JP2000258606A - Antidazzle and antireflection film and image display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To easily obtain an antidazzle and antireflection film having enough antireflection properlies, scratch resistance and contamination-proof properties with little color irregularity at a low cost by forming only two layers of a hard coating layer 2 and a low refractive index layer 3 on a supporting body 1. SOLUTION: The optical film is produced by forming a hard coating layer 2 on a transparent supporting body 1 and forming a low refractive index layer 3 having 1.43 to 1.49 refractive index on the hard coating layer 2. The refractive index of the material which constitutes the hard coating layer ranges from 1.58 to 2.00, and the hard coating layer 2 contains irregular silica particles having 1.0 to 10.0 μm average particle size. The low refractive index layer 3 consists of a crosslinked fluorine-contg. compd. having 0.03 to 0.15 coefft. of dynamic friction and 90 to 120 deg. contact angle with water. The antidazzle and antireflection film has 3.0 to 20.0% haze and <=1.8% average reflectance for 450 to 650 nm wavelength.

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 and a liquid crystal display device using the same.

[0002]

2. Description of the Related Art In general, an antireflection film is used in an image display device such as a liquid crystal display device, a plasma display panel, and an electroluminescence display in order to prevent a decrease in contrast and reflection of an image due to reflection of external light. Is disposed on the outermost surface of the display to reduce the reflectivity using the principle described above.

[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 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.

In Japanese Patent Application Laid-Open No. 7-287102, a low refractive index layer of SiO _x (1.5 ≦ x ≦ 4.00) is formed by a vapor phase method, and the refractive index of a hard coat layer is increased to thereby reflect light. It is stated to reduce the rate.
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. It is an object of the present invention to provide a simple and inexpensive and sufficient antireflection performance, scratch resistance, and stain resistance by simply forming a hard coat layer and a low refractive index layer on a support. An object of the present invention is to provide an antiglare antireflection film with less unevenness.

[0005]

The object of the present invention has been attained as follows. (1) A material for forming the hard coat layer in an optical film in which a hard coat layer and a low refractive index layer having a refractive index of 1.43 to 1.49 on the hard coat layer are sequentially provided on a transparent support. Has a refractive index of 1.58 to 2.00 and an average particle size of 1.0 to 10.0 in the hard coat layer.
μm amorphous silica particles, and the low refractive index layer has a dynamic friction coefficient of 0.03 to 0.15 and a contact angle of 90 to water.
To 120 °, comprising a crosslinked product of a fluorine-containing compound, wherein the haze of the optical film is 3.0 to 20.0%,
An antiglare antireflection film, wherein the average reflectance at 450 nm to 650 nm is 1.8% or less. (2) The protection according to (1), wherein the silica particles having a particle diameter larger than half of the thickness of the hard coat layer occupy 40 to 100% of the whole silica particles by weight. Dazzling anti-reflection film. (3) The particle size of the material forming the hard coat layer is composed of a monomer having two or more ethylenically unsaturated groups and at least one oxide selected from titanium, aluminum, indium, zinc, tin, and antimony. 100nm
An antiglare antireflection film, which is obtained by crosslinking the following fine particles (preferably by ionizing radiation). (4) The antiglare antireflection film according to any one of (1) to (3) is used as at least one of two protective films of a polarizing layer in a polarizing plate. Polarizer. (5) The anti-glare anti-reflection film according to any one of (1) to (3) or the anti-reflection layer of the anti-glare anti-reflection polarizing plate according to claim 4 is reflected on the outermost surface layer of a display. A liquid crystal display device used for prevention.

