Anti-glare film, its manufacturing method and use

Abstract

To provide an anti-glare film capable of achieving both color tone and anti-glare property.SOLUTION: An anti-glare film is prepared, in which a ratio R / V of diffuse specular reflection intensity R to a total sum V of diffuse reflection intensity is 0.01 to 0.12, haze of 44% or more, 60-degree gloss is 0.2 to 10%, and an absolute value of chromaticity b*of transmitted light is 3 or less. A display device may include the anti-glare film. The display device may be an organic EL display or a liquid crystal display device.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention is applicable to liquid crystal displays (LCDs) and organic electroluminescent (EL) displays. Anti-glare film that can be used in various display devices such as LCDs, and its manufacturing method and uses . [Background technology]

[0002] Anti-glare films are used on the display surfaces of image display devices such as LCDs and organic EL displays. It is widely used as a film to prevent reflections of outside scenery and improve visibility. The optical properties required for anti-glare films are high haze, which provides anti-glare performance. In addition to improving the performance, it has high transparency (total light transmittance) and is not biased towards yellow or red. The property of providing a neutral white light to the viewer rather than a dark color, improving visibility In order to realize such a function, anti-glare films have conventionally contained fine particles. A mixture of the binder resin or the curable resin is applied to a substrate to form fine irregularities on the surface. There is a known method for preventing regular reflection and exhibiting anti-glare properties by using fine particles. The anti-glare film used controls the intensity distribution of transmitted and scattered light by adjusting the particle size. Therefore, it is not possible to effectively prevent glare or blurred characters on the display surface. The anti-glare film is made by the difference in refractive index between the matrix material that makes up the anti-glare film and the dispersed particles. The larger the haze value, the higher the light diffusion. The light is scattered over a wide angle, so when the display is viewed from the front, it appears yellowish and dull. Visibility is reduced. Also, backscattering is likely to occur, which reduces transparency.

[0003] Therefore, we have developed a method to form a rough surface by utilizing the spinodal decomposition of incompatible resin components. A method for producing a resin composition comprising a plurality of resin components is also known. The antiglare film includes an antiglare layer having long, thin convex portions formed on the surface thereof due to phase separation of the antiglare layer. Therefore, the long thin projections have a branched structure and a total length of 100 μm or more. The long and thin convex portions are 1 mm thick on the surface of the antiglare layer. 2 There is more than one anti-glare film per This antiglare film has an excellent balance between haze and clarity, and provides a high-definition display. Display devices (for example, liquid crystal display devices with a resolution of 200 ppi or more, organic EL display devices) Even if it is installed in a room with a screen, it can improve anti-glare properties, highly suppress glare, and also suppress blurred text. It can be controlled.

[0004] However, even with this anti-glare film, improving transparency can sometimes result in a decrease in anti-glare properties. Furthermore, with conventional methods, it is difficult to produce a film that is transparent, has little yellowing, and has high anti-glare properties. To prepare the film, the haze and gloss are mainly adjusted, but this does not necessarily correlate with the anti-glare properties. That is, in order to improve the antiglare property, it is necessary to reduce the light scattering that causes high haze. It is necessary to improve the anti-glare property, and there is a trade-off between anti-glare property and transparency (especially suppression of yellowing). It was difficult to balance the two.

[0005] In Japanese Patent No. 5531388 (Patent Document 2), an optical sheet with good contrast is developed. As a method for supplying the transparent substrate at a predetermined temperature, a method is provided in which a functional layer is provided on at least one surface of the transparent substrate, and the functional layer In a manufacturing method of an optical sheet having a diffusing element on the outermost surface and / or inside thereof, The ratio of the diffuse specular reflection intensity to the total diffuse reflection intensity measured in the This discloses a method for stably producing an optical sheet with excellent contrast by controlling the are.

[0006] However, even optical sheets obtained by this method do not have sufficient anti-glare properties depending on the application. . [Prior art documents] [Patent documents]

[0007] [Patent Document 1] JP 2014-85371 A (Claim 1, paragraph

[0021] ) [Patent Document 2] Patent No. 5531388 (Claim 1) Summary of the Invention [Problem to be solved by the invention]

[0008] Therefore, an object of the present invention is to provide an antiglare film that can achieve both color and antiglare properties, and a method for producing the same. The present invention aims to provide a method and an application thereof.

[0009] Another object of the present invention is to provide an antiglare film having little yellow tint and high transparency, and a method for producing the same. and uses thereof. [Means for solving the problem]

[0010] As a result of extensive research to achieve the above object, the present inventors have found that The ratio of the intensity of diffuse specular reflection R to the intensity of diffuse specular reflection R is 0.01 to 0.12, and the chromaticity of transmitted light b * By preparing an anti-glare film with an absolute value of 3 or less, both color and anti-glare properties can be achieved. This has led to the completion of the present invention.

[0011] That is, the antiglare film of the present invention has a ratio of the diffuse specular reflection intensity R to the total diffuse reflection intensity V. R / V is the ratio of (In the formula, the diffuse specular reflection intensity R is the intensity of the reflection measured from the normal to the surface of the anti-glare film.) The direction of diffuse reflection when irradiated with visible light at an angle of 5 degrees, measured at an aperture angle of 1 degree using a variable angle photometer. The measured diffuse reflection intensity is the sum of the diffuse reflection intensities, V, which is the measurement target of the anti-glare film. The direction of diffuse reflection when visible light is irradiated onto the surface at an angle of 45 degrees from the normal , measured at an aperture angle of 1 degree from -45 degrees to +45 degrees, including 0 degrees, using a variable angle photometer. (The sum of the diffuse reflection intensities) is 0.01 to 0.12, and the chromaticity of the transmitted light b * The absolute value of the antiglare property is 3 or less. The film comprises a transparent substrate layer and an antiglare layer formed on at least one surface of the transparent substrate layer. The antiglare layer comprises one or more polymer components and one or more cured resin precursor components. The curable composition may be a cured product of the curable composition containing the polymer component and the curable resin precursor component. At least two components selected from the group consisting of: The polymer component may be a cellulose ester and / or a polymerizable group. The curable resin precursor component may contain a (meth)acrylic polymer. (meth)acrylate, epoxy (meth)acrylate, polyester (meth)acrylate acrylate, urethane (meth)acrylate and silicone (meth)acrylate. The curable resin precursor component may contain at least one of silica nanoparticles and and / or fluorine atoms.

