JP5210748B2 - Method for producing antiglare antireflection film - Google Patents

Description

  The present invention relates to a method for producing an antireflection film having antiglare properties, an antiglare antireflection film, a polarizing plate using the same, and a liquid crystal display device.

  Anti-reflection films generally prevent contrast degradation and image reflection due to reflection of external light in image display devices such as cathode ray tube display devices (CRT), plasma display panels (PDP), and liquid crystal display devices (LCD). In order to do this, it is placed on the outermost surface of the display that reduces the reflectivity using the principle of optical interference.

  However, in the antireflection film having only the hard coat layer and the low refractive index layer on the transparent support, the low refractive index layer must be sufficiently lowered in order to reduce the reflectance. For example, in order to reduce the average reflectance in the range of 450 nm to 650 nm with an antireflective film having triacetylcellulose as a support and a UV-coated film of dipentaerythritol hexaacrylate as a hard coat layer to 1.6% or less, The refractive index must be 1.40 or less. Examples of materials having a refractive index of 1.40 or less include fluorine-containing compounds such as magnesium fluoride and calcium fluoride for inorganic materials, and fluorine-containing compounds having a high fluorine content for organic materials. These fluorine-containing compounds have cohesive strength. Therefore, the film placed on the outermost surface of the display was insufficient in scratch resistance. Therefore, in order to have sufficient scratch resistance, a compound having a refractive index of 1.43 or more is 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, since such a high refractive index hard coat layer has a large difference in refractive index from the support, color unevenness of the film occurs, and the wavelength dependence of the reflectance also greatly increases.

  Japanese Patent Application Laid-Open No. 7-333404 describes an antiglare antireflection film excellent in gas barrier properties, antiglare properties and antireflection properties. However, since a silicon oxide film by a CVD method is essential, a coating liquid is used. It is inferior in productivity as compared with the wet coating method in which a film is formed by coating.

  Japanese Patent Publication No. 6-98703 and Japanese Patent Laid-Open No. 63-21601 disclose a technique for reducing reflected light by applying a composition comprising a hydrolyzed partial condensate of an alkoxysilane compound to the surface of a plastic substrate. Has been. In the techniques described in these publications, an inorganic film is obtained by a wet coating method by a sol-gel method. Although it is an inorganic film, it is expected to have a very high film strength. However, the inorganic film generally has poor adhesion to many substrates, and has a drawback that a peeling failure is likely to occur. Furthermore, heating for a long time is indispensable for curing, and there is a disadvantage that productivity is poor.

JP 7-287102 A JP 7-333404 A Japanese Examined Patent Publication No. 6-98703 Japanese Patent Laid-Open No. 63-21601

  The object of the present invention is to produce an antiglare hard coat layer and a low refractive index layer on a support, which can be easily and inexpensively manufactured, and have sufficient antireflection performance, scratch resistance, and antifouling properties. It is in providing the anti-glare antireflection film which has the property. Another object of the present invention is to provide a polarizing plate and a liquid crystal display device that are sufficiently prevented from reflecting external light and that have excellent antifouling properties and scratch resistance.

According to this invention, the manufacturing method of the anti-glare antireflection film of the following structure is provided, and the said objective is achieved.
<1>
A method for producing an antiglare antireflection film having an antiglare hard coat layer and a low refractive index layer having a refractive index of 1.35 to 1.49 in this order on a transparent substrate,
The low refractive index layer is formed from a composition containing at least one of hydrolyzate of organosilane and partial condensate thereof,
Applying and curing an antiglare hard coat layer on a transparent substrate; and
A method for producing an antiglare antireflection film comprising a step of subjecting an antiglare hard coat layer to an alkali treatment.
<2>
The method for producing an antiglare and antireflection film according to <1>, wherein the alkali concentration of the aqueous alkali solution used for the alkali treatment is 0.1 to 25% by weight.
<3>
The method for producing an antiglare antireflection film according to <1> or <2>, wherein the temperature in the alkali treatment is 10 to 80 ° C.
<4>
The method for producing an antiglare antireflection film according to any one of the above <1> to <3>, which comprises a step of washing with water and coating a low refractive index layer after alkali treatment.
<5>
The method for producing an antiglare and antireflection film according to any one of <1> to <4>, wherein the transparent substrate is triacetylcellulose.
<6>
The refractive index of the film formed by removing the particles having an average particle diameter of 1 to 10 μm from the composition for forming the antiglare hard coat layer, wherein the antiglare hard coat layer contains particles having an average particle diameter of 1 to 10 μm. Is a manufacturing method of the anti-glare antireflection film described in any one of the above items <1> to <5> in the range of 1.57 to 2.00.
<7>
The method for producing an antiglare antireflection film according to any one of the above <1> to <6>, wherein the film thickness of the antiglare hard coat layer is 1 to 10 μm.
<8>
The antiglare property according to any one of the above <1> to <7>, wherein the antiglare hard coat layer contains silica particles having an average particle diameter of 1 to 10 μm and an inorganic compound. A method for producing an antireflection film.
<9>
<1> to <7>, wherein the antiglare hard coat layer contains at least one kind of resin particles of crosslinked acrylic particles, crosslinked styrene particles, melamine resin particles, and benzoguanamine resin particles having an average particle diameter of 1 to 10 μm. The manufacturing method of the anti-glare antireflection film of any one of these.
<10>
The method for producing an antiglare antireflection film according to any one of <1> to <9>, wherein the low refractive index layer has a thickness of 0.05 to 0.2 μm.
The present invention relates to the above <1> to <10>, but other matters (for example, items described in the following 1 to 11) are also described for reference.
1. A method for producing an antiglare antireflection film having an antiglare hard coat layer and a low refractive index layer having a refractive index of 1.35 to 1.49 in this order on a transparent substrate,
Applying and curing an antiglare hard coat layer on a transparent substrate; and
A method for producing an antiglare antireflection film comprising a step of subjecting an antiglare hard coat layer to an alkali treatment.
2. 2. The method for producing an antiglare antireflection film as described in 1 above, wherein the alkali concentration of the aqueous alkali solution used for the alkali treatment is 0.1 to 25% by weight.
3. 3. The method for producing an antiglare antireflection film as described in 1 or 2 above, wherein the temperature in the alkali treatment is 10 to 80 ° C.
4). 4. The method for producing an antiglare antireflection film according to any one of the above 1 to 3, which comprises a step of washing with water and coating a low refractive index layer after alkali treatment.
5. 5. The method for producing an antiglare antireflection film according to any one of 1 to 4 above, wherein the transparent substrate is triacetylcellulose.
6). The refractive index of the film formed by removing the particles having an average particle diameter of 1 to 10 μm from the composition for forming the antiglare hard coat layer, wherein the antiglare hard coat layer contains particles having an average particle diameter of 1 to 10 μm. The manufacturing method of the anti-glare antireflection film in any one of said 1-5 which exists in the range of 1.57-2.00.
7). The method for producing an antiglare antireflection film according to any one of 1 to 6 above, wherein the film thickness of the antiglare hard coat layer is 1 to 10 μm.
8). The method for producing an antiglare antireflection film according to any one of the above 1 to 7, wherein the antiglare hard coat layer contains at least one kind of particles of silica particles and an inorganic compound having an average particle diameter of 1 to 10 μm. .
9. Any one of the above 1 to 7 containing at least one kind of resin particles of crosslinked acrylic particles, crosslinked styrene particles, melamine resin particles, and benzoguanamine resin particles having an average particle diameter of 1 to 10 μm in the antiglare hard coat layer The manufacturing method of the anti-glare antireflection film of description.
10. 10. The method for producing an antiglare antireflection film according to any one of 1 to 9 above, wherein the low refractive index layer has a thickness of 0.05 to 0.2 μm.
11. 11. The antiglare antireflection film as described in any one of 1 to 10 above, wherein the low refractive index layer is formed from a composition containing at least one of hydrolyzate of organosilane and partial condensate thereof. Manufacturing method.

