JP2001318207A - Antireflection film and image display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an antireflection film having high antireflection performance, superior also in stain-proofing property and scuffing resistance and producible at a low cost and to provide an image display device, using the antireflection film. SOLUTION: The antireflection film is an optical film with a low refractive index layer, whose refractive index is 1.35-1.49 on a transparent base and the low refractive index layer contains a hydrolyzate of an organosilane and/or its partial condensation product, a compound which generates a reaction accelerator under light and a fluoropolymer. The optical film has 3.0-20.0% haze and 1.8% or lower average reflectance in the range of 450-650 nm.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antireflection film, particularly to an antireflection film having an antiglare property, and 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.

In recent years, the display of an image display device has been required to have higher precision, higher luminance, and higher color reproducibility, and further improvement in antireflection performance of antireflection films has been desired.

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 in order to reduce the reflectance. UV of dipentaerythritol hexaacrylate using triacetyl cellulose as a support
An anti-reflection film with a cured coating as a hard coat layer.
1.6% average reflectance from 50 nm to 650 nm
In order to make the refractive index below, the refractive index must be made below 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, in order to have sufficient scratch resistance, a compound having a refractive index of 1.43 or more was required.

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

JP-A-7-333404 describes an anti-glare anti-reflection film having excellent gas barrier properties, anti-glare properties and anti-reflection properties. Poor productivity compared to coating.

JP-B-6-98703, JP-A-63-2
No. 1601 discloses a technique for applying a composition comprising a hydrolyzed partial condensate of an alkoxysilane compound to the surface of a plastic substrate to reduce reflected light. According to the techniques described in these publications, an inorganic film is obtained by wet coating by a sol-gel method. Although an extremely high film strength is expected because it is an inorganic film, the above-mentioned inorganic film generally has poor adhesion to many base materials, and has a drawback that peeling failure easily occurs. Furthermore, a long time heating is essential for curing, and there is a disadvantage that productivity is poor.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to provide an antireflection film having excellent antireflection performance. Further, an object of the present invention is to form an antiglare hard coat layer and a low refractive index layer on a support, and have sufficient antireflection performance and scratch resistance, which is simple and inexpensive, and has antifouling properties. In addition, an object of the present invention is to provide an antireflection film with less color unevenness.

[0009]

The above object has been achieved by the following inventions. (1) A low refractive index having a refractive index of 1.35 to 1.49 comprising a hydrolyzate of organosilane and / or a partial condensate thereof, a compound generating a reaction accelerator by light, and a fluoropolymer on a transparent support. Anti-reflection film having a refractive index layer. (2) An antiglare hard coat layer on a transparent support and a refractive index of 1.35 to 1.49 on the antiglare hard coat layer.
In the optical film having a low refractive index layer, the antiglare hard coat layer contains fine particles having an average particle size of 1.0 to 10.0 μm, and the low refractive index layer has a hydrolyzate of organosilane and / or The optical film contains a partial condensate, a compound generating a reaction accelerator by light, and a fluoropolymer, and the haze of the optical film is 3.0 to 20.0%;
An anti-reflection film, wherein the average reflectance at 450 nm to 650 nm is 1.8% or less. (3) In the antiglare hard coat layer, the material forming the antiglare hard coat layer has a refractive index of 1.57 to 2.
00, wherein the antireflection film according to (2) is used. (4) The antireflection film according to any one of (1) to (3), wherein the compound that generates a reaction accelerator by light in the low refractive index layer is a photoacid generator. (5) The antireflection film according to any one of (1) to (4), wherein the fluorine-containing polymer in the low refractive index layer is a polymer obtained by polymerizing a fluorine-containing vinyl monomer. (6) The antireflection film according to any one of (1) to (5), wherein the fluoropolymer has a functional group capable of covalently bonding to the organosilane. (7) The antireflection film according to any one of (1) to (6), wherein the transparent support is triacetyl cellulose, polyethylene terephthalate, polyethylene naphthalate, ARTON, or ZEONEX. (8) The transparent support is a triacetylcellulose film, and the triacetylcellulose dope prepared by dissolving triacetylcellulose in a solvent is subjected to single-layer casting, multiple-layer co-casting or multiple-layer sequential casting. 8. The antireflection film according to any one of the above 1 to 7, wherein the antireflection film is produced by casting by any casting method. (9) The triacetylcellulose dope is characterized by being prepared by dissolving triacetylcellulose in a solvent substantially free of dichloromethane by a cooling dissolution method or a high-temperature dissolution method. 9. The antireflection film according to the above item 8, (10) A polarizing plate, wherein the 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 the polarizing plate. (11) The antireflection film according to any one of items (1) to (9) or the antireflection layer of the antireflection polarizing plate according to item (10) is used as the outermost layer of a display. Liquid crystal display.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The antireflection film of the present invention comprises a low-refractive-index layer comprising the following organosilane hydrolyzate and / or partial condensate thereof, a compound capable of generating a reaction accelerator by light, and a fluorine-containing polymer. Have. The refractive index is 1.
35 to 1.49, preferably 1.35 to 1.44.

Next, a basic structure of an antireflection film suitable as one embodiment of the present invention will be described with reference to FIG. The embodiment shown in FIG. 1 is an example of the antireflection film of the present invention, and has a layer structure in the order of a transparent support 1, a hard coat layer 2, an antiglare hard coat layer 3, and a low refractive index layer 4. Reference numeral 5 denotes particles, and the hard coat layer 3 has an antiglare property.
The material other than the particles 5 preferably has a refractive index of 1.5
7 to 2.00, more preferably 1.60 to 1.8
0, and the refractive index of the low refractive index layer 4 is 1.35 to 1.4.
9, preferably 1.35 to 1.44. The hard coat layer 2 is not essential, but is preferably applied to impart film strength. Average reflectance is 1.8% or less.
In the antireflection film, the low refractive index layer preferably satisfies the following expression (1).

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

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.