[0012] The present invention also provides the method for producing the curable composition, comprising the step of curing the curable composition with heat or active energy rays. A method for producing an antiglare film is also included. This method comprises depositing one or more polymers on a support. and one or more curable resin precursor components, and then drying the curable composition. At least two components selected from the polymer component and the curable resin precursor component are mixed by humidifying. The curing step may further include a phase separation step of performing phase separation by spinodal decomposition. The step is a curing step in which the phase-separated curable composition is cured by heat or active energy rays. That's fine.

[0013] The present invention also includes a display device equipped with the antiglare film. It may be an LCD or liquid crystal display device.

[0014] In the present invention, the R / V and chromaticity b * The absolute values ​​of 0.01 to 0.12 and 3 Also included is a method of adjusting the content within the following ranges to improve the antiglare properties and transparency of the antiglare film.

[0015] In this specification and claims, (meth)acrylate refers to methacrylic acid. This includes both esters and acrylate esters. [Effects of the Invention]

[0016] In the present invention, the R / V of the antiglare film is 0.01 to 0.12, and the chromaticity of the transmitted light is b * Since the absolute value of is 20 or less, both color and anti-glare properties can be achieved. By subjecting the polymer composition to wet spinodal decomposition, it is possible to reduce yellowness while maintaining anti-glare properties. This can reduce yellowing and improve transparency. DETAILED DESCRIPTION OF THE INVENTION

[0017] [Optical properties of anti-glare film] The antiglare film of the present invention has a ratio of the diffuse specular reflection intensity R to the sum of the diffuse reflection intensities V, R / V and transmitted light chromaticity b * The absolute value of is adjusted to a specific range, so anti-glare and transparent You can balance sex.

[0018] The R / V of the antiglare film of the present invention may be 0.01 to 0.12. to 0.1, preferably 0.01 to 0.08, more preferably 0.01 to 0.05 (especially If R / V is too large, the antiglare properties will decrease and If it is too thin, the transparency decreases.

[0019] In this specification and claims, R / V is the same as that in Japanese Patent No. 5531388 In detail, the measurement can be performed by the method described in the Examples below.

[0020] The antiglare film of the present invention also has reduced yellowness, and the chromaticity (transmitted hue) of transmitted light is * of The absolute value should be 3 or less (for example, 0 to 3), but it should be 2.5 or less (for example, 0.01 to 1.0). 2.5), preferably 2 or less (e.g., 0.05 to 2), and more preferably 1 or less (e.g., If the yellowness is too high, the color will become dull due to increased yellow or blue hues. Visible and less transparent.

[0021] In this specification and claims, the transmitted hue b * is in accordance with JIS Z8781 In accordance with the above, measurements were taken using a spectrophotometer (Hitachi High-Tech Science Corporation "U-3010"). It can be determined.

[0022] The antiglare film of the present invention may have a high haze. The haze of the film is 30% or more (e.g., 30-100%), e.g., 50-98%; Preferably, it is about 70 to 97%, more preferably about 80 to 96% (particularly about 85 to 95%). If the haze is too low, the antiglare properties may be reduced.

[0023] The total light transmittance of the antiglare film of the present invention is, for example, 70% or more (for example, 70 to 100%). Preferably, it is about 80 to 99.9%, more preferably about 85 to 99% (particularly about 90 to 98%). If the total light transmittance is too low, there is a risk of the transparency decreasing.

[0024] In this specification and claims, the haze and total light transmittance are determined in accordance with JIS K In accordance with 7105, a haze meter (Nippon Denshoku Industries Co., Ltd. "NDH-5000W") was used. It can be measured using

[0025] The 60-degree gloss of the antiglare film of the present invention (the antiglare film is a laminate of an antiglare layer and a transparent substrate layer) In the case of a transparent antiglare layer, the 60 degree gloss of the surface of the antiglare layer may be 90% or less, for example, 0 to 2 5%, preferably 0.1 to 20% (for example, 0.2 to 10%), and more preferably 0.3 to 5% (especially 0.5 to 1%). If the 60-degree gloss is too high, the anti-glare properties will decrease. There is a risk.

[0026] In this specification and claims, 60 degree gloss is in accordance with JIS K8741. The gloss can be measured using a gloss meter ("IG-320" manufactured by Horiba, Ltd.).

[0027] [Anti-glare layer] The antiglare film of the present invention may include an antiglare layer for exhibiting the optical properties described above, There are no restrictions on the material or structure, but it is usually made of a transparent material with a finely textured surface. This uneven surface reduces the glare of the outside world caused by surface reflection, improving anti-glare properties. It can be done.

[0028] The antiglare film of the present invention may be formed of an antiglare layer alone, or may be formed of a transparent substrate layer and the antiglare layer. The light-transmitting layer may further include an antiglare layer formed on at least one surface of the light substrate layer.

[0029] The antiglare layer may be made of any transparent material, either organic or inorganic. However, from the viewpoint of productivity and handling, it is preferable to form the film from a composition containing a resin component. As described above, the surface of the antiglare layer usually has an uneven shape. The uneven shape is not particularly limited, and may be formed by physical processing or transfer using a mold. However, from the viewpoint of productivity, it is preferable to use a composition containing a resin component. In the anti-glare layer, the fine irregularities and particle structure formed by the phase separation structure of the resin component are In particular, it is preferable that the surface of the substrate is formed of one or more cured resin precursor components. In the cured product of a curable composition containing the component, spinodal decomposition (wet spinodal decomposition) from the liquid phase occurs. The uneven shape formed by the decomposition of the particles (e.g., thermoplastic resin particles such as polyamide particles) Fat particles, cross-linked poly(meth)acrylate particles, cross-linked polystyrene particles, cross-linked poly The depressions formed by the particle shape are formed by including cross-linked polymer particles such as polyurethane particles. A convex shape is preferred, and a wet-spun film is preferred because it is easy to form a convex-concave shape that can achieve both transparency and antiglare properties. The irregular shape formed by pinodal decomposition is particularly preferred.

