JP2002071904A - Glare-proof antireflection film and liquid crystal display - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a glare-proof antireflection film having both uniformity in the surface state and various performances such as antireflection performance, antifouling property, scuffing resistance and clearness of a transmitted image and obtained by an all-wet coating method and to provide a liquid crystal display excellent in contrast, visibility, image sharpness, etc., and also having good uniformity in the surface state. SOLUTION: The glare-proof antireflection film 1 has a transparent substrate 2, at least one low refractive index layer 5 and a glare-proof layer 4 between the substrate 2 and the low refractive index layer 5. The substrate 2 is a triacetylcellulose film comprising plural layers. A polarizing plate using the glare-proof antireflection film and a liquid crystal display are provided.

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 an antiglare property and a liquid crystal display device using the same.

[0002]

2. Description of the Related Art An antireflection film is generally used for CRT, P
In an image display device such as a DP or an LCD, it is disposed on the outermost surface of a display that uses a principle of optical interference to reduce the reflectance in order to prevent a decrease in contrast and reflection of an image due to reflection of external light.

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 in order to reduce the reflectance. For example, an antireflection film using triacetyl cellulose as a support and a UV cured film of dipentaerythritol hexaacrylate as a hard coat layer has a refractive index of 1 to obtain an average reflectance at 450 to 650 nm of 1.6% or less. .40 or less. Materials having a refractive index of 1.40 or less include inorganic compounds such as fluorine compounds such as magnesium fluoride and calcium fluoride, and organic compounds such as fluorine-containing compounds having a large fluorine content. The film disposed on the outermost surface 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.

In Japanese Patent Application Laid-Open No. Hei 7-287102, the refractive index of the hard coat layer is increased,
It is described that the reflectance is reduced. However, such a high-refractive-index hard coat layer has a large difference in refractive index from the support, so that color unevenness of the film occurs, and the wavelength dependence of the reflectivity also has a large amplitude. Also, JP-A-7-333404 describes an antiglare antireflection film having excellent gas barrier properties, antiglare properties, and antireflection properties. However, since a silicon oxide film formed by CVD is indispensable,
The productivity is inferior to the wet coating method of forming a film by applying a coating liquid. Further, the antireflection properties of the antiglare antireflection film thus obtained were not satisfactory.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to achieve both antireflection properties, antifouling properties, scratch resistance, and clearness of a transmitted image, as well as surface uniformity, and to obtain an all-wet coating method. To provide an anti-glare anti-reflection film. Another object of the present invention is to provide a liquid crystal display device which is excellent in contrast, visibility, image clarity, etc., and has good surface uniformity.

[0006]

Means for Solving the Problems The present inventors have found that all-wet coating provides excellent antireflection properties, antifouling properties, scratch resistance and clearness of a transmitted image, and minimizes surface unevenness during wet coating. In order to obtain an antiglare antireflection film having excellent surface uniformity by pressing, it is preferable to use a transparent support having excellent smoothness, and in particular, a transparent substrate used for an antiglare layer having excellent transmission image clarity. The present inventors have found that a high smoothness is required for the support, and have reached the present invention. That is, according to the present invention, an antiglare antireflection film, a polarizing plate and a liquid crystal display having the following constitutions are provided, and the above object is achieved. 1. In an antiglare antireflection film having a transparent support and at least one low refractive index layer and an antiglare layer between the support and the low refractive index layer, the transparent support is composed of a plurality of layers An antiglare antireflection film, which is a triacetyl cellulose film. 2. A triacetylcellulose film composed of a plurality of layers, a film containing a high concentration of triacetylcellulose and a film containing a low concentration of triacetylcellulose on both sides of the solution. 2. The antiglare antireflection film according to the above item 1, wherein 3. An antiglare antireflection film comprising a transparent support and at least one low refractive index layer on one surface thereof and an antiglare layer between the support and the low refractive index layer, wherein the low refractive index layer of the transparent support And a surface on the side on which the anti-glare layer is provided is a triacetyl cellulose film having a specific pitch, and having no surface unevenness having a height of 1 / 10,000 or more of the pitch. Anti-glare anti-reflection film. 4. The antiglare antireflection film according to the above item 3, wherein the specific pitch is 3 to 10 mm. 5. The low refractive index layer is composed of a cured product of a thermosetting or ionizing radiation curable fluorine-containing resin and ultrafine particles of oxide of Si, and has a refractive index of 1.45 or less. The antiglare antireflection film according to any one of the above. 6. The binder of the antiglare layer is a mixture of at least one metal oxide ultrafine particle selected from zirconium, titanium, aluminum, indium, zinc, tin, and antimony and a trifunctional or higher (meth) acrylate monomer. It is a cured product of heat or ionizing radiation and has a refractive index of 1.
The above-mentioned item 1 is characterized by being in the range of 57 to 2.00.
5. The antiglare antireflection film according to any one of 5. 7. 7. The anti-glare according to the above item 6, wherein the binder of the anti-glare layer is an ultraviolet cured product of a composition containing ultrafine particles of zirconium oxide and a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate. Anti-reflective film. 8. 8. The antiglare antireflection film according to any one of the above items 1 to 7, wherein the antiglare layer contains crosslinked polystyrene as mat resin particles. 9. A polarizing plate, wherein the antiglare antireflection film according to any one of the above 1 to 8 is used for at least one of two protective films of a polarizing layer in the polarizing plate. 10. 9. A liquid crystal display device, wherein the anti-glare anti-reflection film according to any one of 1 to 8 or the anti-reflection layer of the polarizing plate according to 9 is used as the outermost layer of a display.

