed disper, followed by filtration 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 dispersion of zirconium oxide (particle size: about 30 nm) in a mixed solvent of 104.1 g of cyclohexanone and 61.3 g of methyl ethyl ketone while stirring with an air disper. Name: KZ-7886A, manufactured by JSR Corporation) 21
7.0 g were added. In addition, the refractive index of the coating film obtained by applying this solution and curing with ultraviolet light was 1.61. Further, 5 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 the mixture was stirred and dispersed at 5000 rpm for 1 hour using a high-speed disperser. The solution was filtered through a polypropylene filter to prepare a coating solution for the antiglare layer.

(Preparation of Coating Solution C for Antiglare Layer) A hard coat coating solution containing a dispersion of zirconium oxide (particle size: about 30 nm) in a mixed solvent of 104.1 g of cyclohexanone and 61.3 g of methyl ethyl ketone while stirring with an air disper. Name: KZ-7991, manufactured by JSR Corporation) 217.
0 g was added. In addition, the refractive index of the coating film obtained by applying this solution and curing with ultraviolet light was 1.70. Further, 5 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 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 D for Hard Coat Layer) A mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.) (250 g) 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. In addition, 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
46 heat-crosslinkable fluoropolymer (trade name: JN-72)
21, manufactured by JSR Corporation), 200 g of methyl isobutyl ketone was added, and the mixture was stirred and filtered with a polypropylene filter having a pore size of 1 μm to prepare a coating solution for a low refractive index layer.

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. Then, apply the coating solution for the low refractive index layer
After drying at 80 ° C., a further 12
Thermally crosslinked at 0 ° C for 10 minutes, low refraction of 0.096μm thickness
A rate layer was formed.

Example 2 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 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 on a triacetylcellulose 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. . 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. An anti-glare layer coating solution exactly the same as the above-mentioned anti-glare layer coating solution A was applied thereon using a bar coater, except that all of the MPSMA was replaced with DPHA, and dried under the same conditions as the above hard coat layer. UV cured, about 1.5μ thick
m of the anti-glare layer was formed. In the anti-glare layer coating solution used in this comparative example, the refractive index of the coating film obtained by applying the solution before adding SX-200H and curing with ultraviolet light was 1.5.
It was one. The coating solution for the low refractive index layer was applied thereon using a bar coater, dried at 80 ° C., and further dried for 1 hour.
Thermal crosslinking was performed at 20 ° C. for 10 minutes to form a 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 refractive index of 1.43 was formed.

(Evaluation of Antireflection Film) The following items were evaluated for the obtained film. (1) 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. (2) Haze The haze of the obtained film was measured using a haze meter MODEL.
The measurement was performed using 1001DP (trade name, manufactured by Nippon Denshoku Industries Co., Ltd.). (3) Pencil hardness evaluation 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, a scratch test was performed with a 1 kg load using a 3H test pencil specified in JIS S 6006. 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: × (4) 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: ×

(5) 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.
After that, using HEIDON-14 (trade name) dynamic friction measuring machine
5mmφ stainless steel ball, load 100g, speed 60c
The value measured at m / min was used. (6) Evaluation of anti-glare property Exposed fluorescence without louver on the prepared anti-glare 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: × (7) 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.
Examples 1, 2 and 3 were all excellent in antireflection performance, and all the properties required for an antiglare antireflection film such as pencil hardness, fingerprint adhesion, antiglare properties, and glare were good.
In Comparative Example 1, sufficient antireflection performance (reflectance) was not obtained because the refractive index of the antiglare layer was low. In Comparative Example 2, the contact angle of the low refractive index layer was high, and the fingerprint adhesion was poor.

[0040]

[Table 1]

Next, an antiglare antireflection polarizing plate was prepared using the film of Example 2. 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, no color unevenness, and good fingerprints.

The anti-glare anti-reflection film of the present invention is simple and inexpensive and has sufficient anti-glare properties, anti-reflection performance, scratch resistance and stain resistance, and has an excellent effect of less color unevenness. It works. Therefore, an image display device using the antiglare antireflection film on the front surface of the display device does not have a decrease in contrast or reflection of an image due to reflection of external light, has no color unevenness in an image, has scratch resistance on a display surface, and has stain resistance. It has an excellent effect of high performance.

[Brief description of the drawings]

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

[Explanation of symbols]

 Reference Signs List 1 transparent support composed of triacetyl cellulose 2 hard coat layer 3 antiglare layer 4 low refractive index layer 5 antiglare particles

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 2H049 BA04 BA24 BB30 BB49 BB65 2H091 FA08X FA08Z FA37X FB12 FB13 FC22 FC23 GA16 KA01 LA02 LA12 2K009 AA02 AA15 BB28 CC21 CC24 DD02 EE00 EE05 4F100 AA17AAAAAAAC19 AA28C AA28H AJ06A AK17B AR00C AR00D AR00E AS00C AT00A BA03 BA04 BA05 BA07 BA10A BA10B BA10E CC00D DE01C DE01H EJ08B EJ08C GB41 JA20C JA20H JB04B JB13B JB14B JB14C JK12D JK14 JK16B JL06 JN06 JN10E JN18B JN18C YY00B YY00C YY00H 5G435 AA00 AA01 AA02 AA04 AA14 FF02 HH02 HH03 KK07

Claims (11)

[Claims] 1. An anti-glare anti-reflection film comprising a base material and at least one low-refractive-index layer comprising a fluorine-containing resin having a refractive index of 1.38 to 1.49. ,
The refractive index between the base material and the low refractive index layer is 1.57 to 2.00.
An anti-glare anti-reflection film, characterized in that an anti-glare layer containing a binder is provided. 2. The anti-glare anti-reflection film according to claim 1, further comprising at least one hard coat layer between the substrate and the anti-glare layer. 3. The resin according to claim 1, wherein the fluorine-containing resin is a resin cured by heat or ionizing radiation.
Or the anti-glare anti-reflection film according to 2. 4. The anti-glare property according to claim 1, wherein the anti-glare layer comprises anti-glare particles and a binder containing a compound cured by ionizing radiation. Anti-reflection film. 5. The anti-glare anti-reflection film according to claim 4, wherein the refractive index difference between the anti-glare particles and the binder is less than 0.05. 6. The anti-glare particles have an average particle size of 1 to 10 μm.
The anti-glare anti-reflection film according to claim 4, wherein m is m. 7. The binder for the anti-glare layer comprises a compound obtained by curing a mixture of a high refractive index monomer and a (meth) acrylate monomer having at least three functional groups by heat or ionizing radiation. The antiglare antireflection film according to any one of claims 1 to 6. 8. The method according to claim 8, wherein the binder of the anti-glare layer is Al, Zr,
At least one selected from Zn, Ti, In and Sn
The compound according to any one of claims 1 to 6, comprising a compound obtained by curing a mixture of ultrafine particles of a metal oxide and a (meth) acrylate monomer having at least three functional groups by heat or ionizing radiation. The antiglare antireflection film according to claim 1 or 2. 9. The low refractive index layer has a dynamic friction coefficient of 0.03 to 0.03.
The antiglare antireflection film according to any one of claims 1 to 8, wherein the antiglare film has a contact angle of 0.15 and a water contact angle of 90 to 120 °. 10. 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. 11. A liquid crystal display device comprising the antiglare antireflection film according to claim 1 or the polarizing plate according to claim 10 as an outermost layer of a display.