  The production method of the antiglare antireflection film of the present invention has high antireflection performance, excellent antifouling properties and scratch resistance, and can be produced 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 antiglare antireflection film are excellent in antifouling property and scratch resistance in addition to sufficiently preventing reflection of external light.

  A basic configuration of an antiglare antireflection film suitable as an embodiment of the present invention will be described with reference to the drawings. The embodiment schematically shown in FIG. 1 is an example of the antiglare antireflection film of the present invention. In this case, the antiglare antireflection film 1 has a layer structure in the order of a transparent support 2, a hard coat layer 3, an antiglare hard coat layer 4, and a low refractive index layer 5. Particles 6 are dispersed in the antiglare hard coat layer 4. The refractive index of the portion other than the particles 6 of the antiglare hard coat layer 4 is preferably in the range of 1.57 to 2.00, and the refractive index of the low refractive index layer 5 is in the range of 1.35 to 1.49. It is in. The hard coat layer 3 is not necessarily required, but is preferably applied for imparting film strength.

  As the transparent support of the antiglare antireflection film of the present invention, it is preferable to use a plastic film. Polymers that form plastic films include cellulose esters (eg, triacetyl cellulose, diacetyl cellulose), polyamides, polycarbonates, polyesters (eg, polyethylene terephthalate, polyethylene naphthalate), polystyrene, polyolefin, arton (trade name, JSR Corporation) ), Substance name: norbornene-based polyolefin resin), ZEONEX (trade name, manufactured by Nippon Zeon Co., Ltd., substance name: norbornene-based polyolefin resin), and the like. Of these, triacetyl cellulose, polyethylene terephthalate, polyethylene naphthalate, arton, and ZEONEX are preferable, and triacetyl cellulose is particularly preferable. Since triacetyl cellulose is usually used as a protective film for protecting the polarizing layer of the polarizing plate of the liquid crystal display device, the anti-glare reflection when the transparent support of the anti-glare anti-reflection film is a triacetyl cellulose film. The prevention film can be used as it is for the protective film, which is preferable. In this case, the antiglare antireflection film can be disposed as a protective film on the outermost surface of the display of the liquid crystal display device by means such as providing an adhesive layer on one side of the antiglare antireflection film.

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

  The antiglare hard coat layer is preferably a refractive index nonuniform layer in which particles having an average particle size of 1 μm or more are dispersed in a binder polymer. A film formed of a composition composed of components excluding the above-mentioned particles forming the antiglare hard coat layer, that is, a binder polymer or a dispersion in which fine particle components of a metal oxide having a particle size of 100 nm or less are dispersed. The refractive index of the film is preferably 1.57 to 2.00, more preferably 1.60 to 1.80, which is a high refractive index. If this value is too small, the antireflection performance will be small, and if it is too large, the color may be too large.

  In the antiglare hard coat layer, internal scattering of light occurs due to particles having a particle diameter of 1 μm or more dispersed in the high refractive index layer, and therefore, no influence of optical interference in the antiglare hard coat layer occurs. In the high refractive index antiglare hard coat layer having no particle of the above particle size, the reflectivity is dependent on the wavelength dependence of the reflectivity due to optical interference due to the refractive index difference between the antiglare hard coat layer and the support. A large amplitude is seen, resulting in a deterioration of the antireflection effect and at the same time uneven color.

  As the binder polymer, a polymer having a saturated hydrocarbon chain or a polyether chain as a main chain is preferable, and a polymer having a saturated hydrocarbon chain as a main chain is more preferable. The binder polymer preferably has a crosslinked structure. As the binder polymer having a saturated hydrocarbon chain as a main chain, a polymer of an ethylenically unsaturated monomer is preferable. As the binder polymer having a saturated hydrocarbon chain as the main chain and having a crosslinked structure, a (co) polymer of monomers having two or more ethylenically unsaturated groups is preferable. In order to obtain a high refractive index, the monomer structure preferably contains an aromatic ring or at least one atom selected from halogen atoms other than fluorine, sulfur atoms, phosphorus atoms, and 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, trimethylolethane tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, Pentaerythritol hexa (meth) acrylate, 1,2,3-cyclohexanetetramethacrylate, polyurethane polyacrylate, polyester polyacrylate), vinylbenzene and its derivatives ( 1,4-divinylbenzene, 4-vinylbenzoic acid-2-acryloylethyl ester, 1,4-divinylcyclohexanone), vinylsulfone (eg, divinylsulfone), acrylamide (eg, methylenebisacrylamide) and methacrylamide. It is done.

  Specific examples of the high refractive index monomer include bis (4-methacryloylthiophenyl) sulfide, vinyl naphthalene, vinyl phenyl sulfide, 4-methacryloxyphenyl-4′-methoxyphenyl thioether, and the like.