The refractive index of the antiglare hard coat layer in the present invention is not described by a single value, but is a non-uniform refractive index layer in which fine particles are dispersed in a material forming the antiglare hard coat layer. The material for forming the antiglare hard coat layer preferably has a refractive index of 1.57 to 2.00. If this is too small, the antireflection performance will be small, and if it is too large, the color may be too large. High refractive index material from a monomer having two or more ethylenically unsaturated groups and titanium, zirconium, aluminum, indium, zinc, tin, fine particles having a particle diameter of 100 nm or less consisting of at least one oxide selected from antimony For example, Japanese Patent Application Laid-Open No. H8-110401 discloses that fine particles have a sufficiently small particle size smaller than the wavelength of light, so that scattering does not occur and the particles behave as optically uniform substances.

In the hard-coating antiglare layer, internal scattering is caused by fine particles having a particle diameter of 1.0 μm or more dispersed in the high refractive index material, so that the hard-coating layer is affected by optical interference in the hard-coating antiglare layer. Absent. In the case of the high refractive index antiglare hard coat layer having no particles, a large amplitude of the reflectance is seen in the wavelength dependence of the reflectance due to optical interference due to the refractive index difference between the antiglare hard coat layer and the support. As a result, the antireflection effect deteriorates and color unevenness occurs at the same time. However, in the antireflection film of the present invention, these problems were solved by the internal scattering effect of fine particles.

The antireflection film of the present invention has an antiglare hard coat layer on a transparent support and a low refractive index layer thereon. If necessary, the antiglare hard coat layer A smooth hard coat layer can be provided as a lower layer.

The compound used for the antiglare hard coat layer is
A polymer having a saturated hydrocarbon or polyether as a main chain is preferable, and a polymer having a saturated hydrocarbon as a main chain is more preferable. 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, an aromatic ring, a halogen atom other than fluorine, sulfur, phosphorus,
It preferably contains at least one selected from nitrogen atoms.

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, pentaerythritol 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.

Examples of the high refractive index monomer include bis (4-methacryloylthiophenyl) sulfide, vinylnaphthalene, vinylphenylsulfide, 4-methacryloxyphenyl-4'-methoxyphenylthioether and the like. These monomers having an ethylenically unsaturated group need to be cured by a polymerization reaction using ionizing radiation or heat after application using a photo radical initiator or a thermal radical initiator.

The polymer having a polyether as a main chain is preferably synthesized by a ring-opening polymerization reaction of a polyfunctional epoxy compound. It is necessary to use a photoacid generator or a thermal acid generator, and after application, cure by a polymerization reaction using ionizing radiation or heat.

In place of or in addition to the monomer having two or more ethylenically unsaturated groups, a crosslinkable group is introduced into the polymer by using a monomer having a crosslinkable group, and the reaction of the crosslinkable group causes a crosslinkable structure. May be introduced into the binder polymer. Examples of the crosslinkable functional group include an isocyanate group, an epoxy group, an aziridine group, an oxazoline group, an aldehyde group, a carbonyl group, a hydrazine group, a carboxyl group, a methylol group, and an active methylene group.
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 crosslinkable group is not limited to the above compound, but may be a compound which shows reactivity as a result of decomposition of the above functional group. These compounds having a crosslinkable group need to be crosslinked by heat or the like after coating.

In order to increase the refractive index of the material, the antiglare hard coat layer has a particle diameter of at least 100 nm comprising at least one oxide selected from titanium, zirconium, aluminum, indium, zinc, tin and antimony. And preferably contains fine particles of 50 nm or less. Examples of the fine particles include TiO ₂ , ZrO ₂ , A
l ₂ O ₃ , In ₂ O ₃ , ZnO, SnO ₂ , Sb ₂ O ₃ , IT
O and the like. The addition amount of these inorganic fine particles is preferably 10 to 90%, more preferably 20 to 80% of the total mass of the antiglare hard coat layer,
Particularly preferred is 30 to 60%.

The antiglare hard coat layer is made of particles of a resin or an inorganic compound for the purpose of imparting antiglare properties and preventing deterioration in reflectance due to interference of the antiglare hard coat layer and color unevenness. Silica particles, TiO ₂ particles, crosslinked acrylic particles, crosslinked styrene particles, melamine resin particles, benzoguanamine resin particles, and the like are preferably used. The average particle size is preferably from 1.0 to 10.0 μm, more preferably from 1.5 to 7.0 μm. Further, as the shape of the particles, any of a true sphere and an irregular shape can be used. Two or more different particles may be used in combination. The amount of particles applied is
Preferably it is 10 to 1000 mg / m ² , more preferably 30 to 100 mg / m ² . Further, it is preferable that silica particles having a particle diameter larger than half of the thickness of the antiglare hard coat layer occupy 40 to 100% of the whole silica particles. 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. Anti-glare hard coat layer thickness is 1 to 1
0 μm is preferable, and 1.2 to 6 μm is more preferable.

In the present invention, the resin used for the smooth hard coat layer is the same as that described for the antiglare hard coat layer except that fine particles imparting antiglare properties are not used. The smooth hard coat layer is provided between the transparent support and the antiglare hard coat layer as needed for the purpose of improving the film strength. The thickness of the smooth hard coat layer is preferably 1 to 10 μm, more preferably 1.2 to 6 μm.

In the low refractive index layer of the present invention, a hydrolyzate of organosilane and / or a partial condensate thereof, a so-called sol-gel component (hereinafter referred to as such) is used to improve film strength and abrasion resistance. Has contributed. Fluorine-containing polymers are also used and contribute to antifouling properties and slip properties. As the fluorinated polymer, a polymer obtained by polymerizing a fluorinated vinyl monomer is preferable, and it is more preferable that the fluorinated polymer has a functional group that can be covalently bonded to the sol-gel component from the viewpoint of compatibility with the sol-gel component and film strength. The sol-gel component is in a sol state at the stage of the coating solution, and is rapidly cured by light irradiation after application by the action of a compound that generates a reaction accelerator by light.

The organosilane used in the low refractive index layer of the present invention is represented by the following general formula (2).