[0007]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The basic structure of the antiglare antireflection film of the present invention will be described with reference to the drawings. The embodiment shown in FIG. 1 is an example of the antiglare antireflection film of the present invention. The antiglare antireflection film 1 includes a transparent support 2 made of triacetyl cellulose, a hard coat layer 3, an antiglare layer 4, Further, the low refractive index layer 5 has a layer configuration in the order. Matt particles 6 are dispersed in the antiglare layer 4. The refractive index of the low refractive index layer 5 is preferably in the range of 1.38 to 1.49. The hard coat layer 3 is not necessarily required, but is preferably applied to impart film strength.

[Transparent support] As the transparent support used in the antiglare antireflection film of the present invention, a triacetyl cellulose film composed of a plurality of layers is used. The preferred number of layers is 3 to 5 layers, particularly preferably 3 layers. Such a triacetyl cellulose film comprising a plurality of layers is disclosed in JP-A-61-94725, JP-B-62-43846 and the like, and can be prepared by a so-called co-casting method. That is, raw flakes of triacetyl cellulose are converted into halogenated hydrocarbons (eg, dichloromethane), alcohols (eg, methanol, ethanol, butanol), esters (eg, methyl formate, methyl acetate), and ethers (eg, dioxane, dioxolan, and diethyl ether). Dissolved in a solvent such as a plasticizer, an ultraviolet absorber, a deterioration inhibitor,
A solution containing various additives such as a slipping agent and a peeling accelerator (hereinafter referred to as “dope”) is placed on a horizontal endless metal belt or a substrate composed of a rotating drum, and supplied to a dope supply unit (hereinafter referred to as “dope”). (Referred to as "die") when co-casting a low-concentration dope on both sides of a high-concentration triacetylcellulose dope, peeling a film which has been dried to some extent on the substrate and imparted rigidity from the substrate, and This is a method comprising removing the solvent by passing through a drying step by various transporting means.

[0009] The triacetylcellulose film produced by this method is characterized in that the low concentration dope is co-cast on both sides of the high concentration triacetylcellulose dope, so that the film surface has excellent smoothness and productivity. By using such a support, streak-like coating unevenness due to poor flatness of the support caused when the antiglare layer of the antiglare antireflection film of the present invention is wet-coated is significantly improved, and is excellent. In addition, an antiglare antireflection film having both a clear transmitted image and a uniform surface state during wet application can be obtained. In addition, the triacetyl cellulose film prepared by the above method is composed of a plurality of layers, but there is no clear interface between the layers, and each layer forms a continuous layer, and reflection between the interfaces and the like. Does not cause optical loss.