[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 antiglare antireflection film of the present invention. The transparent support 1, which is made of triacetyl cellulose, the hard coat layer 2, and the low refractive index layer 3 are arranged in this order. Have. Reference numeral 4 denotes amorphous silica particles, the protruding portion of which is protruded from the hard coat layer and has a low refractive index layer 3.
Covered with. The material other than the silica particles of the hard coat layer has a refractive index of 1.58 to 2.00, and the low refractive index layer has a refractive index of 1.43 to 1.49. 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 hard coat layer of the present invention is not described by a single value. Since the refractive index of the material forming the hard coat layer is 1.58 to 2.00, the refractive index of the silica particles is 1.47, and the refractive index of triacetyl cellulose that can be used as a support is 1.48, The hard coat layer is a non-uniform refractive index layer in which silica particles having a low refractive index are dispersed in a matrix having a higher refractive index than the support. In the hard coat layer of the present invention, the material has a refractive index of 1.58 to 2.00. If the refractive index is too small, sufficient antireflection performance cannot be obtained, and if it is too large, coloring deteriorates. When the high-refractive-index material is composed of a monomer having two or more ethylenically unsaturated groups and fine particles having a particle diameter of 100 nm or less composed of at least one oxide selected from titanium, aluminum, indium, zinc, tin, and antimony. Since the particle diameter of the fine particles is sufficiently smaller than the wavelength of light, scattering does not occur, and the fine particles behave as optically uniform substances. This is described in JP-A-8-110401.

In the present invention, the hard coat layer is not affected by optical interference in the hard coat layer because internal scattering is caused by low refractive index silica particles dispersed in the high refractive index material. In the high refractive index hard coat layer having no silica 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. The anti-reflection effect deteriorates and color unevenness occurs at the same time. However, in the anti-reflection film of the present invention, these problems were solved by the internal scattering effect of silica particles.

As the transparent support, 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 for 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.
In order to obtain a high refractive index, the structure of the monomer preferably contains at least one selected from an aromatic ring, a halogen atom other than fluorine, sulfur, phosphorus, and nitrogen.

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, pentaerythritol hexa (meth) acrylate, 1,2,3-cyclohexanetetramethacrylate, polyurethane polyacrylate, polyester polyacrylate), vinylbenzene and 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. Examples of the high refractive index monomer include bis (4-methacryloylthiophenyl) sulfide, vinylnaphthalene, vinylphenylsulfide, 4-methacryloxyphenyl-4′-methoxyphenylthioether and the like. 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 must be cured by a polymerization reaction using ionizing radiation, heat, or the like after coating.

[0015] 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.

The hard coat layer is formed of at least one oxide selected from titanium, aluminum, indium, zinc, tin and antimony in order to increase the refractive index of the material forming the hard coat layer.
It is preferable to contain fine particles having a particle size of 50 nm or less. Examples of the fine particles include TiO ₂ , Al ₂ O
₃ , In ₂ O ₃ , ZnO, SnO ₂ , Sb ₂ O ₃ , IT
O and the like. The addition amount of the inorganic fine particles is preferably from 10 to 90% by weight, more preferably from 20 to 80% by weight, and particularly preferably from 30 to 60% by weight based on the total weight of the hard coat layer.

In the hard coat layer, amorphous silica particles 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 1.
0 to 10.0 μm is preferable, and 2.0 to 8.0 μm
Is more preferred. The reason for using irregular-shaped silica particles is to prevent glare on the surface. In addition, true spherical silica, crosslinked acrylic particles, TiO ₂ particles, and the like may be used in combination. Also, one half of the thickness of the hard coat layer
It is preferable that amorphous silica particles having a larger particle diameter occupy 40 to 100% by weight of the whole silica particles. The bottom surface of the silica particles in the hard coat layer is not always in contact with the support, but rather, the silica particles are usually in a floating state during coating. The amorphous silica particles having a particle size larger than half the thickness of the hard coat layer are preferably 3 to 50% by weight in the material of the hard coat layer, and 5 to 30% by weight.
% Is more preferred. Particle size distribution is a method of measuring the particle size of amorphous silica that can be measured by the Coulter counter method, centrifugal sedimentation method, etc.In the case of the Coulter counter method, the particle number distribution is used, so in this case it is decided to convert it to weight distribution. I have. Incidentally, the volume distribution (= weight distribution) is also required by the laser method (master sizer). This is, in principle, a sphere-converted diameter (a volume converted to the diameter of a sphere of that volume). The distribution is converted into a particle number distribution. The thickness of the hard coat layer is preferably 2 to 10 μm, more preferably 3 to 6 μm.