R _x Si (OR ') _4-x (2)

(However, R and R ′ may be the same or different and each represents hydrogen, an alkyl group, an aryl group,
It represents an allyl group or a fluoroalkyl group, and the alkyl group may have an epoxy group, an amino group, an acryl group, an isocyanate group, or a mercapto group as a functional group. x is an integer of 0 to 3. )

As specific examples of the organosilane represented by the general formula (2), when x = 0, tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, etc. 1 includes methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, CF ₃ CH ₂
CH ₂ Si (OCH ₃ ) ₃ , CF ₃ (CF ₂ ) ₅ CH ₂ CH ₂ S
i (OCH ₃ ) ₃ , γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-trimethoxysilylpropylisocyanate, γ-mercaptopropyltrimethoxysilane , Γ-methacryloxypropyltrimethoxysilane, γ-acryloxypropyltrimethoxysilane, etc., where x = 2 is dimethyldimethoxysilane, dimethyldiethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-aminopropyl Examples include methyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, and γ-methacryloxypropylmethyldimethoxysilane, but the present invention is not limited to these. It is also common practice to use a mixture of two or more different organosilanes, and it is preferable to appropriately adjust the hardness, the brittleness, and the purpose of introducing a functional group.

The hydrolysis-condensation reaction of the organosilane can be carried out without a solvent or in a solvent. As the solvent, an organic solvent is preferable, and acetone, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, methanol, ethanol, isopropyl alcohol, butanol, toluene, xylene, tetrahydrofuran,
4-dioxane and the like can be mentioned. The solvent used here must also dissolve the fluoropolymer. The hydrolysis condensation reaction is preferably performed in the presence of a catalyst. As the catalyst, inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid,
Organic acids such as oxalic acid, acetic acid, formic acid, methanesulfonic acid, and toluenesulfonic acid; inorganic bases such as sodium hydroxide, potassium hydroxide and ammonia; organic bases such as triethylamine and pyridine; triisopropoxy aluminum and tetrabutoxy Metal alkoxides such as zirconium; metal chelate compounds of the metal alkoxides with ethyl acetoacetate, acetylacetone and the like. The hydrolysis-condensation reaction is performed by adding 0.3 to 2.0 mol, preferably 0.5 to 1.0 mol of water to 1 mol of the alkoxy group, at 25 to 100 ° C. in the presence of the solvent and the catalyst. This is performed by stirring. The amount of the catalyst added is 0.1 to the alkoxy group.
The content is from 01 to 10 mol%, preferably from 0.1 to 5 mol%. The reaction conditions are preferably adjusted as appropriate depending on the reactivity of the organosilane.

Examples of the fluorine-containing polymer used in the low refractive index layer of the present invention include a fluorine-containing vinyl polymer, a fluorine-containing polyether, and a fluorine-containing polysiloxane, and a fluorine-containing vinyl polymer is preferable. further,
It is more preferable that the fluorine-containing vinyl polymer has a reactive group and is covalently bonded to the sol-gel component after application and curing. The fluorinated vinyl polymer of the present invention can be obtained by radical polymerization of a fluorinated vinyl monomer. Specific examples of the fluorine-containing monomer include, for example, fluoroolefins (eg, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, 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)), fully or partially fluorinated vinyl ethers, etc. is there. Of these, hexafluoropropylene and fluorinated vinyl ethers are preferred.

The vinyl monomer having a functional group capable of covalently bonding to organosilane will be described below. Examples of the functional group for imparting reactivity with a silanol group generated by hydrolysis of the organosilane include an alkoxysilyl group. As the alkoxysilyl group-containing monomer, γ
-Methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, and the like. By using the organosilane having a functional group, an epoxy group, an amino group, an isocyanate group, a mercapto group, and the like can be introduced into the sol-gel component. Examples of the functional group capable of covalently bonding to these functional groups include a hydroxy group, an epoxy group, and a carboxyl group. Examples of the vinyl monomer having these functional groups include 2-hydroxyethyl methacrylate having a hydroxy group, -Hydroxyethyl acrylate, 2-hydroxyethyl vinyl ether, 3
-Hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, glycidyl methacrylate having an epoxy group, glycidyl acrylate, vinyl glycidyl ether, acrylic acid having a carboxyl group,
Methacrylic acid, β-carboxyethyl acrylate, crotonic acid, itaconic acid, α-vinyl acetic acid, vinyl fumarate, vinyl maleate, and the like,
The present invention is not limited to these.

Vinyl monomers other than those described above can also be used as copolymer monomers. Such monomers include, 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, divinyl benzene, vinyl toluene, α-methyl styrene, etc.), vinyl ethers (methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, n-
Butyl vinyl ether, etc.), vinyl esters (vinyl acetate, vinyl propionate, vinyl cinnamate, etc.), acrylamides (N-tertbutylacrylamide, N-
Cyclohexyl acrylamide), methacrylamides, acrylonitrile derivatives and the like.
Of these, vinyl ethers are preferred.

In the present invention, the mixing ratio of the above monomers is 20 to 80% for the fluorine-containing monomer, 0 to 30% for the functional group-containing monomer, and 0 to 7% for the other monomers.
0% is preferred. The monomer mixture can be polymerized by ordinary radical polymerization.

The compound used in the low refractive index layer of the present invention to generate a reaction accelerator by light is not particularly limited, but a photoacid generator or a photobase generator is preferable.
In any case, the condensation reaction of the sol-gel component can be promoted. Specifically, benzoin tosylate, tri (nitrobenzyl) phosphate, diaryliodonium salt, triarylsulfonium salt, etc. are used as the photoacid generator, and nitrobenzylcyclohexylcarbamate, di (methoxybenzyl) are used as the photobase generator. Hexamethylene dicarbamate and the like can be mentioned. Of these, photoacid generators are preferred, and specifically, triarylsulfonium salts and diaryliodonium salts are preferred.
Sensitizing dyes can also be preferably used in combination with these compounds. The addition amount of the compound that generates a reaction accelerator by light according to the present invention is preferably 0.1 to 15%, more preferably 0.5 to 5%, based on the total solid content of the coating solution for the low refractive index layer. .

The sol-gel component and the fluoropolymer component of the low refractive index layer of the present invention are preferably connected by a covalent bond after curing, from the viewpoint of film strength and transparency. For this purpose, it is also preferable to modify the functional group of the fluoropolymer into an alkoxysilyl group in the state of a coating solution. As a modification method, an organosilane having a functional group capable of reacting with the functional group of the fluoropolymer may be reacted in advance. The thickness of the low refractive index layer of the present invention is preferably 0.05 to 0.2 μm, more preferably 0.08 to 0.28 μm.
To 0.12 μm.