[0010] The triacetyl cellulose film produced by the above method has particularly improved surface irregularities in the width direction, and has a great effect of improving unevenness in the width direction when an upper layer is formed by wet application. Such smoothness in the width direction can be evaluated over a wide measurement range (up to about several centimeters to ten centimeters) of the surface unevenness of each pitch component by measuring surface displacement by a laser displacement meter described later. The triacetylcellulose films prepared by various methods were subjected to such an evaluation.Anti-glare layers, surface defects occurring when providing a low-refractive-index layer, and in particular, thickness unevenness in the width direction. It has been clarified that the lower the height of the surface irregularities at a pitch of 3 to 10 mm, the better against the streak-like failure that occurs continuously in the longitudinal direction.
By the above method, a support having a low surface unevenness at a pitch of 3 to 10 mm can be obtained. In particular, it is possible not to include surface irregularities having a height of 1 / 10,000 or more of the pitch. If necessary, a hard coat layer, an antiglare layer and a low refractive index layer as essential layers are sequentially formed to obtain an antiglare antireflection film with less planar failure such as streak failure. it can. Here, the pitch is a horizontal distance between adjacent protrusions of the surface unevenness.

When the antiglare antireflection film of the present invention is used for a liquid crystal display device, it is arranged on the outermost surface of the display by providing an adhesive layer on one side. Since triacetyl cellulose is used for a protective film for protecting a polarizing layer of a polarizing plate, it is more preferable to use the antiglare antireflection film of the present invention as it is for a protective film. In order to use the protective film as a protective film for the polarizing layer, it is preferable to saponify the protective film from the viewpoint of adhesiveness. Since the antiglare antireflection film of the present invention has saponification resistance, it can be subjected to a saponification treatment immediately before lamination to a protective film. The saponification treatment may be performed directly on the triacetyl cellulose film, after forming the hard coat layer, or after forming the antiglare layer, but from the viewpoint of productivity, it is performed after forming all the layers. Is preferred.

[Hard Coat Layer] In the antireflection film of the present invention, a hard coat layer may be provided between the transparent support and the antiglare layer, if necessary, for the purpose of improving the film strength. The 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.

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 diester). Acrylate, pentaerythritol tetra (meth) acrylate), pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethanetri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,3,5-
Cyclohexanetriol trimethacrylate, polyurethane polyacrylate, polyester polyacrylate), vinylbenzene derivatives (eg, 1,4-divinylbenzene, 4-vinylbenzoic acid-2-acryloylethyl ester, 1,4-divinylcyclohexanone), vinyl sulfone (Eg, divinyl sulfone), acrylamide (eg, methylenebisacrylamide) and methacrylamide. Among these, a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate is commercially available, and is particularly preferably used.

These monomers having an ethylenically unsaturated group need to be dissolved in a solvent together with various polymerization initiators and other additives, applied, dried, and then cured by a polymerization reaction using ionizing radiation or heat.

[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. That is, the crosslinkable functional group is not limited to the above-mentioned functional group, but may be one that shows reactivity as a result of decomposition of the functional group. These compounds having a cross-linking group need to be cross-linked by heat or the like after coating.

[Anti-glare layer] The material of the binder portion forming the anti-glare layer of the present invention preferably has a refractive index of 1.57 to 2.00.
And more preferably 1.60 to 1.80. The material forming the low refractive index layer preferably has a refractive index of 1.38.
~ 1.49. The refractive index of triacetyl cellulose used as a transparent support is 1.48. If the refractive index of the binder forming the anti-glare layer is too small, the anti-reflection property will decrease. Further, if this is too large, the tint of the reflected light of the antiglare antireflection film becomes strong, which is not preferable.
The antireflection property is such that the refractive index of the low refractive index layer is 1.38 to
The lower the value is between 1.49, the better, but the color of the reflected light becomes stronger.