  Polymerization of the monomer having an ethylenically unsaturated group can be performed by irradiation with ionizing radiation or heating in the presence of a photo radical initiator or a thermal radical initiator. Accordingly, a coating liquid containing a monomer having an ethylenically unsaturated group, the above-mentioned particles, and a photo radical initiator or a thermal radical initiator is prepared, and the coating liquid is applied onto a transparent support and then polymerized by ionizing radiation or heat. It can be cured by reaction to form an antiglare hard coat layer.

  The polymer having a polyether as the main chain is preferably a ring-opening polymer of a polyfunctional epoxy compound. The ring-opening polymerization of the polyfunctional epoxy compound can be performed by irradiation with ionizing radiation or heating in the presence of a photoacid generator or a thermal acid generator. Accordingly, a coating liquid containing a polyfunctional epoxy compound, the above-mentioned particles, and a photoacid generator or a thermal acid generator is prepared, and the coating liquid is applied on a transparent support and then cured by ionizing radiation or heat polymerization. Thus, an antiglare hard coat layer can be formed.

  Instead of or in addition to a monomer having two or more ethylenically unsaturated groups, a monomer having a crosslinkable functional group is used to introduce a crosslinkable functional group into the polymer, and by reaction of this crosslinkable functional group, A crosslinked structure may be introduced into the binder polymer. Examples of the crosslinkable functional group include isocyanate group, epoxy group, aziridine group, oxazoline group, aldehyde group, carbonyl group, hydrazine group, carboxyl group, methylol group and active methylene group. Vinylsulfonic 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 the decomposition reaction, such as a block isocyanate group, may be used. Thus, in this invention, a crosslinkable functional group is not restricted to the said functional group, The thing which shows the reactivity as a result of decomposition | disassembly may be sufficient. These binder polymers having a crosslinkable functional group can form a crosslinked structure by heating after coating.

The antiglare hard coat layer has an average particle size of 1 μm or more, preferably 1 to 10 μm, more preferably for the purpose of preventing the deterioration of reflectance due to interference between the antiglare property and the antiglare hard coat layer. In which particles of 1.5 to 7.0 μm, for example, inorganic compound particles or resin particles are dispersed. Specific examples of the particles include preferably particles of inorganic compounds such as silica particles and TiO ₂ particles; resin particles such as crosslinked acrylic particles, crosslinked styrene particles, melamine resin particles, and benzoguanamine resin particles. Of these, silica particles are preferable. The particle shape can be either a true sphere or an indefinite shape. Two or more different kinds of particles may be used in combination. The particles are contained in the antiglare hard coat layer so that the amount of particles in the formed antiglare hard coat layer is preferably 10 to 1000 mg / m ² , more preferably 30 to 100 mg / m ^2. . In a particularly preferred embodiment, silica particles are used as the particles, and the silica particles having a particle size larger than one half of the film thickness of the antiglare hard coat layer occupy 40 to 100% of the entire silica particles. It is. Here, the particle size distribution of the particles is measured by a Coulter counter method, and the measured distribution is converted into a particle number distribution.

In order to increase the refractive index of the antiglare hard coat layer, in addition to the above particles, oxidation of at least one metal selected from titanium, zirconium, aluminum, indium, zinc, tin, and antimony is performed. It is preferable that the inorganic fine particle which consists of a thing and whose particle size is 100 nm or less, Preferably it is 50 nm or less is contained. Specific examples of the inorganic fine particles include fine particles such as TiO ₂ , ZrO ₂ , Al ₂ O ₃ , In ₂ O ₃ , ZnO, SnO ₂ , Sb ₂ O ₃ and ITO. The amount of these inorganic fine particles added is preferably 10 to 90% by weight, more preferably 20 to 80% by weight, based on the total weight of the antiglare hard coat layer containing the above particles having an average particle size of 1 μm or more. Especially preferably, it is 30 to 60% by weight. Such fine particles have a particle size sufficiently smaller than the wavelength of light and therefore do not scatter, and a dispersion in which the fine particles are dispersed in a binder polymer behaves as an optically uniform substance.

  As described above, the components excluding the particles having an average particle diameter of 1 μm or more forming the antiglare hard coat layer, that is, the film made of the binder polymer or the inorganic fine particles of the metal oxide having the particle diameter of 100 nm or less are formed on the binder polymer. The refractive index of the film made of the dispersed dispersion is preferably 1.57 to 2.00, more preferably 1.60 to 1.80. In order to make the refractive index within the above range, the type and amount ratio of the binder polymer and metal oxide fine particles may be appropriately selected. How to select can be easily known experimentally in advance.

  The film thickness of the antiglare hard coat layer is preferably 1 to 10 μm, and more preferably 1.2 to 6 μm.

  In the antiglare antireflection film of the present invention, a smooth hard coat layer is coated between the transparent support and the antiglare hard coat layer as necessary for the purpose of improving the film strength. The film thickness of the smooth hard coat layer is preferably 1 to 10 μm, more preferably 1.2 to 6 μm. As components used for the smooth hard coat layer, those mentioned in the anti-glare hard coat layer can be used except that no anti-glare imparting particles having an average particle diameter of 1 μm or more are used.

  In the present invention, the alkali treatment is performed after the antiglare hard coat layer is applied and cured. As a result, the adhesion with the low refractive index layer coated on the antiglare hard coat layer is greatly improved, and the film strength is greatly improved. The alkali treatment performed here is the adhesion between the TAC and the polarizing plate substrate when the antiglare antireflection film of the present invention uses triacetyl cellulose (TAC) as a support and the film is used for LCD. It is preferable to also serve as an alkali treatment that is generally performed in order to obtain the properties because the burden on the process can be reduced.

  The alkali treatment method is not particularly limited as long as it is a method of immersing a film coated up to the antiglare hard coat layer in an alkaline aqueous solution. The alkali treatment conditions are appropriately adjusted within a range in which the surface shape of the antiglare layer does not change significantly. As the aqueous alkali solution, an aqueous sodium hydroxide solution, an aqueous potassium hydroxide solution, an aqueous ammonia solution or the like can be used, and an aqueous sodium hydroxide solution is preferred. 0.1-25 weight% is preferable and, as for the alkali concentration (for example, sodium hydroxide density | concentration) of aqueous alkali solution, 0.5-15 weight% is more preferable. The alkali treatment temperature is 10 to 80 ° C, preferably 20 to 60 ° C. The alkali treatment time is 5 seconds to 5 minutes, preferably 30 seconds to 3 minutes. The film after the alkali treatment is preferably neutralized with acidic water and then thoroughly washed with water. The film after the water washing treatment is sufficiently dried and then subjected to a step of coating the next low refractive index layer.