It is preferable to use a plastic film as the transparent support of the present invention. Examples of the polymer forming the plastic film include cellulose ester (eg, triacetyl cellulose, diacetyl cellulose), polyamide, polycarbonate, polyester (eg, polyethylene terephthalate, polyethylene naphthalate), polystyrene, polyolefin, ARTON, ZEONEX and the like. Of these, triacetyl cellulose, polyethylene terephthalate, polyethylene naphthalate, ARTON and ZEONEX are preferred. When the 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 side. When the transparent support is triacetyl cellulose, triacetyl cellulose is used as a protective film for protecting the polarizing layer of the polarizing plate. Therefore, it is preferable in terms of cost to use the antireflection film of the present invention as it is as the protective film. The thickness of the support is not particularly limited, but is preferably 50 to 150 μm, and 70 to 120 μm.
μm is more preferred.

As the transparent support, a triacetylcellulose dope prepared by dissolving triacetylcellulose in a solvent is subjected to any one of a single-layer casting method, a multi-layer co-casting method and a multi-layer sequential casting method. It is preferable to use a triacetylcellulose film produced by casting. In particular, from the viewpoint of environmental conservation, triacetyl cellulose prepared using a triacetyl cellulose dope prepared by dissolving triacetyl cellulose in a solvent substantially free of dichloromethane by a cooling dissolution method or a high-temperature dissolution method. Films are preferred.

Examples of the monolayer casting of triacetyl cellulose include drum casting and band casting disclosed in JP-A-7-11055 and the like. Co-casting of triacetyl cellulose comprising a plurality of layers is available. JP-A-61-9472
5, and JP-B-62-43846. Sequential casting is performed by repeating single layer casting. In each casting, the raw material flakes are formed from halogenated hydrocarbons (dichloromethane, etc., alcohols (methanol, ethanol, butanol, etc.), esters (methyl formate, methyl acetate), ethers (dioxane, dioxolan, diethyl ether, etc.). And a solution (called a dope) to which various additives such as a plasticizer, an ultraviolet absorber, a deterioration inhibitor, a slipping agent, and a peeling accelerator are added if necessary. When casting on a support consisting of an endless metal belt or a rotating drum by a dope supplying means (referred to as a die), a single layer is cast with a single dope, and a single layer is cast with a dope. If co-casting a low concentration dope on both sides of a high concentration cellulose ester dope, peeling the rigidity-imparted film dried to some extent on the support, Ide passed through a drying section by a variety of transport means is a method comprising removing the solvent.

As a solvent for dissolving triacetyl cellulose as described above, dichloromethane is typical. However, technically, halogenated hydrocarbons such as dichloromethane can be used without any problem.However, when a triacetyl cellulose dope prepared by dissolving in a solvent substantially containing dichloromethane is produced by a monolayer casting method. , Since dichloromethane is released into the atmosphere during the manufacturing process, from the viewpoint of environmental protection and working environment,
It is preferable that halogenated hydrocarbons such as dichloromethane are not substantially contained. “Substantially free” means that the proportion of halogenated hydrocarbon in the organic solvent is less than 5% by mass (preferably less than 2% by mass). In the case of the co-casting method, even if a dope using a solvent containing substantially dichloromethane is cast by a multi-layer co-casting method, a dope having a higher triacetyl cellulose concentration than the outer casting layer is obtained. Can be used for the inner casting layer, thereby reducing the amount of dichloromethane released into the atmosphere. Further, the casting speed can be increased, and the productivity is excellent. Of course, even in the case of the co-casting method, it is preferable that halogenated hydrocarbons such as dichloromethane are not substantially contained. When adjusting the dope of triacetylcellulose using a solvent that does not substantially contain dichloromethane or the like, a special dissolution method as described below is essential.

The first melting method is called a cooling melting method and will be described below. First, the temperature around room temperature (-10 to 40 ° C)
And gradually add triacetyl cellulose to the solvent with stirring. Next, the mixture is -100 to -10C (preferably -80 to -10C, more preferably -50 to-
(20 ° C., most preferably −50 to −30 ° C.). Cooling is performed, for example, in a dry eye / methanol bath (−7).
5 ° C) or a cooled diethylene glycol solution (-30 to
-20 ° C). Upon such cooling, the mixture of triacetyl cellulose and the solvent solidifies. Further, the temperature is raised to 0 to 200 ° C (preferably 0 to 15 ° C).
Heating to 0 ° C., more preferably 0 to 120 ° C., and most preferably 0 to 50 ° C.) results in a solution in which triacetyl cellulose flows in the solvent. The temperature may be raised only by leaving it at room temperature or may be heated in a warm bath.

The second method is called a high-temperature melting method and will be described below. First, triacetyl cellulose is gradually added to a solvent at a temperature around room temperature (−10 to 40 ° C.) with stirring. The triacetyl cellulose is preferably added to a mixed solvent containing various solvents and swelled in advance. In the present method, the dissolution concentration of triacetyl cellulose is preferably 30% by mass or less, but from the viewpoint of drying efficiency during film formation, the concentration is preferably as high as possible. Next, the mixed solution of the organic solvent in which triacetyl cellulose is dissolved is mixed under pressure of 0.2 MPa to 30 MPa.
-240 ° C, preferably 80-220 ° C, more preferably 100-200 ° C, most preferably 100-190 ° C, then these heated solutions cannot be applied as such, so the lowest boiling point of the solvent used Cool below. In that case, it is common to cool to −10 to 50 ° C. and return to normal pressure. For cooling, the high-pressure high-temperature vessel or line in which the triacetylcellulose solution is incorporated may be simply left at room temperature, and more preferably, the apparatus may be cooled using a cooling medium such as cooling water.

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).

The polarizing plate of the present invention comprises the above-mentioned antireflection film for at least one of the two protective films of the polarizing layer. By using the antireflection film of the present invention as the outermost layer, reflection of external light and the like can be prevented, and a polarizing plate having excellent scratch resistance, stain resistance, and the like can be obtained. Further, in the polarizing plate of the present invention, since the antireflection film also functions as the protective film, the production cost can be reduced.