The haze value of the antiglare layer is preferably 5 to 15
%. Although the antiglare property and the haze value do not always correspond linearly, if the haze value is less than 5%, an antiglare film having sufficient antiglare property cannot be obtained. On the other hand, when the haze value is larger than 15%, scattering on the surface and inside is too strong, which causes problems such as deterioration of image clarity and whitening, which is not preferable. Further, in the antiglare layer, light scattering due to surface irregularities occurs due to mat particles dispersed in the high refractive index material, and therefore, there is no influence of optical interference in the antiglare layer.
In the high refractive index hard coat layer having no matte particles, a large amplitude of the reflectance is seen in the wavelength dependence of the reflectance due to the optical interference due to the refractive index difference between the hard coat layer and the support. Although the prevention effect deteriorates and color unevenness occurs at the same time, in the antiglare antireflection film of the present invention, these problems do not occur due to the scattering effect due to the surface unevenness of the antiglare layer.

The compound forming the antiglare layer contains, in addition to the material forming the hard coat layer, a monomer having a high refractive index or ultrafine metal oxide particles having a high refractive index. Examples of the high refractive index monomer include bis (4-methacryloylthiophenyl) sulfide, vinylnaphthalene, vinylphenylsulfide, 4-methacryloxyphenyl-4′-methoxyphenylthioether and the like.
Examples of metal oxide ultrafine particles having a high refractive index, zirconium, titanium, aluminum, indium, zinc,
A particle size of 100 nm or less, preferably 5 particles, made of an oxide of at least one metal selected from tin and antimony.
Fine particles of 0 nm or less can be mentioned. Preferred examples of the fine particles include ZrO ₂ , TiO ₂ , Al ₂ O ₃ , and In.
Examples include ₂ O ₃ , ZnO, SnO ₂ , Sb ₂ O ₃ , and ITO. Among these, ZrO ₂ is particularly preferably used. The addition amount of the inorganic fine particles is preferably 10 to 90% by weight based on the total weight of the hard coat layer, and is preferably 20 to 80% by weight.
It is more preferred that the content is% by weight.

For the anti-glare layer, transparent mat resin particles are used for the purpose of imparting anti-glare properties, preventing deterioration in reflectance due to interference of the hard coat layer, and preventing color unevenness. The average particle size of the mat particles is 1.0 to 5.0 as a number average particle size by a Coulter method.
μm is preferable, and 1.7 to 3.5 μm is more preferable.
If this is less than 1.0 μm, the anti-glare property is insufficient and 5.0 μm
If it exceeds, the clearness of a transmitted image is degraded. The particle size distribution of the mat resin particles is such that the standard deviation of the particle size is 2 times the number average particle size.
It is preferably at most 5%. If this exceeds 25%, the coating form of the binder on each resin particle becomes non-uniform, and desired surface irregularities cannot be formed. In addition, the ratio of coarse particles whose particle diameter is larger than the number average particle diameter by 3.0 μm or more or coarse particles larger than the number average particle diameter by 2.5 times or more may be less than 5/1 × 10 ^8. preferable.
Such coarse particles, in the anti-glare anti-reflection film of the present invention, because it becomes the core of a bumpy planar failure,
Desirably, it is not included at all. If the number is 5/1 × 10 ⁸ or more, the number of bumpy defects per 1 m ² exceeds an allowable level, and the production yield of the antiglare antireflection film of the present invention is unfavorably deteriorated. As the mat resin particles used for the antiglare layer, crosslinked polystyrene particles are preferably used from the viewpoints of particle size distribution and refractive index.

[Low Refractive Index Layer] The low refractive index layer of the antiglare antireflection film preferably satisfies the following formula (I). (Mλ / 4) × 0.7 <n ₁ d ₁ <(mλ / 4) × 1.3 (Formula (I)) In the formula, m is a positive odd number (generally 1), and n ₁ is low refraction. Is the refractive index of the refractive index layer, and d ₁ is the thickness (nm) of the low refractive index layer. Further, λ is a set wavelength of the antireflection layer, and is a value in a range of 500 to 525 (nm). In addition,
Satisfying the formula (I) means that m (a positive odd number, usually 1) that satisfies the formula (I) exists in the wavelength range.