For the low refractive index layer, a fluorine-containing compound (polymer) crosslinked by heat or ionizing radiation having a dynamic friction coefficient of 0.03 to 0.15 and a contact angle to water of 90 to 120 ° is used. The refractive index of the low refractive index layer is 1.43 or more.
If this value is too low, the scratch resistance is remarkably deteriorated, and if it is too high, sufficient antireflection performance cannot be obtained. The coefficient of kinetic friction of this layer is 0.03 to 0.15. If the coefficient is too small, slipping occurs on the roll in the manufacturing process to cause damage, and if it is too large, the scratch resistance itself deteriorates. As the crosslinkable fluoropolymer compound constituting the polymer, a perfluoroalkyl group-containing silane compound (for example, (heptadecafluoro-1,1,2,2,2)
-Tetradecyl) triethoxysilane) and the like, and a fluorine-containing copolymer having a fluorine-containing monomer component and a monomer component for providing a crosslinkable group as constituent components. Specific examples of the fluorine-containing monomer component constituting the polymer,
For example, a portion of fluoroolefins (eg, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, hexafluoroethylene, hexafluoropropylene, perfluoro-2,2-dimethyl-1,3-dioxole), (meth) acrylic acid or Perfluorinated alkyl ester derivatives (for example, Biscoat 6F
M (manufactured by Osaka Organic Chemicals) and M-2020 (manufactured by Daikin)
Etc.), fully or partially fluorinated vinyl ethers, etc. 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.). It is known from JP-A-10-25388 and JP-A-10-147739 that the latter can introduce a crosslinked structure after copolymerization.

In addition to a polymer containing the above-mentioned fluorine-containing monomer component as a constituent component, a copolymer with a monomer containing no fluorine atom may be used. There is no particular limitation on the monomer components 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, 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.

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 each layer is not particularly limited, and the transparent support is completely different depending on the use. The hard coat layer is as described above, and the low refractive index layer is preferably 90 to 110 μm, more preferably 9 to 110 μm.
5 to 105 μm.

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)).

[0022]

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 Titanium Dioxide Dispersion) Titanium dioxide (primary particle weight average particle diameter: 50 nm, refractive index 2.7)
0) 30 parts by weight, 4.5 parts by weight of anionic diacrylate monomer (trade name: PM21, manufactured by Nippon Kayaku Co., Ltd.), cationic methacrylate monomer (trade name: DM)
0.3 parts by weight of AEA (produced by Kojin Co., Ltd.) and 65.2 parts by weight of methyl ethyl ketone were dispersed by a sand grinder to prepare a titanium dioxide dispersion.

(Preparation of Coating Solution A for Hard Coat Layer) 125 g of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.), bis (4-methacryloylthiophenyl) sulfide ( 125 g of MPSMA (manufactured by Sumitomo Seika Co., Ltd.) was dissolved in 439 g of a mixed solvent of methyl ethyl ketone / cyclohexanone = 50/50% by weight. 7.5 g of a photopolymerization initiator (Irgacure 907, manufactured by Ciba Geigy) and 5.0 g of a photosensitizer (Kayacure DETX, manufactured by Nippon Kayaku Co., Ltd.) are added to the obtained solution.
Was dissolved in 49 g of methyl ethyl ketone. The refractive index of the coating film obtained by applying this solution and curing with ultraviolet light was 1.62. In addition, the average particle size of 3
μm amorphous silica particles (trade name: Mizukasil P-52)
6, 10 g of Mizusawa Chemical Industry Co., Ltd.), and the mixture is stirred and dispersed at 5000 rpm for 1 hour with a high-speed disper.
The solution was 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 B for Hard Coat Layer) 104.1 g of cyclohexanone, methyl ethyl ketone
217.0 g of the titanium dioxide dispersion, a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.) in 3 g of a mixed solvent while stirring with an air disper
110.4 g were added in order. After stirring the solution at room temperature for 30 minutes while shielding the solution from light, the photopolymerization initiator Irgacure 907 was used.
5.44 g (manufactured by Ciba-Geigy) and 1.81 g of photosensitizer Kayacure DETX (manufactured by Nippon Kayaku Co., Ltd.) were added, and the mixture was further stirred at room temperature for 1 hour. Apply this solution,
The coating film obtained by ultraviolet curing had a refractive index of 1.66. Further, 5 g of amorphous silica particles having an average particle diameter of 3 μm (trade name: Mizukasil P-526, manufactured by Mizusawa Chemical Industry Co., Ltd.) was added to the solution, and the dispersion was 5,000 with a high-speed disper.
After stirring and dispersion at 1 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 hard coat layer.