The antireflection film is made of 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.

[0046]

The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto.

(Preparation of Coating Solution A for Antiglare Hard Coat Layer) A mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DP
HA, manufactured by Nippon Kayaku Co., Ltd.) 250 g of a mixed solvent of methyl ethyl ketone / cyclohexanone = 50/50% 439
g. 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.), stirred and dispersed at 5,000 rpm for 1 hour with a high-speed disperser, and then filtered through a polypropylene filter having a pore size of 30 μm to obtain a coating solution for the antiglare hard coat layer. Prepared.

(Preparation of Coating Solution B for Antiglare Hard Coat Layer) A mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DP
125 g of HA (manufactured by Nippon Kayaku Co., Ltd.) and 125 g of bis (4-methacryloylthiophenyl) sulfide (MPSMA, manufactured by Sumitomo Seika Co., Ltd.) are dissolved in 439 g of a mixed solvent of methyl ethyl ketone / cyclohexanone = 50/50%. did. To the resulting solution, 5.0 g of a photopolymerization initiator (Irgacure 907, manufactured by Ciba Geigy) and 3.0 g of a photosensitizer (Kayacure DETX, manufactured by Nippon Kayaku Co., Ltd.)
Was dissolved in 49 g of methyl ethyl ketone. The refractive index of the coating film obtained by applying this solution and curing with ultraviolet light was 1.60. In addition, the average particle size
μm crosslinked polystyrene particles (trade name: SX-200)
H, manufactured by Soken Chemical Co., Ltd.), 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 an antiglare hard coat layer. did.

(Preparation of Coating Solution C for Antiglare Hard Coat Layer) A hard coat coating solution containing a zirconium oxide dispersion (K) was stirred in a mixed solvent of 104.1 g of cyclohexanone and 61.3 g of methyl ethyl ketone with an air disper.
217.9 g of Z-7991 (manufactured by JSR Corporation) was added. The coating film obtained by applying this solution and curing with ultraviolet light had a refractive index of 1.70. Further, crosslinked polystyrene particles having an average particle size of 2 μm (trade name: SX-200) were added to this solution.
H, manufactured by Soken Chemical Co., Ltd.), and the mixture was stirred and dispersed at 5000 rpm for 1 hour with a high-speed disperser.
The solution was filtered through a 0 μm polypropylene filter to prepare a coating solution for an antiglare hard coat layer.

(Preparation of Coating Solution D for Antiglare Hard Coat Layer) A hard coat coating solution containing a zirconium oxide dispersion (KZ-7118, manufactured by JSR Corporation) was added to 32.2 g of cyclohexanone while stirring with an air disper. 3
g, and 123.4 g of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.). 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-200) were added to this solution.
H, manufactured by Soken Chemical Co., Ltd.), stirred and dispersed at 5,000 rpm for 1 hour with a high-speed disperser, and then filtered through a polypropylene filter having a pore size of 30 μm, followed by coating with an antiglare hard coat layer. Was prepared.

(Preparation of Coating Solution E 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. % Of the mixed solvent. 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 1.53. Further, the solution was added with a pore size of
Then, the mixture was filtered through a polypropylene filter of m to prepare a coating solution for a hard coat layer.

(Preparation of Coating Solution A for Low Refractive Index Layer) A photocurable sol-gel compound containing a fluorine-containing polymer having a refractive index of 1.41 and a compound capable of generating a reaction accelerator by light (Opster TM501A, solid content: 15%) %, JSR
After adding 72 g of methyl isobutyl ketone to 28 g and 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.

(Preparation of Coating Solution B for Low Refractive Index Layer) A photocurable sol-gel compound containing a fluorine-containing polymer having a refractive index of 1.43 and a compound capable of generating a reaction accelerator by light (Opster TM505, solid content of 15%) %, JSR
After adding 72 g of methyl isobutyl ketone to 28 g and 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.

(Preparation of Coating Solution C for Low Refractive Index Layer) A thermally crosslinkable fluoropolymer having a refractive index of 1.40 (JN-722)
3, 12 g of methyl isobutyl ketone was added to 28 g of a solid content concentration of 6% (manufactured by JSR Corporation), and after stirring, the pore size was 1 μm.
To prepare a coating solution for a low refractive index layer.

(Preparation of Coating Solution D for Low Refractive Index Layer) Tetraethoxysilane / methyltrimethoxysilane / γ-glycidoxypropyltrimethoxysilane having a refractive index of 1.45 = 40/40/20% hydrolyzed portion 28 g of the condensate (solid content 15%) was added to a photoacid generator (Siracure UVI-
(6990, solid content 50%) 0.084 g and methyl isobutyl ketone 72 g were added, and after stirring, the mixture was filtered through a polypropylene filter having a pore size of 1 μm to prepare a coating solution for a low refractive index layer.

(Preparation of Coating Solution E for Low Refractive Index Layer) Tetraethoxysilane / methyltrimethoxysilane / γ-glycidoxypropyltrimethoxysilane having a refractive index of 1.45 = 40/40/20% hydrolyzed portion 25.2 g of a condensate (solid content 15%) was added to a thermally crosslinkable fluoropolymer (J
N-7223, solid content concentration 6%, 7 g, manufactured by JSR Corporation)
And 0.084 g of a photoacid generator (Siracure UVI-6990, solid content 50%) and methyl isobutyl ketone 67.
After adding 8 g and stirring, the mixture was 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 An antiglare hard coat layer coating solution A was coated on a triacetyl cellulose film (TAC-TD80U, Fuji Photo Film Co., Ltd.) having a thickness of 80 μm using a bar coater. After applying and drying at 120 ° C., an illuminance of 400 W / cm was applied using an air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) of 160 W / cm.
The coating layer was cured by irradiating an ultraviolet ray having an irradiation amount of 300 mJ / cm ^{2 with} an irradiation amount of 300 mJ / cm ² to form an antiglare hard coat layer having a thickness of 6 μm. 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.
The coating solution A for a low refractive index layer was coated thereon using a bar coater, dried at 60 ° C., and then irradiated with an illuminance of 400 mW / c.
The coating layer was cured by irradiating ultraviolet rays having an irradiation amount of 300 mJ / cm ² at m ² and then heated at 120 ° C. for 8 minutes to form a low refractive index layer having a thickness of 0.096 μm.