The low refractive index layer is made of a cured product of a thermosetting fluorine-containing compound or an ionizing radiation-curable fluorine compound. The dynamic friction coefficient of the cured product is preferably 0.03 to 0.03.
0.15, contact angle with water is preferably 90-120
Degrees. As the curable fluorine-containing polymer compound, in addition to a perfluoroalkyl group-containing silane compound (for example, (heptadecafluoro-1,1,2,2-tetradecyl) triethoxysilane), a fluorine-containing monomer and a crosslinkable group are provided. And a fluorine-containing copolymer having a monomer as a structural unit. Specific examples of the fluorine-containing monomer unit include, for example, fluoroolefins (for example, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, hexafluoroethylene, hexafluoropropylene, perfluoro-2,2-dimethyl-1,3-dioxole and the like) ), Partially or fully fluorinated alkyl ester derivatives of (meth) acrylic acid (eg, 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 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, a monomer having a carboxyl group, a hydroxyl group, an amino group, a sulfonic acid group, etc. ) Acrylate monomers (for example, (meth) acrylic acid, methylol (meth) acrylate, hydroxyalkyl (meth) acrylate, allyl acrylate, etc.). It is disclosed in JP-A-10-25388 and JP-A-10-147739 that the latter can introduce a crosslinked structure after copolymerization.

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

The fluorine-containing resin used for forming the low-refractive-index layer is preferably used by adding ultrafine particles of Si oxide to impart scratch resistance. From the viewpoint of antireflection properties, the lower the refractive index, the better. However, the lower the refractive index of the fluororesin, the worse the scratch resistance. Thus, by optimizing the refractive index of the fluorine-containing resin and the amount of the ultrafine particles of Si oxide, the best balance between the scratch resistance and the low refractive index can be found. As Si oxide ultrafine particles,
The silica sol dispersed in a commercially available organic solvent may be directly added to the coating composition, or various commercially available silica powders may be dispersed in an organic solvent and used.

[Formation of Each Layer] 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.
681294) can be formed by coating. Two or more layers may be applied simultaneously. For the method of simultaneous coating, see U.S. Pat. Nos. 2,761,791; 2,918,898; 3,508,947;
No. 28 and in Yuji Harazaki, Coating Engineering, page 253, Asakura Shoten (1973).

[Liquid Crystal Display Device and Polarizing Plate] The antiglare antireflection film of the present invention comprises a liquid crystal display device (LCD), a plasma display panel (PDP), an electroluminescent display (ELD), and a cathode ray tube display device (C).
RT) and the like. The antiglare antireflection film of the present invention is used by adhering the transparent support side to the image display surface of an image display device. When applied to the surface or inner surface of an LCD, it protects the polarizing layer of the polarizing plate. More preferably, it is used as it is as a film on one side of the protective film.

[0026]

EXAMPLES The present invention will be described in detail with reference to the following examples, but the present invention is not limited to these examples.

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

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

(Preparation of Coating Solution for Antiglare Layer) 91 g of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.), ultrafine zirconium oxide dispersion having a particle size of about 30 nm Containing hard coat coating solution (Desolite Z
-7041 (manufactured by JSR Corp.), 199 g, and a hard coat coating solution containing a zirconium oxide ultrafine particle dispersion having a particle size of about 30 nm (Desolite Z-7042, JSR Corp.)
Was dissolved in 52 g of a mixed solvent of methyl ethyl ketone / cyclohexanone = 54/46% by weight. To the obtained solution, 10 g of a photopolymerization initiator (Irgacure 907, manufactured by Ciba Fine Chemicals Co., Ltd.) was added. The refractive index of the coating film obtained by applying this solution and curing with ultraviolet light was 1.61. Further, the number average particle size of the solution was 1.
Crosslinked polystyrene particles having a particle diameter of 99 μm and a standard deviation of the particle diameter of 0.32 μm (16% of the number average particle diameter) (trade name: SX-2)
20HS (manufactured by Soken Chemical Co., Ltd.) was stirred and dispersed in 80 g of a mixed solvent of methyl ethyl ketone / cyclohexanone = 54/46% by weight at 5000 rpm for 1 hour with a high-speed disperser, and a polypropylene filter (pore size: 10 μm, 3 μm, 1 μm) PPE-10, PPE-0
3, PPE-01, both Fuji Photo Film Co., Ltd.
Was added, and the mixture was stirred and filtered through a polypropylene filter having a pore size of 30 μm to prepare a coating solution for an antiglare layer.