[0030] The anti-glare layer having a rough surface formed by wet spinodal decomposition is made of one or more polymers. The curable composition may be a cured product of a curable composition containing the component and one or more curable resin precursor components. Specifically, the antiglare layer is made of one or more polymer components, one or more curable resin precursor components, and a solvent. A composition (mixture) containing the above is used, and the solvent is evaporated or removed from the liquid phase of the composition by drying or the like. During the removal process, as the concentration increases, phase separation occurs due to spinodal decomposition, and the interphase distance More specifically, the wet spinodal decomposition can form a relatively regular phase separation structure. In general, the composition (homogeneous solution) is coated on a support, and the solvent is evaporated from the coating layer. When a peelable support is used as the support, By peeling the antiglare layer from the support, an antiglare film consisting of only the antiglare layer can be obtained. By using a transparent non-peeling support (transparent substrate layer) as the support, Therefore, an antiglare film having a laminated structure composed of a polymer layer and an antiglare layer can be obtained.

[0031] (polymer component) As the polymer component, a thermoplastic resin is usually used. There are no particular limitations as long as the clarity is high and the aforementioned surface irregularities can be formed by spinodal decomposition. However, for example, styrene-based resins, (meth)acrylic polymers, organic acid vinyl ester polymers, Polymers, vinyl ether polymers, halogen-containing resins, polyolefins (alicyclic polyolefins) (including vinyl), polycarbonate, polyester, polyamide, thermoplastic polyurethane, Polysulfone resin (polyethersulfone, polysulfone, etc.), polyphenylene ether ester resins (polymers of 2,6-xylenol, etc.), cellulose derivatives (cellulose esters, esters, cellulose carbamates, cellulose ethers, etc.), silicone resins (polyesters, polydimethylsiloxane, polymethylphenylsiloxane, etc.), rubber or elastomer ( Diene rubbers such as polybutadiene and polyisoprene, styrene-butadiene copolymers, Acrylonitrile-butadiene copolymer, acrylic rubber, urethane rubber, silicone rubber These thermoplastic resins may be used alone or in combination. Can be used.

[0032] Among these polymer components, styrene resins, (meth)acrylic polymers, vinyl acetate vinyl ether polymers, halogen-containing resins, alicyclic polyolefins, poly Carbonate, polyester, polyamide, cellulose derivatives, silicone resin, rubber In addition, the polymer component is generally non-crystalline. and organic solvents (especially common solvents that can dissolve multiple polymer components and cured resin precursor components). ) soluble polymer components are used. In particular, it is highly moldable or film-forming, transparent, and weather-resistant. Polymer components, such as styrene-based resins, (meth)acrylic polymers, alicyclic polyolefins Preferred are vinyl resins, polyester resins, cellulose derivatives (cellulose esters, etc.), etc. Of these, (meth)acrylic polymers and cellulose esters are particularly preferred.

[0033] The (meth)acrylic polymer may be a homopolymer or copolymer of a (meth)acrylic monomer; Copolymers of (meth)acrylic monomers and copolymerizable monomers can be used. Acrylic monomers include, for example, (meth)acrylic acid; methyl (meth)acrylate; ) Ethyl acrylate, (meth) butyl acrylate, (meth) t-butyl acrylate, (meth) acrylate p) Isobutyl acrylate, hexyl (meth)acrylate, octyl (meth)acrylate (Meth)acrylic acid C such as 2-ethylhexyl (meth)acrylate 1-10 Alkyl ; (meth) acrylate aryl such as phenyl (meth) acrylate; hydroxyethyl ( hydroxyalkyl (meth)acrylate, hydroxypropyl (meth)acrylate, etc. Glycidyl (meth)acrylate; Glycidyl (meth)acrylate; N,N-Dialkylamino Alkyl (meth)acrylate; (meth)acrylonitrile; tricyclodecane and other fats Examples of the copolymerizable monomer include (meth)acrylates having a cyclic hydrocarbon group. Styrene-based monomers such as styrene, vinyl ester-based monomers, maleic anhydride, maleic These monomers may be used alone or in combination of two or more. Can be used.

[0034] Examples of the (meth)acrylic polymer include poly(meth)acrylate and the like. (meth)acrylic acid ester, methyl methacrylate-(meth)acrylic acid copolymer, methacrylate Methyl methacrylate-(meth)acrylic acid ester copolymer, Methyl methacrylate-acrylic acid ester copolymer Steryl-(meth)acrylic acid copolymer, (meth)acrylic acid ester-styrene copolymer (MS resin, etc.) are examples. Among these, polymethyl (meth)acrylate, etc. Poly(meth)acrylic acid C 1-6 Alkyl, especially methyl methacrylate, is the main component (50- 100% by weight, preferably about 70 to 100% by weight) of a methyl methacrylate polymer is preferred.

[0035] Examples of cellulose esters include aliphatic organic acid esters (cellulose diacetate, cellulose acetates such as cellulose acetate and cellulose triacetate; cellulose propionate cellulose acetate, cellulose butyrate, cellulose acetate propionate, cellulose acetate C such as butylate 1-6 Aliphatic carboxylic acid esters, etc.), aromatic organic acid esters ( C such as cellulose phthalate and cellulose benzoate 7-12 Aromatic carboxylic acids esters), inorganic acid esters (e.g., cellulose phosphate, cellulose sulfate, etc.), etc. These may be mixed acid esters such as cellulose acetate and cellulose nitrate esters. The cellulose esters can be used alone or in combination of two or more. Cellulose diacetate, cellulose triacetate, cellulose acetate propionate Cellulose C such as cellulose acetate and cellulose acetate butyrate 2―4 Acylates are preferred. , cellulose acetate C such as cellulose acetate propionate 3-4 Acylates is particularly preferred.