  The refractive index of the low refractive index layer of the antiglare antireflection film of the present invention is 1.35 to 1.49, preferably 1.35 to 1.45. Furthermore, the low refractive index layer preferably satisfies the following formula (I) in order to obtain good antireflection performance.

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

In the formula, m is a positive odd number, n ₁ is the refractive index of the low refractive index layer, and d ₁ is the film thickness (nm) of the low refractive index layer. Also, λ is a wavelength and is a value in the range of 500 to 550 (nm). In addition, satisfy | filling said numerical formula (I) means that m (positive odd number, usually 1) which satisfy | fills numerical formula (I) exists in the said wavelength range.

  As a material that can be used to form the low refractive index layer, various materials having a refractive index of 1.35 to 1.49 can be used. Either a coating film or a vapor deposition film can be used, but a coating film is more preferable. Examples of coating-type low refractive index materials include fluorine-containing polymers, polymers of fluorine-containing oligomers, low-refractive-index inorganic fine particles (magnesium fluoride, calcium fluoride, silica, etc.) / Binder mixtures, organosilane hydrolysates and / or Alternatively, a cured product of a partial condensate (so-called silica sol-gel film) or the like can be used. Among these, a cured product of hydrolyzate and / or partial condensate of organosisilane is preferable because it has high film strength and excellent scratch resistance, and more preferably a photocured organosilane hydrolyzate and / or partial condensate. It is a cured product.

  When the low refractive index layer of the present invention is a photo-cured organosilane hydrolyzate and / or a partial condensate thereof, a so-called sol-gel component (hereinafter referred to as a cured product), the sol-gel component and other components are added. A composition to be contained is prepared, and the composition is applied, dried, and then cured to form a low refractive index layer. Since the photocurable sol-gel component alone has a large volume shrinkage at the time of curing, the adhesiveness is reduced and the scratch resistance is not sufficient, so by adding inorganic fine particles to the composition, the volume shrinkage at the time of curing is reduced, Prevents a decrease in scratch resistance by improving adhesion. Further, the hardness of the inorganic fine particles improves film strength and scratch resistance. Furthermore, it is preferable to mix | blend a fluorine-containing polymer with a composition, and the antifouling property and slipperiness | lubricity of an anti-glare antireflection film improve by mixing | blending a fluorine-containing polymer. As the fluorine-containing polymer, a polymer obtained by polymerizing a fluorine-containing vinyl monomer is preferable, and a polymer having a functional group capable of covalently bonding to the sol-gel component is preferable from the viewpoint of compatibility with the sol-gel component and film strength.

  The photocurable sol-gel component is not particularly limited as long as it is a sol-gel component having a property of being cured by light irradiation, and any commercially available or synthetic one can be preferably used. As a commercial item, Opstar TM505 and TM501A (made by JSR Corporation) etc. which are photocuring sol gel components containing a fluorine-containing polymer are mentioned preferably.

  The photocurable sol-gel component can be obtained by, for example, hydrolysis of organosilane represented by the following general formula (1) and subsequent condensation reaction.

  RxSi (OR ′) 4-x ...... General formula (1)

(In the formula, R and R ′ are the same or different and each represents a hydrogen atom, an alkyl group, an aryl group, an allyl group or a fluoroalkyl group. Here, the alkyl group is an epoxy group, amino group, (It may have an acrylic group, an isocyanate group, and / or a mercapto group. X is an integer of 0 to 3, preferably an integer of 0 to 2.)

Specific examples of the organosilane represented by the general formula (1) include the following, but the present invention is not limited to these examples.
If x = 0:
Tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, etc. When x = 1:
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 Si (OCH ₃ ) ₃ , γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-trimethoxysilylpropyl Isocyanate, γ-mercaptopropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-acryloxypropyltrimethoxysilane, etc. x = 2:
Dimethyldimethoxysilane, dimethyldiethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-aminopropylmethyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, etc. Two or more different organosilanes can be used in combination for the purpose of adjusting the thickness and brittleness and introducing functional groups.

  The hydrolysis / condensation reaction of organosilane can be carried out without solvent or in the presence of an organic solvent. Preferred organic solvents include acetone, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, methanol, ethanol, isopropyl alcohol, butanol, toluene, xylene, tetrahydrofuran, 1,4-dioxane and the like. The organic solvent used here is preferably used as a coating solution as it is in the process, and when a fluorine-containing polymer is added later, it is preferable to dissolve the fluorine-containing polymer. The hydrolysis / condensation reaction is preferably performed in the presence of a catalyst. Catalysts include 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; triethylamine, Examples thereof include organic bases such as pyridine; metal alkoxides such as triisopropoxyaluminum and tetrabutoxyzirconium; metal chelate compounds of the metal alkoxides with ethyl acetoacetate, acetylacetone and the like.

  In the hydrolysis / condensation reaction, 0.3 to 2 mol, preferably 0.5 to 1 mol of water is added to 1 mol of the alkoxy group of the organosilane, in the presence or absence of the solvent, and Preferably, it is carried out by stirring at 25 to 100 ° C. in the presence of a catalyst. The usage-amount of a catalyst is 0.01-10 mol% with respect to an alkoxy group, Preferably it is 0.1-5 mol%. The reaction conditions are preferably adjusted as appropriate depending on the reactivity of the organosilane.

  In this hydrolysis / condensation reaction, first, an alkoxy group of organosilane reacts with water to hydrolyze the alkoxy group to produce a silanol group. Subsequently, two silanol groups are dehydrated and condensed to form a siloxane bond. Therefore, the product of this reaction varies in proportion depending on the amount of water added and other reaction conditions, but contains unreacted alkoxy groups, silanol groups, and siloxane bonds. In the present invention, the organosilane partial condensate means that all the alkoxy groups of the organosilane do not form silanol bonds via silanol groups, some of the alkoxy groups form silanol bonds, and the rest are unreacted or The one in a silanol group state.