[Example 2] A sample was prepared in the same manner as in Example 1 except that the coating liquid B of the low refractive index layer was used instead of the coating liquid A of the low refractive index layer, and coating was performed using a spin coater.

Comparative Example 1 An antiglare hard coat layer was formed in the same manner as in Example 1. A low-refractive-index coating solution C was applied thereon using a bar coater, dried at 80 ° C., and further dried for 1 hour.
Heating was performed at 20 ° C. for 10 minutes to form a low-refractive-index layer having a thickness of 0.096 μm, thereby preparing a comparative sample.

Comparative Example 2 A comparative sample was prepared in the same manner as in Example 1, except that the low refractive index coating solution D was used instead of the low refractive index layer coating solution A.

Example 3 A coating solution E 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 in 16
Using an air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) of 0 W / cm, illuminance 400 mW / cm ² ,
The coating layer was cured by irradiating an ultraviolet ray having an irradiation amount of 300 mJ / cm ² to form a hard coat layer having a thickness of 4 μm. An antiglare hard coat 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 a hard coat layer having a thickness of about 1.5 μm. Formed. The coating liquid A for a low refractive index layer was applied thereon using a bar coater, dried at 60 ° C., and irradiated with ultraviolet light having an illuminance of 400 mW / cm ² and an irradiation amount of 300 mJ / cm ² to form a coating layer. After curing, 8 hours at 120 ° C
The mixture was heated for minutes to form a low refractive index layer having a thickness of 0.096 μm.

Example 4 A sample was prepared in the same manner as in Example 3 except that coating liquid C for an antiglare hard coat layer was used instead of coating liquid B for an antiglare hard coat layer.

Example 5 A sample was prepared in the same manner as in Example 3 except that a coating liquid D for an antiglare hard coat layer was used instead of the coating liquid B for an antiglare hard coat layer, and the coating was performed using a gravure coater. It was created.

Example 6 A sample was prepared in the same manner as in Example 4 except that the coating liquid B for a low refractive index layer was used in place of the coating liquid A for a low refractive index layer.

Comparative Example 3 An antiglare hard coat layer was formed in the same manner as in Example 4. On top of that, a coating solution C for a low refractive index layer
Was applied using a bar coater, dried at 80 ° C., and further heated at 120 ° C. for 10 minutes to form a low refractive index layer having a thickness of 0.096 μm to prepare a comparative sample.

Comparative Example 4 A comparative sample was prepared in the same manner as in Example 4 except that the low refractive index layer coating liquid D was used instead of the low refractive index layer coating liquid A.

Example 7 A coating solution E for a hard coat layer was coated on a triacetyl cellulose film (TAC-TD80U, manufactured by Fuji Photo Film Co., Ltd.) with a thickness of 80 μm using a bar coater. After drying in 160
Using a W / cm air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.), the coating layer is cured by irradiating ultraviolet rays with an illuminance of 400 mW / cm ² and an irradiation amount of 300 mJ / cm ² to form a hard coat having a thickness of 4 μm. A layer was formed. The coating solution A for a low refractive index layer was coated thereon using a bar coater, dried at 60 ° C., and then irradiated with an illuminance of 400 mW / c.
The coating layer was cured by irradiating ultraviolet rays having an irradiation amount of 300 mJ / cm ² at m ² and then heated at 120 ° C. for 8 minutes to form a low refractive index layer having a thickness of 0.096 μm.

(Evaluation of Antireflection Film) The obtained film was evaluated for the following items. (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) Evaluation of Pencil Hardness Pencil hardness evaluation described in JIS K 5400 was performed as an index of scratch resistance. Antireflection film at a temperature of 25 ° C and a humidity of 60
% RH for 2 hours, using a 3H test pencil specified in JIS S 6006, with a load of 1 kg, and no scratches are observed in the evaluation of n = 5: ○ In the evaluation of n = 5 1 or 2 scratches: Δ 3 or more scratches in the evaluation of n = 5: ×

(4) Evaluation of Contact Angle and Fingerprint Adhesion As an index of surface contamination resistance, an 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. The coefficient of kinetic friction was adjusted at 25 ° C. and a relative humidity of 60% for 2 hours, and then 5 mmφ using a HEIDON-14 kinetic friction measuring instrument.
Stainless steel ball, load 100g, speed 60cm / min
The value measured in was used.

(6) Evaluation of Antiglare Property A bare fluorescent lamp (8000 cd / m ² ) without a louver was projected on the produced antiglare film, and the degree of blurring of the reflected image was evaluated according to the following criteria. The outline of the fluorescent lamp is not known at all: ◎ The outline of the fluorescent lamp is slightly recognized: ○ The fluorescent lamp is blurred, but the outline can be identified: △ The fluorescent lamp is hardly blurred: ×

(7) Glare Evaluation A louver-equipped fluorescent lamp diffused light was projected on the produced antiglare 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.
All of Examples 1 to 6 were excellent in antireflection performance, and all properties required for an antiglare antireflection film such as pencil hardness, fingerprint adhesion, antiglare property, and glare were good.
Example 7 does not have an anti-glare property because it does not have an anti-glare layer, but has little haze, is excellent in image clarity, is excellent in antireflection performance, and has a reflection such as pencil hardness and fingerprint adhesion. All the performances required for the barrier film were good.
In Comparative Examples 1 and 3, since no sol-gel component was present in the low refractive index layer, the pencil hardness was poor and the scratch resistance was insufficient. In Comparative Examples 2 and 4, since there was no fluoropolymer component, the contact angle was low, there was no fingerprint adhesion, and the antifouling property was insufficient.

[0075]

[Table 1]

Next, an antireflection polarizing plate was prepared using the films of Examples 1 to 6. When a liquid crystal display device in which an antireflection layer was disposed on the outermost layer using this polarizing plate was produced, 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. Further, an antireflection polarizing plate was produced using the film of Example 7. When a liquid crystal display device was similarly manufactured using this polarizing plate, excellent contrast was obtained because of no reflection of external light, and excellent visibility was obtained.