[0036] The polymer component [particularly the (meth)acrylic polymer] has a functional group (or The polymer may be a polymer having a functional group capable of reacting with the curable resin precursor component. The functional group may be present in the main chain or in the side chain. Although it may be introduced into the main chain by polymerization or co-condensation, it is usually introduced into the side chain. The functional groups include condensable groups and reactive groups (e.g., hydroxyl groups, acid anhydride groups, carboxyl groups, etc.). silyl group, amino group or imino group, epoxy group, glycidyl group, isocyanate group, etc.), Polymerizable groups (e.g., C2 such as vinyl, propenyl, isopropenyl, butenyl, and allyl) -6 Alkenyl groups, such as ethynyl, propynyl, and butynyl 2-6 Alkynyl group, vinyl C such as Liden 2-6 Alkenylidene groups or groups having these polymerizable groups [(meth)alkenylidene groups] Among these functional groups, polymerizable groups are preferred. stomach.

[0037] As a method for introducing a polymerizable group into a side chain, for example, a functional group such as a reactive group or a condensable group can be introduced. a method of reacting a thermoplastic resin having a functional group with a polymerizable compound having a group reactive with the functional group; Examples include laws.

[0038] In the thermoplastic resin having a functional group, the functional group is a carboxyl group or an acid-free group thereof. Examples include a hydrate group, a hydroxyl group, an amino group, and an epoxy group.

[0039] The thermoplastic resin having a functional group is a thermoplastic resin having a carboxyl group or an acid anhydride group thereof. In the case of the polymerizable compound having a group reactive with the functional group, for example, an epoxy resin may be used. Examples include polymerizable compounds with hydroxyl, amino, and isocyanate groups. Among these, polymerizable compounds having an epoxy group, such as epoxycyclohexyl Epoxycyclo C such as xenyl (meth)acrylate 5-8 Alkenyl(meth)acrylate Glycidyl (meth)acrylate, allyl glycidyl ether, etc. are commonly used. .

[0040] A typical example is a thermoplastic resin having a carboxyl group or an acid anhydride group thereof and an epoxy resin. Compounds containing hydroxy groups, especially (meth)acrylic polymers ((meth)acrylic acid-(meth)acrylic acid acrylate copolymer, etc.) and epoxy group-containing (meth)acrylate (epoxycyclo Alkenyl (meth)acrylate and glycidyl (meth)acrylate Specifically, a polymerizable compound is polymerized to a part of the carboxyl group of the (meth)acrylic polymer. Polymers into which a non-saturated group has been introduced, such as (meth)acrylic acid-(meth)acrylic acid esters Some of the carboxyl groups of the ester copolymer are substituted with 3,4-epoxycyclohexenylmethyl acrylate. The epoxy group of the acrylate was reacted to introduce a polymerizable group (photopolymerizable unsaturated group) into the side chain ( A methacrylic polymer (Cyclomer P, manufactured by Daicel Corporation) or the like can be used.

[0041] The amount of functional groups (especially polymerizable groups) involved in the hardening reaction of thermoplastic resins is determined by the amount of thermoplastic resin. The amount of the hydroxybenzoate is 0.001 to 10 mol, preferably 0.01 to 5 mol, more preferably 0.01 to 5 mol, per 1 kg of the hydroxybenzoate resin. The amount is preferably about 0.02 to 3 moles.

[0042] These polymer components can be used in appropriate combination. The polymer may be composed of a plurality of polymers. The plurality of polymers may be produced by wet spinodal decomposition. Alternatively, the polymers may be incompatible with each other. When multiple polymers are combined, the combination of the first polymer and the second polymer is not particularly limited, but may be a plurality of polymers that are incompatible with each other near the processing temperature, for example, Two incompatible polymers can be used in combination. For example, the first polymer (meth)acrylic polymers (e.g., polymethyl methacrylate, (meth)acrylic polymers having a polymerizable group When the second polymer is a cellulose ester (cellulose ester, etc.), Cellulose acetate C, such as cellulose acetate propionate 3-4 Acylates, etc. ), or polyester (urethane-modified polyester, etc.).

[0043] Furthermore, from the viewpoint of scratch resistance after curing, at least one of the multiple polymers is For example, one of the polymers that are incompatible with each other (the first polymer and the second polymer) When a polymer is combined with the cured resin precursor component, at least one of the polymers reacts with the cured resin precursor component. It is preferable that the polymer has a reactive functional group (particularly a polymerizable group) on the side chain.

[0044] The weight ratio of the first polymer to the second polymer is, for example, the former / the latter=1 / 99 to 9 The ratio can be selected from the range of about 9 / 1, preferably 5 / 95 to 95 / 5, and the first polymer is ( When the first polymer is an acrylic polymer and the second polymer is a cellulose ester, both polymers The weight ratio of the polymer to the former is 50 / 50 to 99 / 1, preferably 55 / 45 to 90 / 10, more preferably 60 / 40 to 80 / 20 (especially 65 / 35 to 75 / 25) is.

[0045] The polymer for forming the phase separation structure may be any polymer other than the two incompatible polymers described above. In addition, the thermoplastic resins and other polymers may be included.

[0046] The glass transition temperature of the polymer component is, for example, −100° C. to 250° C., preferably −50° C. to 230°C, more preferably in the range of about 0 to 200°C (for example, about 50 to 180°C) From the viewpoint of surface hardness, the glass transition temperature is preferably 50°C or higher (for example, 70°C to 200°C), preferably 100°C or higher (for example, about 100 to 170°C). The weight average molecular weight of the polymer component is, for example, 1,000,000 or less, preferably can be selected from a range of approximately 1,000 to 500,000.