(Preparation of Coating Solution C for Hard Coat Layer) 125 g of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.), bis (4-methacryloylthiophenyl) sulfide ( 125 g of MPSMA (manufactured by Sumitomo Seika Co., Ltd.) was dissolved in 439 g of a mixed solvent of methyl ethyl ketone / cyclohexanone = 50/50% by weight. 7.5 g of a photopolymerization initiator (Irgacure 907, manufactured by Ciba Geigy) and 5.0 g of a photosensitizer (Kayacure DETX, manufactured by Nippon Kayaku Co., Ltd.) are added to the obtained solution.
Was dissolved in 49 g of methyl ethyl ketone. The refractive index of the coating film obtained by applying this solution and curing with ultraviolet light was 1.62. This solution was 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 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, to this solution, amorphous silica particles having an average particle diameter of 3 μm (trade name: Mizukasil P-5)
26, manufactured by Mizusawa Chemical Industry Co., Ltd.), and the mixture was stirred and dispersed at 5000 rpm for 1 hour with a high-speed disperser, and then 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 E for Hard Coat Layer) 104.1 g of cyclohexanone, methyl ethyl ketone
217.0 g of the titanium dioxide dispersion, a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.) in 3 g of a mixed solvent while stirring with an air disper
110.4 g were added in order. After stirring the solution at room temperature for 30 minutes while shielding the solution from light, the photopolymerization initiator Irgacure 907 was used.
5.44 g (manufactured by Ciba-Geigy) and 1.81 g of photosensitizer Kayacure DETX (manufactured by Nippon Kayaku Co., Ltd.) were added, and the mixture was further stirred at room temperature for 1 hour. Apply this solution,
The coating film obtained by ultraviolet curing had a refractive index of 1.66. Further, 10 g of true spherical silica particles having an average particle size of 1.5 μm (trade name: Seahoster KE-P150, manufactured by Nippon Shokubai Co., Ltd.) was added to the 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 hard coat layer.

(Preparation of Coating Solution A for Low Refractive Index Layer) A thermally crosslinkable fluoropolymer having a refractive index of 1.46 (JN-722)
1. 200 g of methyl isobutyl ketone was added to 200 g of JSR Corporation, 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.

(Preparation of Coating Solution B for Low Refractive Index Layer) A thermally crosslinkable fluoropolymer having a refractive index of 1.40 (JN-722)
3, 200 g of methyl isobutyl ketone was added to 200 g of JSR Corporation, 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 A for a hard coat layer was applied to a 80 μm-thick triacetyl cellulose film (TAC-TD80U, manufactured by Fuji Photo Film Co., Ltd.) 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 6 [mu] m. About 50% of the silica particles have a particle size larger than 3 μm, which is one half of the thickness of the hard coat layer. in addition,
The coating liquid A for a low refractive index layer was applied 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.

Example 2 The above coating solution B 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 6 [mu] m. About 50% of the silica particles have a particle size larger than 3 μm, which is one half of the thickness of the hard coat layer. in addition,
The coating liquid A for a low refractive index layer was applied 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.

Comparative Example 1 The above-mentioned coating solution C 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 6 [mu] m. This hard coat layer does not contain silica particles. 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.
The composition was thermally crosslinked at 10 ° C. for 10 minutes to form a low refractive index layer having a thickness of 0.096 μm.

[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., 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 6 [mu] m. About 50% of the silica particles have a particle size larger than 3 μm, which is one half of the thickness of the hard coat layer. in addition,
The coating liquid A for a low refractive index layer was applied 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.