  Examples of the fluorine-containing polymer used in the low refractive index layer include a fluorine-containing vinyl polymer, a fluorine-containing polyether, and a fluorine-containing polysiloxane. Of these, a fluorine-containing vinyl polymer is preferable. The fluorine-containing vinyl polymer can be obtained by radical polymerization of a fluorine-containing 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.), (meth) A part of acrylic acid or a fully fluorinated alkyl ester derivative (for example, Biscoat 6FM (manufactured by Osaka Organic Chemical) or M-2020 (manufactured by Daikin)), a fully or partially fluorinated vinyl ether, and the like. Of these, hexafluoropropylene and fluorinated vinyl ethers are preferred.

  Furthermore, it is more preferable if the fluorine-containing vinyl polymer has a reactive group, and this reactive group can react with the photocurable sol-gel component to form a covalent bond. By this, the cured film of the photocurable sol-gel component and the fluorine-containing polymer component are covalently bonded in the low refractive index layer, and preferable results such as improved film strength and transparency can be obtained. Such a fluorine-containing vinyl polymer having a reactive group can be obtained by copolymerizing a fluorine-containing vinyl monomer and a vinyl monomer having a reactive group.

The vinyl monomer having a reactive group capable of covalent bonding with the photocurable sol-gel component will be described below. A preferred reactive group capable of reacting with a silanol group generated by hydrolysis of organosilane includes an alkoxysilyl group. Examples of the alkoxysilyl-containing vinyl monomer include γ-methacryloxypropyltrimethoxysilane and vinyltrimethoxysilane. Moreover, an epoxy group, an amino group, an isocyanate group, a mercapto group, or the like can be introduced into the photocurable sol-gel component by hydrolyzing / condensing an organosilane having a functional group. Examples of reactive groups that can be covalently bonded to these functional groups include hydroxy groups, epoxy groups, and carboxyl groups. Although the following monomers can be mentioned as a vinyl monomer which has these reactive groups, It is not limited to these.
(1) Monomer having a hydroxy group:
2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether and the like (2) monomers having an epoxy group:
Glycidyl methacrylate, glycidyl acrylate, vinyl glycidyl ether and the like (3) Monomers having a carboxyl group:
Acrylic acid, methacrylic acid, β-carboxyethyl acrylate, crotonic acid, itaconic acid, α-vinylacetic acid, vinyl fumarate, vinyl maleate, etc.

  In the copolymerization, vinyl monomers other than those described above can also be used as the copolymerization monomer. Examples of such monomers include olefins (ethylene, propylene, isoprene, vinyl chloride, vinylidene chloride, etc.), acrylic esters (methyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate), methacrylic esters (methyl methacrylate). , Ethyl methacrylate, butyl methacrylate, ethylene glycol dimethacrylate, etc.), styrene derivatives (styrene, divinylbenzene, vinyl toluene, α-methylstyrene, 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, - cyclohexyl acrylamide), methacrylamides, and acrylonitrile derivatives. Of these, vinyl ethers are preferred.

  The proportion of each monomer used in the copolymerization is preferably 20 to 80% by weight for the fluorine-containing vinyl monomer, 0 to 30% by weight for the reactive group-containing monomer, and 0 to 70% by weight for the other monomers. The copolymerization of the monomers can be performed by a radical polymerization method known per se.

  In addition to the method of introducing a reactive group into the fluorine-containing vinyl polymer by the above-described copolymerization method, the reaction with the reactive group of the fluorine-containing vinyl polymer reacts with an organosilane having a functional group capable of forming a covalent bond. By doing so, an alkoxysilyl group can be introduced into the fluorine-containing vinyl polymer. The introduction of the alkoxysilyl group by this method can be carried out in the coating solution of the composition for forming the low refractive index layer, so that it is simple and preferable.

  When a photocurable sol-gel component is used in the low refractive index layer of the antiglare antireflection film, the compound for forming the layer generates a curing reaction accelerator upon irradiation with light in order to accelerate curing. It is preferable to contain. Specifically, a photoacid generator or a photobase generator is preferred, and both can accelerate the condensation reaction of the photocurable sol-gel component and accelerate the curing. Specific examples of the photoacid generator include benzoin tosylate, tri (nitrobenzyl) phosphate, diaryl iodonium salt, triaryl sulfonium salt and the like. Specific examples of the photobase generator include nitrobenzyl cyclohexyl carbamate, di (methoxybenzyl) hexamethylene dicarbamate, and the like. Of these, photoacid generators are more preferred, and triarylsulfonium salts and diaryliodonium salts are particularly preferred. Sensitizing dyes can also be preferably used in combination with these compounds.

  The compounding amount of the compound that generates the curing reaction accelerator upon irradiation with light is preferably 0.1 to 15% by weight, more preferably 0, of the composition (total solid content) for forming the low refractive index layer. It is an amount that occupies 5 to 5% by weight.

  As the inorganic fine particles used in the low refractive index layer of the antiglare antireflection film, amorphous particles are preferably used, and preferably composed of metal oxides, nitrides, sulfides or halides. Metal oxides are particularly preferred. As metal atoms, Na, K, Mg, Ca, Ba, Al, Zn, Fe, Cu, Ti, Sn, In, W, Y, Sb, Mn, Ga, V, Nb, Ta, Ag, Si, B Bi, Mo, Ce, Cd, Be, Pb and Ni are preferred, and Mg, Ca, B and Si are more preferred. Inorganic fine particles containing two or more metals may be used. Particularly preferred inorganic fine particles are silicon dioxide fine particles, that is, silica fine particles. The average particle size of the inorganic fine particles is preferably 0.001 to 0.2 μm, and more preferably 0.005 to 0.05 μm. The particle diameter of the fine particles is preferably as uniform (monodispersed) as possible. If the particle size of the inorganic fine particles is too large, the film becomes opaque, and if it is too small, the particles tend to aggregate and are difficult to synthesize and handle.

  The blending amount of the inorganic fine particles is preferably 3 to 90% by weight, more preferably 5 to 70% by weight, and particularly preferably 7 to 50% by weight based on the total weight of the low refractive index layer. If the amount of inorganic fine particles added is too large, a continuous layer of a photocurable sol-gel component as a binder cannot be formed and becomes brittle, and if too small, the effect of adding fine particles cannot be obtained.