[0047] (cured resin precursor component) The curable resin precursor component is a material that can be cured by heat or active energy rays (ultraviolet rays, electron beams, etc.). It is a compound that has a reactive functional group and is cured or crosslinked by heat or active energy rays. Various curable compounds capable of forming a resin (particularly a cured or crosslinked resin) can be used. The curable resin precursor component may be, for example, a thermosetting compound or resin [epoxy group, polymerizable group]. , low molecular weight compounds having an isocyanate group, an alkoxysilyl group, a silanol group, etc. ( For example, epoxy resin, unsaturated polyester resin, urethane resin, silicone resin photocurable compounds that can be cured by actinic rays (ultraviolet rays, etc.) Examples of photo-curable compounds include ultraviolet curable compounds such as monomers and oligomers. EB (electron beam) curable compounds, etc. Photocurable compounds such as photocurable resins, which may be of low molecular weight or low molecular weight, are simply referred to as "photocurable resins." " Sometimes it is said that

[0048] The photocurable compound may be, for example, a monomer or an oligomer (or a resin, particularly a low-molecular-weight resin). Included.

[0049] Examples of the monomer include monofunctional monomers [(meth)acrylates and the like] ) Acrylic monomers, vinyl monomers such as vinylpyrrolidone, isobornyl (meth)acrylate (meth)acrylate, adamantyl (meth)acrylate, and other methacrylates having a bridged cyclic hydrocarbon group acrylate, etc.], a polyfunctional monomer having at least two polymerizable unsaturated bonds [ Ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate Butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate alkylene glycol di(meth)acrylate, hexanediol di(meth)acrylate, etc. meth)acrylate; diethylene glycol di(meth)acrylate, dipropylene glycol Polyoxytetramethylene glycol di(meth)acrylate (Poly)oxyalkylene glycol di(meth)acrylates such as tricyclodecane; Candimethanol di(meth)acrylate, adamantane di(meth)acrylate, etc. Di(meth)acrylates containing bridged cyclic hydrocarbon groups; glycerin tri(meth)acrylate acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri( meth)acrylate, pentaerythritol tri(meth)acrylate, ditrimethylol Dipropane tetra(meth)acrylate, Pentaerythritol tetra(meth)acrylate Dipentaerythritol penta(meth)acrylate, Dipentaerythritol hexa(meth)acrylate Polyfunctional monomers with 3 to 6 polymerizable unsaturated bonds, such as hexa(meth)acrylate Examples include:

[0050] As the oligomer or resin, bisphenol A-alkylene oxide adduct (methacrylamide, methyl methacrylate ... bisphenol A epoxy (meth)acrylate, epoxy (meth)acrylate ) acrylate, novolac epoxy (meth) acrylate, etc.], polyester (meth) acrylate (meth)acrylates [e.g., aliphatic polyester (meth)acrylates, aromatic polyesters, steric (meth)acrylates, etc.], (poly)urethane (meth)acrylates [polyester Sterile urethane (meth)acrylate, polyether urethane (meth)acrylate etc.], silicone (meth)acrylate, etc. can be exemplified.

[0051] These photocurable compounds can be used alone or in combination of two or more. , photo-curable compounds that can be cured in a short time, such as ultraviolet curable compounds (monomers, oligomers, etc.) EB-curable compounds are preferred. The resin precursor advantageous for this purpose is an ultraviolet curable resin. In order to achieve this, the photocurable resin has two or more (preferably 2 to 6, more preferably 2 to 6) groups in the molecule. It is preferable that the compound has a polymerizable unsaturated bond of about 4.

[0052] The weight average molecular weight of the curable resin precursor component is not particularly limited, but may be selected from the group consisting of gel permeation In chromatography (GPC), compatibility with polymers is considered in terms of polystyrene. It is about 5000 or less, preferably 2000 or less, and more preferably about 1000 or less. .

[0053] The curable resin precursor component may be selected from a group consisting of a film, a glass, a glass substrate ... It may contain fillers and / or fluorine atoms.

[0054] Examples of the filler include silica particles, titania particles, zirconia particles, and alumina particles. inorganic particles, cross-linked (meth)acrylic polymer particles, cross-linked styrene resin particles, etc. These fillers may be used alone or in combination of two or more. Can be used.

[0055] Among these fillers, the one with excellent optical properties is the one with transparency and anti-glare properties due to spinodal decomposition. Nanometer-sized silica particles (silica nanoparticles) are used because they are easy to form uneven shapes that can achieve both high and low thermal conductivity. Silica nanoparticles are preferred because they can suppress the yellowness of the anti-glare film. The average particle size of the silica nanoparticles is, for example, 1 to 800 nm, preferably about 3 to 500 nm, and more preferably about 5 to 300 nm.

[0056] The ratio of filler (especially silica nanoparticles) to the total curable resin precursor components is 10 to 9 It may be about 0% by weight, for example, 10 to 80% by weight, preferably 15 to 70% by weight, More preferably, it is about 20 to 50% by weight.

[0057] A precursor component containing fluorine atoms (a fluorine-containing curable compound or a fluorine-containing compound having a polymerizable group) Examples of the alkyl fluoride compounds include fluorides of the above-mentioned monomers and oligomers, such as alkyl fluorides. (Meth)acrylates [e.g., perfluorooctylethyl (meth)acrylate and trifluorooctylethyl (meth)acrylate] trifluoroethyl (meth)acrylate, etc.], fluorinated (poly)oxyalkylene glycol Di(meth)acrylate [e.g., fluoroethylene glycol di(meth)acrylate] Fluoropolyethylene glycol di(meth)acrylate, Fluoropropylene glycol Fluorine-containing epoxy resin, fluorine-containing urethane Among these, fluoropolymers having (meth)acryloyl groups are The fluorine-containing curable compound is preferably a commercially available fluorine-based polymerizable ether compound. It may also be a blocking agent.

[0058] The curable resin precursor component may further contain a curing agent depending on the type of the component. For example, In the case of a thermosetting resin, a curing agent such as an amine or a polycarboxylic acid may be contained. The curable resin may contain a photopolymerization initiator. The photopolymerization initiator may be a conventional component, such as For example, acetophenones or propiophenones, benzils, benzoins, benzo Examples include phenones, thioxanthones, and acylphosphine oxides. The ratio of the curing agent such as the initiator is 0.1 to 20% by weight based on the total curable resin precursor components, preferably The content is preferably about 0.5 to 10% by weight, and more preferably about 1 to 8% by weight.