<Preparation of Supports Used in Examples 8 to 17 and Comparative Examples 5 to 8> (1) Preparation of Trilayer Co-cast Triacetyl Cellulose Film A (Preparation of Triacetyl Cellulose-Doped A1) Triacetyl Cellulose A raw material composed of 17.4 parts by mass, 2.6 parts by mass of triphenyl phosphate, 66 parts by mass of dichloromethane, 5.8 parts by mass of methanol, and 8.2 parts by mass of normal butanol was mixed and dissolved while stirring, and triacetyl was added. Cellulose dope A was prepared.

(Preparation of Triacetylcellulose Dope A2) Triacetylcellulose 24 parts by mass, triphenylphosphate 4 parts by mass, dichloromethane 66 parts by mass,
A raw material consisting of 6 parts by mass of methanol was mixed and dissolved with stirring to prepare triacetyl cellulose dope A2.

(Preparation of tri-layer co-cast triacetyl cellulose film A) According to JP-A-11-254594, using a three-layer co-casting die, the dope A1 was arranged on both sides of the dope A2 so as to be co-cast. Then, the casting film was simultaneously discharged onto a metal drum to form a multilayer cast, and then the casting film was peeled off from the drum, dried, and then 10 μm, 60 μm, and 1 μm from the drum surface side.
A 0 μm three-layer co-cast triacetyl cellulose film was prepared. In this film, no clear interface was formed between the layers.

(2) Preparation of triacetyl cellulose film B by low-temperature dissolution method (Preparation of triacetyl cellulose dope B) 20 parts by weight of triacetyl cellulose, 48 parts by weight of methyl acetate, 20 parts by weight of cyclohexanone, 5 parts by weight of methanol, ethanol 5 parts by mass, 2 parts by mass of triphenyl phosphate / biphenyldiphenyl phosphate (1/2), 0.1 part by mass of silica (particle size: 20 nm), 2,4-bis- (n
(Octylthio) -6- (4-hydroxy-3,5-di-tert-butylanilino) -1,3,5-triazine (0.2 part by mass) was added thereto, and the mixture was stirred to obtain a heterogeneous gel-like solution. After cooling at −70 ° C. for 6 hours, the mixture was heated to 50 ° C. and stirred to prepare dope B.

(Preparation of triacetyl cellulose film B by low-temperature dissolution method)
The above-mentioned triacetyl cellulose dope B was cast in a single-layer drum, and a 80 μm-thick triacetyl cellulose film B
Was prepared.

(3) Preparation of Triacetyl Cellulose Film C by High-Temperature Dissolution Method (Preparation of Triacetyl Cellulose Dope C) A non-uniform gel-like solution obtained in the same manner as in the above triacetyl cellulose dope B was sealed with stainless steel. 1MPa in container,
After heating at 180 ° C. for 5 minutes, the whole container was put into a 50 ° C. water bath and cooled to prepare triacetyl cellulose dope C.

(Preparation of Triacetyl Cellulose Film C by High Temperature Dissolution Method)
The above triacetyl cellulose dope C was cast in a single-layer drum, and the triacetyl cellulose film C having a thickness of 80 μm was cast.
Was prepared.

Example 8 The above-mentioned coating solution A for an antiglare hard coat layer was applied to the above three-layer co-cast triacetyl cellulose film A using a bar coater,
After drying with a 160 W / cm air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.), the illuminance was 40
The coating layer was cured by irradiating ultraviolet rays at 0 mW / cm ² and an irradiation amount of 300 mJ / cm ² to form an antiglare hard coat layer having a thickness of 6 μm. 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. The coating liquid A for a low refractive index layer was coated thereon using a bar coater, dried at 60 ° C., and then irradiated with an illuminance of 400 mW.
/ Cm ^2, after curing the coating layer by an irradiation dose of 300 mJ / cm ^2, was heated further 8 minutes at 120 ° C., to form a low refractive index layer having a thickness of 0.096Myuemu.

Example 9 A sample was prepared in the same manner as in Example 8, except that the low refractive index layer coating solution B was used instead of the low refractive index layer coating solution A and the coating was performed using a spin coater.

Comparative Example 5 An antiglare hard coat layer was formed in the same manner as in Example 8. A low-refractive-index coating solution C was applied thereon using a bar coater, dried at 80 ° C., and further dried for 1 hour.
Heating was performed at 20 ° C. for 10 minutes to form a low-refractive-index layer having a thickness of 0.096 μm, thereby preparing a comparative sample.

Comparative Example 6 A comparative sample was prepared in the same manner as in Example 8, except that the low-refractive-index layer coating solution D was used instead of the low-refractive-index layer coating solution A.

Example 10 A hard coat layer coating solution E was applied to the above three-layer co-cast triacetyl cellulose film A using a bar coater, dried at 120 ° C., and dried at 160 W / cm ² . Illuminance 400mW using an air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.)
/ 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 antiglare hard coat 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 a hard coat layer having a thickness of about 1.5 μm. Formed. The coating liquid A for a low refractive index layer was applied thereon using a bar coater, dried at 60 ° C., and then irradiated with an illuminance of 400 mW / cm ² and an irradiation amount of 300 mJ / cm ^2.
After the applied layer is cured by irradiating ultraviolet rays of
Heating was performed at 0 ° C. for 8 minutes to form a low refractive index layer having a thickness of 0.096 μm.

Example 11 A sample was prepared in the same manner as in Example 10, except that the antiglare hard coat layer coating solution C was used instead of the antiglare hard coat layer coating solution B.

Example 12 A sample was prepared in the same manner as in Example 10 except that the anti-glare hard coat layer coating liquid D was used instead of the anti-glare hard coat layer coating liquid D and the coating was performed using a gravure coater. did.

Example 13 A sample was prepared in the same manner as in Example 11 except that the low-refractive-index layer coating solution B was used instead of the low-refractive-index layer coating solution A.

Example 14 A sample was prepared in the same manner as in Example 13 except that the transparent support was changed to a triacetyl cellulose film B by a low-temperature dissolution method.