Comparative Example 3 The above coating solution E 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 6 [mu] m. Silica particles having a particle diameter larger than 3 μm, which is one half of the thickness of the hard coat layer, are 0%. On top of this, the low refractive index layer coating solution A was applied using a bar coater,
After drying at 80 ° C., thermal crosslinking was further performed at 120 ° C. for 10 minutes to form a low refractive index layer having a thickness of 0.096 μm.

[Comparative Example 4] The above-mentioned coating solution A 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 10 [mu] m. About 5% of the silica particles have a particle size larger than 5 μm, which is one half of the thickness of the hard coat layer. in addition,
The coating liquid A for a low refractive index layer was applied 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.

Comparative Example 5 The above coating solution A 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 6 [mu] m. About 50% of the silica particles have a particle size larger than 3 μm, which is one half of the thickness of the hard coat layer. in addition,
The low refractive index layer coating solution B was applied 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.

Comparative Example 6 The above-mentioned coating solution A 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 6 [mu] m. About 50% or more of the silica particles having a particle diameter larger than 3 μm, which is one half of the thickness of the hard coat layer.

(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.
It measured using 1001DP (made 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. Further, after attaching a fingerprint to the surface of the sample, the state when the fingerprint was wiped off with a cleaning cloth was observed, and the adhesion of the fingerprint 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 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. (6) Evaluation of anti-glare property Exposed fluorescence without louver on 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 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
Has no anti-glare properties because no silica particles are present. Although not described in the table, the color unevenness of the film was remarkable. In Comparative Example 2, sufficient antireflection performance (reflectance) was not obtained because the material refractive index of the hard coat layer was small. In Comparative Example 3, since spherical silica having a small particle diameter was used, antiglare properties were slightly inferior, and glare was observed in reflected light. In Comparative Example 4, since the hard coat layer was thicker than the silica particles, the antiglare property was insufficient, and the glare was slightly inferior. Comparative Example 5 uses a thermally crosslinkable fluoropolymer having a large fluorine content and a small refractive index for the low refractive index layer. However, although the antireflection performance is slightly excellent, the pencil hardness is extremely poor and the scratch resistance is insufficient. Was. In Comparative Example 6, since there was no low refractive index layer, no antireflection performance was observed, and no fingerprint adhesion was observed.

[0042]

[Table 1]

Next, an antiglare antireflection polarizing plate was prepared using the films of Examples 1 and 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.

[0044]

The antiglare antireflection film of the present invention is simple and inexpensive and has sufficient antireflection performance and scratch resistance by only forming a hard coat layer and a low refractive index layer on a support. It has an excellent effect of antifouling property and less color unevenness. 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 cross-sectional view of an example of an antiglare antireflection film according to the present invention.

[Explanation of symbols]

 Reference Signs List 1 transparent support 2 hard coat layer 3 low refractive index layer 4 amorphous silica particles

Claims (5)

[Claims] 1. An optical film in which a hard coat layer and a low refractive index layer having a refractive index of 1.43 to 1.49 on the transparent support are provided in this order on a transparent support. Material has a refractive index of 1.58 to 2.00
Wherein the hard coat layer has an average particle size of 1.0 to 1
It contains 0.0 μm amorphous silica particles, and the low refractive index layer comprises a crosslinked product of a fluorine-containing compound having a dynamic friction coefficient of 0.03 to 0.15 and a contact angle to water of 90 to 120 °, The haze of the optical film is 3.0 to 20.0
%, Average reflectance from 450 nm to 650 nm is 1.8%
An antiglare antireflection film characterized by the following. 2. The method according to claim 1, wherein the silica particles having a particle diameter larger than one half of the thickness of the hard coat layer occupy 40 to 100% of the total weight of the silica particles.
The antiglare antireflection film according to the above. 3. A material for forming a hard coat layer comprises a monomer having two or more ethylenically unsaturated groups, titanium,
Particle size 1 of at least one oxide selected from aluminum, indium, zinc, tin, and antimony
An antiglare antireflection film, which is obtained by crosslinking fine particles of not more than 00 nm. 4. 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. 5. The anti-glare anti-reflection film according to claim 1 or the anti-glare anti-reflection polarizing plate according to claim 4 is used as an anti-reflection layer on the outermost layer of a display. A liquid crystal display device characterized by the above-mentioned.