[0059] The curable resin precursor component may further contain a curing accelerator. is a photocuring accelerator, for example, tertiary amines (dialkylaminobenzoic acid esters, etc.) , a phosphine-based photopolymerization accelerator, and the like.

[0060] Among these curable resin precursor components, polyfunctional (meth)acrylates (e.g., diphenyl acrylates) Polyacrylates having 2 to 8 polymerizable groups (methacrylates) such as thiaerythritol hexa(meth)acrylate (meth)acrylate, epoxy (meth)acrylate, polyester (meth)acrylate acrylate, urethane (meth)acrylate, silicone (meth)acrylate, etc. are preferred. Furthermore, the curable resin precursor component preferably contains silica nanoparticles and / or fluorine atoms. Preferably, a photocurable compound containing silica nanoparticles [particularly, a polyfunctional (meth)acrylate containing silica nanoparticles] is used. methacrylate, urethane (meth)acrylate containing silica nanoparticles, silica nanoparticles Silicone (meth)acrylates containing fluorine-containing curable compounds are particularly preferable.

[0061] A preferred combination of curable resin precursor components is, for example, a silica nanoparticle-containing photocurable resin. Combination of silicone (meth)acrylate and urethane (meth)acrylate and tri- to hexafunctional (meth)acrylates, silicone (meth)acrylates, and fluorine-containing curing agents and a combination of a photocurable compound containing silica nanoparticles and a fluorine-containing photocurable compound. A particularly preferred combination is a silica nanoparticle-containing photocurable compound. and a fluorine-containing curable compound.

[0062] In the present invention, silica nanoparticles are used because they are easy to form a roughened shape that can achieve both transparency and antiglare properties. The particles are added to the curable resin precursor component in the above proportion relative to the entire curable resin precursor component. Preferably, the curable resin precursor contains a silica nanoparticle-containing curable resin precursor component. The proportion of the compound is, for example, 0.001 to 1% by weight (for example, 0.01 to 0.5% by weight, preferably 0.02 to 0.3% by weight (for example, 0.03 to 0 0.2% by weight, and more preferably about 0.05 to 0.1% by weight.

[0063] (Combination of polymer component and curable resin precursor component) In the present invention, at least two of the polymer component and the curable resin precursor component are The components are used in a combination that causes phase separation near the processing temperature. Examples of the combination include (a) a combination in which multiple polymer components are incompatible with each other and undergo phase separation. (b) a combination in which the polymer component and the curable resin precursor component are incompatible and phase-separated, c) A combination in which multiple curable resin precursor components are incompatible with each other and undergo phase separation. Among these combinations, (a) combinations of multiple polymer components and (b) a combination of a polymer component and a curable resin precursor component, particularly (a) a combination of a plurality of polymer components When the compatibility of the two components to be phase-separated is high, the solvent is preferably During the drying process for evaporation, the two do not effectively separate into phases, and the function as an antiglare layer is reduced.

[0064] The polymer component and the curable resin precursor component are usually incompatible with each other. When the component and the cured resin precursor component are incompatible and undergo phase separation, When multiple polymer components are used, at least one polymer component The component is only required to be incompatible with the curable resin precursor component, and the other polymer components are not required to be compatible with the curable resin precursor component. The resin precursor component may be compatible with the polymer component. Alternatively, two polymer components and a cured resin that are incompatible with each other may be used. Combination with precursor components (especially monomers or oligomers having multiple curable functional groups) This may also be the case.

[0065] When the polymer component is composed of multiple incompatible polymer components and phase separation occurs, The liposome precursor component is processed with at least one polymer component from among multiple incompatible polymers. In other words, multiple polymers that are incompatible with each other are used in combination at temperatures close to the When the component is composed of, for example, a first polymer and a second polymer, the cured resin precursor The component only needs to be compatible with either the first polymer or the second polymer, and both polymers It may be compatible with one of the polymer components, but it is preferably compatible with only one of the polymer components. When the first polymer and the curable resin precursor component are compatible with each other, and a mixture based on at least one of a second polymer and a curable resin precursor component. The mixture also separates into two phases.

[0066] If the selected polymer components are highly compatible, the solvent can be evaporated during the drying process. The polymer components do not effectively separate into phases, and the function of the antiglare layer is reduced. The phase separation of the components was evaluated by preparing a homogeneous solution using a good solvent for both components and gradually removing the solvent. During the evaporation process, it can be easily determined by visually checking whether the remaining solids become cloudy or not. It can be determined.

[0067] Furthermore, the polymer component and the cured or crosslinked resin produced by curing the curable resin precursor component are usually The refractive index of each of the bridge resins is different. The refractive index of the polymer component and the cured or crosslinked resin are different. The difference in refractive index between the multiple polymer components (the first polymer and the second polymer) is, for example, 0. It may be about 0.01 to 0.2, preferably about 0.05 to 0.15.

[0068] The ratio (weight ratio) of the polymer component to the curable resin precursor component is not particularly limited, and may be, for example, Former / latter = 1 / 99~95 / 5, for example, 2 / 98~90 / 10 , preferably 3 / 97 to 80 / 20, and more preferably 5 / 95 to 70 / 30. In addition, when the curable resin precursor component contains a photocurable compound containing silica nanoparticles, the polymer The ratio (by weight) of the component to the curable resin precursor component is, for example, 2 / 98 to 30 / 70, preferably The range is preferably 3 / 97 to 20 / 80, and more preferably 5 / 95 to 15 / 85. Furthermore, when the curable resin precursor component does not contain a silica nanoparticle-containing photocurable compound, e.g. For example, 10 / 90 to 60 / 40, preferably 20 / 80 to 50 / 50, and more preferably 3 It may be around 0 / 70 to 40 / 60.