  The inorganic fine particles are preferably used after being subjected to a surface treatment. The surface treatment method includes physical surface treatment such as plasma discharge treatment and corona discharge treatment and chemical surface treatment using a coupling agent, but the use of a coupling agent is preferred. As the coupling agent, an organoalkoxy metal compound (eg, titanium coupling agent, silane coupling agent, etc.) is preferably used. When the inorganic fine particles are silica, treatment with a silane coupling agent is particularly effective. As the silane coupling agent, an organosilane compound represented by the above general formula (1) can be used.

  The film thickness of the low refractive index layer is preferably 0.05 to 0.2 μm, more preferably 0.08 to 0.12 μm.

  In order to make the refractive index of the low refractive index layer as described above and satisfy the formula (I), the type and amount ratio of each component for forming the low refractive index layer may be appropriately selected. Selection of the kind and amount ratio of each component can be known experimentally in advance.

  The antiglare antireflection film can be formed by the following method, but is not limited to this method. That is, first, a coating liquid (composition) containing components for forming each layer is prepared. Next, a coating solution for forming an antiglare hard coat layer is prepared 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 (USA). (See Japanese Patent No. 2681294), coated on a transparent support, heated and dried. Thereafter, the monomer for forming the antiglare hard coat layer is polymerized and cured by light irradiation or heating. Thereby, an anti-glare hard coat layer is formed. The surface of the antiglare hard coat layer thus formed is subjected to alkali treatment. Next, a coating solution for forming a low refractive index layer is applied on the antiglare hard coat layer in the same manner, heated and dried, and then irradiated with light to cure the photocurable sol-gel component. A refractive index layer is formed. You may heat as needed after light irradiation. Thus, the anti-glare antireflection film of the present invention is obtained.

  The polarizing plate of this invention uses the said anti-glare antireflection film for at least one of the two protective films of the polarizing layer. By using the antiglare 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, antifouling property and the like can be obtained. Moreover, the manufacturing cost can be reduced because the antiglare antireflection film also serves as a protective film in the polarizing plate of the present invention.

  The antiglare antireflection film of the present invention can be applied to an image display device such as a liquid crystal display device (LCD), a plasma display panel (PDP), an electroluminescence display (ELD), or a cathode ray tube display device (CRT). it can. Since the antiglare antireflection film of the present invention has a transparent support, the transparent support side is adhered to the image display surface of the image display device.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited thereto.

(Preparation of coating solution A for antiglare hard coat layer)
250 g of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.) was dissolved in 439 g of a mixed solvent of methyl ethyl ketone / cyclohexanone = 50/50%. A solution obtained by dissolving 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.) in 49 g of methyl ethyl ketone was added to the obtained solution. added. The refractive index of the coating film obtained by applying this solution and curing with ultraviolet rays was 1.53. Further, 10 g of amorphous silica particles having an average particle size of 3 μm (trade name: Mizukasil P-526, manufactured by Mizusawa Chemical Co., Ltd.) were added to this solution, and the mixture was stirred and dispersed at 5000 rpm for 1 hour with a high-speed dispaper. An antiglare hard coat layer coating solution was prepared by filtration through a polypropylene filter having a pore size of 30 μm.

(Preparation of coating solution B for antiglare hard coat layer)
439 g of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, Nippon Kayaku Co., Ltd.) 125 g, bis (4-methacryloylthiophenyl) sulfide (MPSMA, Sumitomo Seika Co., Ltd.) 125 g In a mixed solvent of methyl ethyl ketone / cyclohexanone = 50/50%. In the obtained solution, a solution obtained by dissolving 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.) in 49 g of methyl ethyl ketone. added. The refractive index of the coating film obtained by applying this solution and curing with ultraviolet rays was 1.60. Furthermore, 10 g of crosslinked polystyrene particles having an average particle diameter of 2 μm (trade name: SX-200H, manufactured by Soken Chemical Co., Ltd.) was added to this solution, and the mixture was stirred and dispersed at 5000 rpm for 1 hour with a high-speed dispaper. A coating solution for the antiglare hard coat layer was prepared by filtration through a polypropylene filter.

(Preparation of coating solution C for antiglare hard coat layer)
To a mixed solvent of 104.1 g of cyclohexanone and 61.3 g of methyl ethyl ketone, 217.0 g of a hard oxide coating solution containing zirconium oxide dispersion (KZ-7991, manufactured by JSR Corporation) was added while stirring with an air disperser. The refractive index of the coating film obtained by applying this solution and curing with ultraviolet rays was 1.70. Further, 5 g of a crosslinked polystyrene particle having an average particle diameter of 2 μm (trade name: SX-200H, manufactured by Soken Chemical Co., Ltd.) was added to this solution, and the mixture was stirred and dispersed at 5000 rpm for 1 hour with a high-speed dispaper. A coating solution for the antiglare hard coat layer was prepared by filtration through a polypropylene filter.

(Preparation of coating solution D for antiglare hard coat layer)
While stirring with an air disperser, 33.3 g of cyclohexanone, 303.3 g of a hard coat coating solution containing a zirconium oxide dispersion (KZ-7118, manufactured by JSR Corporation), and a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate ( DPHA, manufactured by Nippon Kayaku Co., Ltd. (123.4 g) was added. The refractive index of the coating film obtained by applying this solution and curing with ultraviolet rays was 1.61. Furthermore, 8.2 g of crosslinked polystyrene particles having an average particle diameter of 2 μm (trade name: SX-200H, manufactured by Soken Chemical Co., Ltd.) was added to this solution, and the mixture was stirred and dispersed at 5000 rpm for 1 hour with a high speed dispaper. The solution was filtered through a 30 μm polypropylene filter to prepare a coating solution for an antiglare hard coat layer.

(Preparation of coating liquid E for hard coat layer)
250 g of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.) was dissolved in 439 g of a mixed solvent of methyl ethyl ketone / cyclohexanone = 50/50%. A solution obtained by dissolving 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.) in 49 g of methyl ethyl ketone was added to the obtained solution. added. The refractive index of the coating film obtained by applying this solution and curing with ultraviolet rays was 1.53. Further, this solution was filtered through a polypropylene filter having a pore diameter of 30 μm to prepare a coating solution for a hard coat layer.