(Preparation of Coating Solution for Hard Coat Layer) An ultraviolet-curable hard coat composition (Desolite Z-7526,
A solution prepared by dissolving 250 g of 72% by weight (manufactured by JSR Corporation) in 62 g of methyl ethyl ketone and 88 g of cyclohexanone was added. The refractive index of the coating film obtained by applying this solution and curing with ultraviolet light was 1.50. Further, this solution was added to a polypropylene filter having a pore size of 30 μm (PP
E-30) to give a coating solution for the hard coat layer.

(Preparation of Coating Solution for Low Refractive Index Layer) Refractive index
42 crosslinkable fluorine-containing polymer (JN-7228, J
MEK-ST (average particle size of 10 to 93 g)
ME of SiO2 sol with 20 nm and solid content concentration of 30% by weight
K dispersion, 8 g of Nissan Chemical Co., Ltd.) and 100 g of methyl ethyl ketone were added, and after stirring, the mixture was filtered through a polypropylene filter (PPE-01) having a pore size of 1 μm.
A coating solution for a low refractive index layer was prepared.

Example 1 According to Japanese Patent Application Laid-Open No. H11-254594 and the like, a three-layer co-casting die is used, and a dope A is arranged on both sides of a dope B so as to be co-cast and discharged simultaneously onto a metal drum. Then, the casting film was peeled off from the drum, dried, and dried at 10 μm, 60 μm from the drum surface side.
A three-layer co-cast triacetyl cellulose film of 10 μm and 10 μm was prepared. In this film, no clear interface was formed between the layers. When the above-mentioned triacetyl cellulose film was measured for displacement in the width direction of the film surface by a measuring method using a laser displacement meter described later, as shown in FIG. None were more than 1 / 10,000 of the pitch. The above-mentioned coating solution for a hard coat layer is applied to the above-mentioned triacetyl cellulose film using a bar coater, dried at 120 ° C., and then cooled with a 160 W / cm air-cooled metal halide lamp (Eye Graphics Co., Ltd.)
Illuminance 400 mW / cm ² , irradiation amount 300
The coating layer was cured by irradiating ultraviolet rays of mJ / cm ² to form a hard coat layer having a thickness of 2.5 μm. in addition,
The anti-glare layer coating solution was applied using a bar coater, dried under the same conditions as the hard coat layer, and cured by ultraviolet light.
An anti-glare layer having a thickness of about 1.5 μm was formed. The coating liquid for a low refractive index layer was applied thereon using a bar coater, and
After drying at 0 ° C., thermal crosslinking was further performed at 120 ° C. for 8 minutes to form a low refractive index layer having a thickness of 0.096 μm.

[Comparative Example 1] A single-layer cast triacetyl cellulose film was prepared in the same manner as in Example except that dope B was a single layer having a thickness of 80 µm. When the above triacetyl cellulose film was measured for displacement in the width direction of the film surface by a laser displacement meter, as shown in FIG.
There were many irregularities of about 0.4 μm. A hard coat layer, an antiglare layer, and a low refractive index layer were formed on the above-mentioned triacetyl cellulose film in the same manner as in the examples, to prepare an antiglare antireflection film.

[Comparative Example 2] A hard coat coating solution containing a zirconium oxide ultrafine particle dispersion in a coating solution for an antiglare layer was mixed with DPHA having the same solid content concentration in a mixed solvent of 50 parts by weight / 50 parts by weight of methyl ethyl ketone / cyclohexanone. The solution was replaced with a dissolved solution, and the low refractive index layer coating solution MEK-ST (SiO 2 having an average particle diameter of 10 to 20 nm and a solid concentration of 30% by weight) was used.
An antiglare antireflection film was prepared in the same manner as in Comparative Example 1 except that the _2- sol MEK dispersion (manufactured by Nissan Chemical Co., Ltd.) was not added, and the solid concentration was adjusted to the coating solution for the low refractive index layer. Created.