[0069] (Other ingredients) The antiglare layer formed from a composition containing a resin component may contain various additives, such as a leveling agent, Stabilizers (antioxidants, UV absorbers, etc.), surfactants, water-soluble polymers, fillers, crosslinking agents , coupling agents, colorants, flame retardants, lubricants, waxes, preservatives, viscosity modifiers, thickeners, extinguishing agents The proportion of the additives may be, for example, 0.01 to 0.01% based on the total amount of the antiglare layer. It is about 0.01 to 10% by weight (particularly 0.1 to 5% by weight).

[0070] (Thickness of anti-glare layer) The thickness (average thickness) of the antiglare layer is, for example, about 0.3 to 20 μm, preferably 1 to 15 μm. (for example, 1 to 10 μm), and usually 3 to 12 μm (particularly 4 to 10 μm). In addition, when the anti-glare film is composed of an anti-glare layer alone, the thickness (average thickness) of the anti-glare layer is, for example, about 1 to 100 μm, and preferably about 3 to 50 μm.

[0071] (Transparent base layer) The transparent substrate layer may be made of any transparent material, and may be selected depending on the intended use. However, organic materials are generally used in terms of strength and moldability. Examples of materials include cellulose derivatives, polyester, polyamide, polyimide, and polyamide. Examples of the polymers include cellulose acetate and (meth)acrylic polymers. Esters, polyesters, etc. are commonly used.

[0072] Cellulose esters include cellulose triacetate (TAC) and other cellulose acetate, cellulose acetate propionate, cellulose acetate butyrate, etc. Which cellulose acetate C 3-4 acylates, etc. Polyesters include , polyethylene terephthalate (PET), polyethylene naphthalate (PEN), etc. Examples include polyalkylene arylates.

[0073] Among these, PET and PEN are preferred due to their excellent balance of mechanical properties and transparency. Which Poly C 2-4 Alkylene arylates are preferred.

[0074] The transparent substrate layer may also contain the conventional additives exemplified in the section on the antiglare layer. The same applies to the antiglare layer.

[0075] The transparent substrate layer may be a uniaxially or biaxially stretched film, but has a low birefringence and is optically The film may be an unstretched film because it has excellent isotropy in terms of the film structure.

[0076] The transparent substrate layer may be subjected to a surface treatment (for example, corona discharge treatment, flame treatment, plasma treatment, ozone treatment, etc.). The adhesive layer may be subjected to treatment such as ultraviolet irradiation or the like, and may have an easy-adhesion layer.

[0077] The thickness (average thickness) of the transparent substrate layer is, for example, 5 to 2000 μm, preferably 15 to 100 0 μm, and more preferably about 20 to 500 μm.

[0078] (Adhesive layer) The antiglare film of the present invention is suitable for various devices including smartphones and PCs (tablet PCs, etc.). It can also be used as a protective film for various touch panel display devices. An adhesive layer may be formed on at least a part of the other surface of the transparent substrate layer.

[0079] The adhesive layer is formed of a conventional transparent adhesive. Examples of the adhesive include rubber-based adhesives. Adhesives, acrylic adhesives, olefin adhesives (modified olefin adhesives, etc.), silicone Among these adhesives, those with optical properties and reworkability are Therefore, silicone-based adhesives are preferred.

[0080] The thickness of the adhesive layer is, for example, 1 to 150 μm, preferably 10 to 100 μm, and more preferably It is preferably about 20 to 70 μm (particularly 25 to 50 μm).

[0081] The adhesive layer may be formed on the entire other surface, or on a part of the other surface (for example, the peripheral portion). Furthermore, when it is formed on the peripheral portion, it is possible to improve the handling property for application. In order to prevent this, a frame-shaped member (for example, a plastic sheet) is attached to the periphery of the anti-glare film. and then forming an adhesive layer on the frame-shaped member.

[0082] [Anti-glare film manufacturing method] The method for producing the antiglare film of the present invention is not particularly limited, and can be appropriately selected depending on the type of material. It can be formed by physical processing or transfer using a mold, but from the viewpoint of productivity, A preferred method for producing the curable composition is a curing step in which the curable composition is cured with heat or active energy rays. In particular, an antiglare layer having an uneven surface formed by wet spinodal decomposition is preferable. In the case of a glare film, one or more polymer components and one or more polymer components are formed on a support (particularly a transparent substrate layer). By applying and drying a curable composition containing the above-mentioned curable resin precursor component, a polymer At least two components selected from the group consisting of a component and a curable resin precursor component are mixed in a wet spinodal a phase separation step of subjecting the phase-separated curable composition to heat or active energy rays; The method may also include a curing step in which the resin is cured by heating.

[0083] In the phase separation step, the curable composition may contain a solvent. The composition can be selected depending on the type and solubility of the component and the curable resin precursor component, and at least the solid content (e.g. For example, multiple polymer components, curable resin precursor components, reaction initiators, and other additives are mixed uniformly. In particular, the solvent for the polymer component and the cured resin precursor is The phase separation structure may be controlled by adjusting the solubility of the solvent. For example, ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexane xanone, ethers (dioxane, tetrahydrofuran, etc.), aliphatic hydrocarbons hydrocarbons (hexane, etc.), alicyclic hydrocarbons (cyclohexane, etc.), aromatic hydrocarbons (trimethylsilyl) toluene, xylene, etc.), halogenated carbons (dichloromethane, dichloroethane, etc.), Esters (methyl acetate, ethyl acetate, butyl acetate, etc.), water, alcohols (ethanol alcohol, isopropanol, butanol, cyclohexanol, etc.), cellosolves [methyl Cellosolve, Ethyl Cellosolve, Propylene Glycol Monomethyl Ether (1-Methoxy) bis-2-propanol), cellosolve acetates, sulfoxides (dimethyl sulfoxides), amides (dimethylformamide, dimethylacetamide, etc.), etc. The solvent may be a mixed solvent.