(Preparation of coating solution A for low refractive index layer)
Fluorine-containing polymer-containing photocurable sol-gel compound having a refractive index of 1.41 (OPSTAR TM501A, solid content concentration 15%, manufactured by JSR Corporation) and silica particle methyl isobutyl ketone dispersion (MIBK-ST, solid content concentration 30%) 2.8 g of Nissan Chemical Co., Ltd.) and 147 g of methyl isobutyl ketone were added, stirred and then filtered through a polypropylene filter having a pore size of 1 μm to prepare a coating solution for a low refractive index layer. The refractive index of the coating film obtained by applying this coating solution and curing with ultraviolet rays was 1.42.

(Preparation of coating solution B for low refractive index layer)
Fluorine-containing polymer-containing photocurable sol-gel compound having a refractive index of 1.43 (OPSTAR TM505, solid content concentration 15%, manufactured by JSR Corporation) and silica particle methyl isobutyl ketone dispersion (MIBK-ST, solid content concentration 30%) 2.8 g of Nissan Chemical Co., Ltd.) and 147 g of methyl isobutyl ketone were added, stirred and then filtered through a polypropylene filter having a pore size of 1 μm to prepare a coating solution for a low refractive index layer. The refractive index of the coating film obtained by applying this coating solution and curing with ultraviolet rays was 1.43.

(Preparation of coating solution C for low refractive index layer)
Fluorine-containing polymer-containing photocurable sol-gel compound having a refractive index of 1.41 (OPSTAR TM501A, solid content 15%, manufactured by JSR Corporation) 28 g, methyl isobutyl ketone 72 g was added, and after stirring, a polypropylene filter having a pore size of 1 μm And a coating solution for a low refractive index layer was prepared. The refractive index of the coating film obtained by applying this coating solution and curing with ultraviolet rays was 1.42.

(Preparation of coating solution D for low refractive index layer)
Fluorine-containing polymer-containing photocurable sol-gel compound with a refractive index of 1.43 (OPSTAR TM505, solid concentration 15%, manufactured by JSR Corporation) 28 g of methyl isobutyl ketone was added, and after stirring, a polypropylene filter having a pore size of 1 μm And a coating solution for a low refractive index layer was prepared. The refractive index of the coating film obtained by applying this coating solution and curing with ultraviolet rays was 1.43.

[Example 1]
(Coating of antiglare hard coat layer)
The above-mentioned anti-glare hard coat layer coating solution A was applied to an 80 μm-thick triacetyl cellulose film (TAC-TD80U, manufactured by Fuji Photo Film Co., Ltd.) using a bar coater and dried at 120 ° C. Then, using a 160 W / cm air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.), the coating layer was cured by irradiating ultraviolet rays with an illuminance of 400 mW / cm ² and an irradiation amount of 300 mJ / cm ² . An antiglare hard coat layer was formed to produce an antiglare hard coat base.
(Alkali treatment)
The above antiglare hard coat base is immersed in an aqueous 1.5 mol / L sodium hydroxide solution at a liquid temperature of 55 ° C. for 2 minutes, followed by washing with running water for 15 seconds, and 0.05 mol / L at a liquid temperature of 30 ° C. It was immersed in sulfuric acid for 15 seconds, washed with running water for 15 seconds, and then dried at 70 ° C. for 3 minutes to prepare an alkali-treated antiglare hard coat base.
(Coating of low refractive index layer)
On the above saponification-treated antiglare hard coat base, the coating solution A for low refractive index layer was applied using a bar coater and dried at 60 ° C., and then the illuminance was 400 mW / cm ² and the irradiation amount was 300 mJ / cm ² . The coating layer was cured by irradiating with ultraviolet rays, and further 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 for low refractive index layer was used instead of the coating liquid A for low refractive index layer.

[Example 3]
A sample was prepared in the same manner as in Example 1 except that the coating liquid C for low refractive index layer was used instead of the coating liquid A for low refractive index layer.

[Example 4]
A sample was prepared in the same manner as in Example 1 except that the coating solution D for low refractive index layer was used instead of the coating solution A for low refractive index layer.

[Comparative Example 1]
A comparative sample was prepared in the same manner as in Example 1 except that the alkali treatment was not performed after coating the antiglare hard coat layer.

[Comparative Example 2]
A comparative sample was prepared in the same manner as in Example 2 except that the alkali treatment was not performed after coating the antiglare hard coat layer.

[Comparative Example 3]
A comparative sample was prepared in the same manner as in Example 3 except that the alkali treatment was not performed after coating the antiglare hard coat layer.

[Comparative Example 4]
A comparative sample was prepared in the same manner as in Example 4 except that the alkali treatment was not performed after coating the antiglare hard coat layer.

[Example 5]
(Coating of hard coat layer)
The coating liquid E for hard coat layer was applied to a triacetyl cellulose film (TAC-TD80U, manufactured by Fuji Photo Film Co., Ltd.) having a thickness of 80 μm using a bar coater, dried at 120 ° C., and then 160 W / cm. Using an 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 4 μm thick hard coat layer did.
(Coating of antiglare hard coat layer)
The anti-glare hard coat layer coating solution B is applied onto the hard coat layer using a bar coater, dried and UV cured under the same conditions as the hard coat layer, and an anti-glare layer having a thickness of about 1.5 μm. An anti-glare hard coat base was prepared by forming a hard coat layer.
(Alkali treatment)
The above antiglare hard coat base is immersed in an aqueous 1.5 mol / L sodium hydroxide solution at a liquid temperature of 55 ° C. for 2 minutes, followed by washing with running water for 15 seconds, and 0.05 mol / L at a liquid temperature of 30 ° C. It was immersed in sulfuric acid for 15 seconds, washed with running water for 15 seconds, and then dried at 70 ° C. for 3 minutes to prepare an alkali-treated antiglare hard coat base.
(Coating of low refractive index layer)
The low-refractive-index layer coating solution A is applied onto an alkali-treated antiglare hard coat base using a bar coater, dried at 60 ° C., and then irradiated with ultraviolet rays having an illuminance of 400 mW / cm ² and an irradiation amount of 300 mJ / cm ² . After the coating layer was cured by irradiation, it was further heated at 120 ° C. for 8 minutes to form a low refractive index layer having a thickness of 0.096 μm.

[Example 6]
A sample was prepared in the same manner as in Example 5 except that the antiglare hard coat layer coating solution C was used instead of the antiglare hard coat layer coating solution B.

[Example 7]
A sample was prepared in the same manner as in Example 5 except that the antiglare hard coat layer coating solution D was used in place of the antiglare hard coat layer coating solution B and a gravure coater was used.