(Evaluation of Surface Displacement of Transparent Support) The smoothness of the transparent support prepared by each casting method was evaluated by the following method. From each transparent support, 17
A sample having a size of 0 mm and a size of 4 mm in the casting direction was cut out, and both ends were fixed to an acrylic plate and fixed using a laser displacement meter (KL130A, manufactured by Anritsu Corporation) with a measurement range of 135 mm and a measurement interval of 100 μm. A mask was provided in the laser light receiving portion so that only surface reflection could be measured under the conditions described above, and the surface displacement was captured as two-dimensional coordinate data. Subsequently, in order to remove the waviness component due to the deflection of the base film, the center line of the two-dimensional coordinate data is set as a curve obtained by fitting the two-dimensional coordinate data curve with a 7th order equation, and the two-dimensional coordinate data Displacement up and down from the center line was expressed as plus and minus, respectively, and the surface displacement of the film at each position was graphed. From such a graph, the height of the surface irregularities having a pitch of 3 to 10 mm was read, and the ratio of the height to the pitch was calculated.

(Evaluation of antireflection film)
Then, the following items were evaluated. (1) Specular reflectance Adapter for spectrophotometer V-550 (manufactured by JASCO Corporation)
-Waves of 380-780nm with ARV-474
In the long region, a mirror with an exit angle of -5 degrees at an incident angle of 5 degrees
The surface reflectance is measured, and the average reflectance of 450 to 650 nm is determined.
It was calculated and the antireflection property was evaluated. (2) Visibility of transmitted image Using image clarity measuring instrument ICM-1 (manufactured by Suga Test Instruments Co., Ltd.)
The transmitted image clarity at an optical comb width of 0.5 mm is represented by n =
The measurement was performed at 3, and the arithmetic mean value was obtained. (3) Evaluation of antiglare properties Exposed fluorescence without louvers on the prepared antiglare film
Light (8000 cd / m ^Two) And the reflection image is blurred
The degree was evaluated in four steps based on the following criteria. ◎: The outline of the fluorescent lamp is completely unknown. ○: The outline of the fluorescent lamp is slightly recognized. △: The fluorescent lamp is blurred, but the outline is discernable. ×: The fluorescent lamp is hardly blurred. The surface opposite to the surface where the body coating layer is provided is black with black ink
Paint, inspect visually with the coated side up,
The evaluation was made in three steps. ：: No streak-like unevenness is observed at all. △: Streak-like unevenness is slightly observed. ×: Streak-like unevenness is clearly seen.
10 reciprocating rubs, scoring was evaluated on a 4-point scale based on the following criteria
Was. ◎: No scratch at all ○: Slight scratch but not noticeable △: Scratch but low refractive index layer remains ×: Scratch at full width

Table 1 shows the results of Examples and Comparative Examples.
Example 1 shows no streak-like coating unevenness due to poor smoothness of the support, excellent transmission image clarity, a good balance of reflectance and antiglare properties, and a very high display quality. there were. In Comparative Example 1, the transparent support was different from that of the example, and as a result of using a single-layer transparent support, the smoothness was insufficient. Was. In Comparative Example 2, in addition to using the single-layer transparent support and not incorporating the SiO ₂ fine particles in the low refractive index layer, the average reflectance was deteriorated in addition to the stripe-shaped coating unevenness. Furthermore, the scratch resistance deteriorated as the steel wool was easily scratched by rubbing.

[0038]

[Table 1]

Example 2 Next, an antiglare antireflection polarizing plate was produced using the film of Example 1. 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, excellent image clarity, and good surface condition.

[0040]

The antiglare antireflection film of the present invention is obtained by an all-wet coating method and is excellent in various properties such as antireflection properties, antifouling properties, scratch resistance, and clearness of a transmitted image, and has a uniform surface. Also excellent in nature. Further, a liquid crystal display device equipped with a polarizing plate using the above excellent anti-glare anti-reflection film,
Since there is no reflection of external light, an excellent contrast is obtained, and a reflected image is not conspicuous due to antiglare properties, has excellent visibility, is excellent in image clarity, and has a good surface condition. The same applies to a liquid crystal display device directly using an antiglare antireflection film.

[Brief description of the drawings]

FIG. 1 is a schematic cross-sectional view schematically showing a layer configuration of an antiglare antireflection film of the present invention.

FIG. 2 is a graph showing a surface displacement of a transparent support in a width direction by a laser displacement meter according to an example.

FIG. 3 is a graph showing a surface displacement of a transparent support of Comparative Example 1 in a width direction by a laser displacement meter.