Example 15 A sample was prepared in the same manner as in Example 13 except that the transparent support was changed to a triacetyl cellulose film C by a high-temperature dissolution method.

Comparative Example 7 An antiglare hard coat layer was formed in the same manner as in Example 11. A low-refractive-index coating solution C was applied thereon using a bar coater, dried at 80 ° C., and further heated at 120 ° C. for 10 minutes to form a low-refractive-index layer having a thickness of 0.096 μm. Was prepared.

Comparative Example 8 A comparative sample was prepared in the same manner as in Example 11, except that the low refractive index coating solution D was used instead of the low refractive index layer coating solution A.

Example 16 A coating solution E for a hard coat layer was applied to the above three-layer co-cast triacetyl cellulose film A.
Is applied using a bar coater and dried at 120 ° C.
Illuminance of 400 mW / c using a 160 W / cm ² air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.)
The coating layer was cured by irradiating ultraviolet rays having an irradiation amount of 300 mJ / cm ² with m ² , and a hard coat layer having a thickness of 4 μm was formed. The coating liquid A for a low refractive index layer was coated thereon using a bar coater, dried at 60 ° C., and then irradiated with an illuminance of 400 mW.
/ Cm ^2, after curing the coating layer by an irradiation dose of 300 mJ / cm ^2, was heated further 8 minutes at 120 ° C., to form a low refractive index layer having a thickness of 0.096Myuemu.

Example 17 A sample was prepared in the same manner as in Example 11 except that the low-refractive-index layer coating solution E was used instead of the low-refractive-index layer coating solution A.

Table 2 shows the results of the same evaluation as described above for Examples 8 to 17 and Comparative Examples 5 to 8.

[0099]

[Table 2]

Examples 8 to 15 and 17 are all excellent in antireflection performance, and all properties required for an antiglare antireflection film such as pencil hardness, fingerprint adhesion, antiglare property and glare are good. there were. Example 16 has no anti-glare property because it does not have an anti-glare layer, but has almost no haze, is excellent in image clarity, is excellent in anti-reflection performance, and has a reflection such as pencil hardness and fingerprint adhesion. All the performances required for the barrier film were good. Comparative Examples 5 and 7 had poor pencil hardness because no sol-gel component was present in the low refractive index layer.
The scratch resistance was insufficient. In Comparative Examples 6 and 8, since there was no fluoropolymer component, the contact angle was low, there was no fingerprint adhesion, and the antifouling property was insufficient.

Next, antiglare antireflection polarizing plates were prepared using the films of Examples 8 to 15 and 17. When a liquid crystal display device in which an antireflection layer was disposed on the outermost layer using this polarizing plate was produced, 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. Further, an antireflection polarizing plate was produced using the film of Example 16. When a liquid crystal display device was similarly manufactured using this polarizing plate, excellent contrast was obtained because of no reflection of external light, and excellent visibility was obtained.

[0102]

The antireflection film of the present invention has high antireflection performance, excellent antifouling property and scratch resistance, and can be manufactured at low cost by forming an antiglare hard coat layer and a low refractive index layer. it can. The polarizing plate and the liquid crystal display device using the antireflection film have excellent properties such that the reflection of external light is sufficiently prevented and the antifouling property and scratch resistance are high.

[Brief description of the drawings]

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

[Explanation of symbols]

 REFERENCE SIGNS LIST 1 transparent support 2 hard coat layer 3 antiglare hard coat layer 4 low refractive index layer 5 particles

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08J 7/04 CFD C09D 5/00 Z C09D 5/00 7/12 7/12 127/12 127/12 183 / 00 183/00 C09K 3/00 U C09K 3/00 G02F 1/1335 G02F 1/1335 510 510 C08L 1:12 // C08L 1:12 67:02 67:02 G02B 1/10 A

Claims (11)

[Claims] 1. A refractive index of 1.35 to 1.49 containing a hydrolyzate of organosilane and / or a partial condensate thereof, a compound generating a reaction accelerator by light, and a fluoropolymer on a transparent support. An antireflection film having a low refractive index layer. 2. An optical film, comprising: an antiglare hard coat layer on a transparent support; and a low refractive index layer having a refractive index of 1.35 to 1.49 on the antiglare hard coat layer.
The hard-coating antiglare layer has an average particle size of 1.0 to 10.0.
The low refractive index layer contains a hydrolyzate of organosilane and / or a partial condensate thereof, a compound generating a reaction accelerator by light, and a fluorine-containing polymer, and the haze of the optical film is reduced. 3.0 to 20.
0%, the average reflectance from 450 nm to 650 nm is 1.8
% Or less. 3. The antiglare hard coat layer, wherein the material forming the antiglare hard coat layer has a refractive index of 1.5.
The anti-reflection film according to claim 2, wherein the thickness is 7 to 2.00. 4. The antireflection film according to claim 1, wherein in the low refractive index layer, a compound that generates a reaction accelerator by light is a photoacid generator. 5. The antireflection film according to claim 1, wherein the fluoropolymer in the low refractive index layer is a polymer obtained by polymerizing a fluorovinyl monomer. 6. The antireflection film according to claim 1, wherein the fluorine-containing polymer has a functional group capable of covalently bonding to the organosilane. 7. The antireflection film according to claim 1, wherein the transparent support is triacetyl cellulose, polyethylene terephthalate, polyethylene naphthalate, ARTON or ZEONEX. 8. The transparent support is a triacetylcellulose film, and a triacetylcellulose dope adjusted by dissolving triacetylcellulose in a solvent is cast in a single layer, co-cast in a plurality of layers, or successively in a plurality of layers. The antireflection film according to any one of claims 1 to 7, wherein the antireflection film is manufactured by casting by any casting method. 9. The triacetylcellulose dope is prepared by dissolving triacetylcellulose in a solvent substantially free of dichloromethane by a cooling dissolution method or a high-temperature dissolution method. The antireflection film according to claim 8, wherein 10. A polarizing plate, wherein the antireflection film according to claim 1 is used for at least one of two protective films of a polarizing layer in the polarizing plate. 11. A liquid crystal display device comprising the antireflection film according to claim 1 or the antireflection layer of the polarizing plate according to claim 10 as the outermost layer of a display.