[Example 8]
A sample was prepared in the same manner as in Example 6 except that the coating solution B for low refractive index layer was used instead of the coating solution A for low refractive index layer.

[Example 9]
A sample was prepared in the same manner as in Example 6 except that the coating liquid C for low refractive index layer was used instead of the coating liquid A for low refractive index layer.

[Comparative Example 5]
A comparative sample was prepared in the same manner as in Example 5 except that the alkali treatment was not performed after coating the antiglare hard coat layer.

[Comparative Example 6]
A comparative sample was prepared in the same manner as in Example 6 except that the alkali treatment was not performed after coating the antiglare hard coat layer.

(Evaluation of antireflection film)
About the obtained film, the following items were evaluated.
(1) Average reflectance Using a spectrophotometer (manufactured by JASCO Corporation), the spectral reflectance at an incident angle of 5 degrees was measured in a wavelength region of 380 to 780 nm. The average reflectance of 450-650 nm was used for the result.
(2) Haze The haze of the obtained film was measured using a haze meter MODEL 1001DP (manufactured by Nippon Denshoku Industries Co., Ltd.).
(3) Scratch resistance evaluation: Steel wool test After the film was conditioned for 2 hours at a temperature of 25 ° C. and a relative humidity of 60%, # 0000 steel wool was reciprocated 60 times at a ground area of 1 cm ² and a load of 200 g. The scratches were judged visually under a fluorescent lamp.
No scratches are recognized: ○
Slight scratches are found: △
Scratches are clearly recognized: ×
(4) Contamination Resistance As an index of surface contamination resistance, the optical material was conditioned at a temperature of 25 ° C. and a humidity of 60% RH for 2 hours, and then the contact angle with water was measured. Further, after the fingerprint was attached to the surface of the sample, the state when the sample was wiped with a cleaning cloth was observed, and the fingerprint adhesion was evaluated as follows.
Fingerprints can be wiped off completely: ○
Some fingerprints are visible: △
Fingerprints can hardly be wiped off: ×

(5) Dynamic friction coefficient measurement The dynamic friction coefficient was evaluated as an index of surface slipperiness. As the dynamic friction coefficient, a sample was conditioned at 25 ° C. and a relative humidity of 60% for 2 hours, and then a value measured with a HEIDON-14 dynamic friction measuring machine at a 5 mmφ stainless steel ball, a load of 100 g, and a speed of 60 cm / min was used.
(6) Evaluation of anti-glare property The exposed anti-louvered fluorescent lamp (8000 cd / m ² ) was projected on the produced anti-glare film, and the degree of blur of the reflected image was evaluated according to the following criteria.
I do not know the outline of the fluorescent lamp at all: ◎
Slightly understand the outline of the fluorescent lamp: ○
The fluorescent lamp is blurred, but the outline can be identified: △
Fluorescent lamp is hardly blurred: ×
(7) Glitter evaluation Fluorescent lamp diffused light with a louver was projected on the created antiglare film, and surface glare was evaluated according to the following criteria.
Almost no glare seen: ○
There is slight glare: △
There is glare of a size that can be discerned by the eyes: ×

  Table 1 shows the evaluation results of Examples and Comparative Examples. The antiglare antireflection films of Examples 1 to 9 are all excellent in antireflection performance, and all the performances required for antiglare antireflection films such as scratch resistance, fingerprint adhesion, antiglare and glare are as follows. It was good. On the other hand, since the antiglare antireflection films of Comparative Examples 1 to 6 were not subjected to the alkali treatment of the antiglare hard coat layer, the scratch resistance was insufficient.

  Next, an antiglare antireflection polarizing plate was prepared using the films of Examples 1 to 9. Using this polarizing plate, a liquid crystal display device in which an antireflection layer was disposed on the outermost layer was created. As a result, there was no reflection of external light, and excellent contrast was obtained. It had visibility.

It is a cross-sectional schematic diagram which shows the layer structure of an anti-glare antireflection film.

Explanation of symbols

1 Antiglare Antireflection Film 2 Transparent Support 3 Hard Coat Layer 4 Antiglare Hard Coat Layer 5 Low Refractive Index Layer 6 Particles

Claims (10)

A method for producing an antiglare antireflection film having an antiglare hard coat layer and a low refractive index layer having a refractive index of 1.35 to 1.49 in this order on a transparent substrate,
The low refractive index layer is formed from a composition containing at least one of hydrolyzate of organosilane and partial condensate thereof,
Applying and curing an antiglare hard coat layer on a transparent substrate; and
A method for producing an antiglare antireflection film comprising a step of subjecting an antiglare hard coat layer to an alkali treatment.   The method for producing an antiglare antireflection film according to claim 1, wherein the alkali concentration of the aqueous alkali solution used for the alkali treatment is 0.1 to 25% by weight.   The method for producing an antiglare antireflection film according to claim 1 or 2, wherein the temperature in the alkali treatment is 10 to 80 ° C. After alkali treatment, antiglare method for producing an antireflection film according to claim 1, comprising the step of Coating a low refractive index layer by washing with water. Method for producing anti-glare and anti-reflection film according to any one of claims 1-4 transparent substrate is a triacetyl cellulose. The refractive index of the film formed by removing the particles having an average particle diameter of 1 to 10 μm from the composition for forming the antiglare hard coat layer, wherein the antiglare hard coat layer contains particles having an average particle diameter of 1 to 10 μm. there antiglare method for producing an antireflection film according to claim 1 in the range of 1.57 to 2.00. Method for producing anti-glare and anti-reflection film according to any one of claims 1 to 6 the film thickness of the antiglare hard coat layer is 1 to 10 [mu] m. The average particle size in the antiglare hard coat layer is 1 to 10 [mu] m, silica particles, and anti-glare and anti-reflection film according to claim 1 containing at least one particle of an inorganic compound Manufacturing method. The antiglare hard coat layer contains at least one kind of resin particles of crosslinked acrylic particles, crosslinked styrene particles, melamine resin particles, and benzoguanamine resin particles having an average particle diameter of 1 to 10 µm. 2. A method for producing an antiglare antireflection film according to item 1 . Method for producing anti-glare and anti-reflection film according to any one of claims 1 to 9 the film thickness of the low refractive index layer is 0.05 to 0.2 [mu] m.

Images