[Explanation of symbols]

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

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) B32B 27/30 C08F 2/44 A 4F205 C08F 2/44 C 4J011 2/48 4J026 2/48 257/02 257 / 02 C08J 7/04 CEPZ C08J 7/04 CEP G02B 5/30 G02B 1/10 G02F 1/1335 500 5/30 B29K 1:00 G02F 1/1335 500 B29L 9:00 // B29K 1:00 C08L 1: 12 B29L 9:00 G02B 1/10 A C08L 1:12 Z (72) Inventor Hidenori Yamazaki 210 Nakanaka, Minamiashigara-shi, Kanagawa Prefecture Fuji Photo Film Co., Ltd. F-term (reference) 2H049 BA02 BB65 BC22 2H091 FA37X FB02 FB13 FB13 FD23 LA11 LA12 2K009 AA02 AA15 BB28 CC03 CC09 CC24 CC26 CC42 DD02 EE00 EE05 4F006 AA02 AB24 AB54 AB74 BA14 CA05 4F100 AA19C AA19H AA20B A A20H AA21C AA21H AA25C AA25H AA27C AA27H AA28C AA28H AA29C AA29H AJ06A AJ06D AJ06E AK12C AK12H AK17B AK25C AK25J AL05C AR00B AR00C BA04 BA05 BA10A BA10B BA13 BA27 CA23B CA23C DD07E GB41 JB13B JB13C JB14B JB14C JB20C JK09 JL06 JN01A JN01D JN01E JN06 JN18B JN18C JN30C YY00B YY00C YY00E 4F205 AA01 AC05 AG03 AH42 GA07 GB02 GB22 GC02 GE24 GF24 4J011 PA04 PA65 PB22 PC02 QA23 QA24 SA00 UA01 4J026 AA17 BA28 BB03 GA07

Claims (10)

[Claims] 1. An antiglare antireflection film comprising a transparent support, at least one low refractive index layer, and an antiglare layer between the support and the low refractive index layer, wherein the transparent support comprises a plurality of layers. An antiglare antireflection film, which is a triacetylcellulose film composed of: 2. A triacetylcellulose film composed of a plurality of layers co-casts a solution containing a high concentration of triacetylcellulose and a solution containing a low concentration of triacetylcellulose on both sides thereof. The anti-glare anti-reflection film according to claim 1, wherein the anti-reflection film is a film produced by: 3. An antiglare antireflection film comprising a transparent support, at least one low refractive index layer on one surface thereof, and an antiglare layer between the support and the low refractive index layer, wherein: The surface on the side where the low refractive index layer and the antiglare layer are provided has a specific pitch,
An antiglare antireflection film, which is a triacetylcellulose film having a height of 1/0000 or more and containing no surface irregularities. 4. The antiglare antireflection film according to claim 3, wherein the specific pitch is 3 to 10 mm. 5. The low-refractive-index layer comprises a thermosetting or ionizing radiation-curable cured product of a fluorine-containing resin and Si oxide ultrafine particles, and has a refractive index of 1.45 or less. The antiglare antireflection film according to claim 1. 6. The binder of the anti-glare layer comprises ultrafine particles of an oxide of at least one metal selected from zirconium, titanium, aluminum, indium, zinc, tin and antimony and trifunctional or higher functional (meth) acrylate. The antiglare antireflection film according to any one of claims 1 to 5, which is a heat or ionizing radiation cured product of a mixture with a monomer, and has a refractive index in a range of 1.57 to 2.00. . 7. The ultraviolet-cured product of a composition containing ultrafine particles of zirconium oxide and a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, wherein the binder of the anti-glare layer is provided. 7. The antiglare antireflection film according to 6. 8. The anti-glare anti-reflection film according to claim 1, wherein the anti-glare layer contains crosslinked polystyrene as mat resin particles. 9. A polarizing plate, wherein the antiglare antireflection film according to claim 1 is used for at least one of two protective films of a polarizing layer in a polarizing plate. 10. A liquid crystal display, wherein the anti-glare anti-reflection film according to claim 1 or the anti-reflection layer of the polarizing plate according to claim 9 is used as the outermost layer of a display. apparatus.