[0084] Among these solvents, ketones such as methyl ethyl ketone are preferred. and alcohols (butanol, etc.) and / or cellosolves (1-methoxy-2-propanol, etc.). In the mixed solvent, alcohols and / or propanol are particularly preferred. The ratio of cellosolves (total amount when both are mixed) to 100 parts by weight of ketones is For example, 10 to 150 parts by weight, preferably 15 to 100 parts by weight, and more preferably 20 The amount is about 1 to 80 parts by weight (particularly 25 to 50 parts by weight). When combined, the ratio of cellosolves to alcohols is, for example, 1 10 to 100 parts by weight, preferably 10 to 80 parts by weight, more preferably 30 to 70 parts by weight (particularly In the present invention, by appropriately combining solvents, By controlling the phase separation caused by pinodal decomposition, it is possible to form a textured surface that achieves both transparency and anti-glare properties. Cut.

[0085] Solutes in the mixture (polymer components, cured resin precursor components, reaction initiators, and other additives) The concentration can be selected within a range that does not cause phase separation and does not impair flowability or coating properties. For example, 1 to 80% by weight, preferably 10 to 70% by weight, and more preferably 20 to 60% by weight. It is about % by weight (particularly 30 to 55% by weight).

[0086] The coating method may be a conventional method, such as a roll coater, an air knife coater, or a blade coater. Rod coater, rod coater, reverse coater, bar coater, comma coater, Dip / squeeze coater, die coater, gravure coater, micro gravure coater -, silk screen coater method, dip method, spray method, spinner method, etc. Among these methods, the bar coater method and gravure coater method are commonly used. If necessary, the coating solution may be applied multiple times.

[0087] After the mixture is cast or applied, the mixture is heated at a temperature lower than the boiling point of the solvent (for example, The solvent is evaporated at a temperature lower than the above temperature (1 to 120°C, preferably 5 to 50°C, particularly 10 to 50°C). By evaporating the solvent, phase separation due to spinodal decomposition can be induced. The decomposition is usually carried out at a temperature of 30 to 200°C (e.g., 30 to 100°C) depending on the boiling point of the solvent. ° C.), preferably 40 to 120 ° C., more preferably 50 to 90 ° C. (particularly 60 to 85 ° C.) This can be done by drying at a temperature of about

[0088] The spinodal decomposition accompanying the evaporation of the solvent causes the average between the domains of the phase-separated structure. The distance can be given regularity or periodicity.

[0089] In the curing process, the dried curable composition is exposed to actinic rays (ultraviolet rays, electron beams, etc.) or heat. By finally hardening the material, the phase separation structure formed by spinodal decomposition is directly resolved. The curable composition can be cured by heating, depending on the type of curable resin precursor component. Light irradiation may also be combined.

[0090] The heating temperature can be selected from an appropriate range, for example, from about 50 to 150° C. The type can be selected depending on the type of curing component, and ultraviolet rays, electron beams, etc. are usually used. The light source is typically an ultraviolet light source.

[0091] For example, in the case of ultraviolet light, a deep UV lamp, a low-pressure mercury lamp, High pressure mercury lamp, ultra-high pressure mercury lamp, halogen lamp, laser light source (helium-cadmium The amount of light emitted (irradiation energy) can be adjusted by using light sources such as ion lasers and excimer lasers. The energy (energy) varies depending on the thickness of the coating, for example, 10 to 10,000 mJ / cm 2 , preferably 20~5000mJ / cm 2 , and more preferably 30 to 3000 mJ / cm 2 To an extent If necessary, the light irradiation may be carried out in an inert gas atmosphere.

[0092] [Display device] The antiglare film of the present invention has both transparency and antiglare properties, and therefore can be used in various display devices, e.g. For example, liquid crystal displays (LCDs), organic EL displays, and displays with touch panels. It can be used as an optical component, and is particularly useful as an optical element for LCD and organic EL displays. be.

[0093] Specifically, an LCD is a reflector that uses external light to illuminate a display unit that contains liquid crystal cells. The display unit may be a projection LCD, and may include a backlight unit for illuminating the display unit. In a reflective LCD, incident light from the outside is reflected by the display unit. The light that passes through the display unit is reflected by the reflecting member. In a reflective LCD, the anti-glare filter of the present invention is inserted in the optical path forward from the reflective member. For example, the antiglare film of the present invention can be disposed on the front surface of a display unit (the front surface on the viewing side). ) and the like, and in particular, it has a collimated backlight unit and It may also be disposed in front of an LCD that does not have a sheet.

[0094] In a transmissive LCD, the backlight unit is a light source (a tubular light source such as a cold cathode fluorescent lamp, a Light from a point light source such as a photodiode is incident on one side and emitted from the front exit surface. The light guide plate may be provided to allow light to exit from the light source (for example, a light guide plate having a wedge-shaped cross section). If necessary, a prism sheet may be disposed on the front side of the light guide plate. A reflecting member is provided on the rear surface of the plate to reflect the light from the light source toward the light exit surface. In such a transmission type LCD, the antiglare film of the present invention is usually placed in the optical path forward from the light source. For example, the above-mentioned and the present invention can be arranged between the light guide plate and the display unit, on the front surface of the display unit, etc. The antiglare film of the invention can be disposed or laminated.

[0095] In an organic EL display, each pixel is made up of a light-emitting element. The light-emitting element is generally made up of a cathode such as a metal, an electron injection layer, an electron transport layer, an emitting layer, and a hole transport layer. Transport layer / hole injection layer / positive electrode such as ITO / substrate such as glass plate or transparent plastic plate In an organic EL display, the antiglare film of the present invention is disposed in the optical path. It may be established.

[0096] The antiglare film of the present invention is also suitable for LCDs (LCDs that are also display devices with touch panels). (including organic EL displays) and organic EL displays (which are also display devices with touch panels) Aftermarket protection or protective film to prevent scratches on the It may also be used as a [Example]

[0097] The present invention will be described in more detail below based on examples, but the present invention will not be limited to these examples. The raw materials used in the examples and comparative examples are as follows, and the obtained materials are as follows: The antiglare films thus obtained were evaluated by the following methods.

[0098] [Raw materials] Acrylic polymer with polymerizable groups: Cyclomer P manufactured by Daicel Allnex Co., Ltd. " Cellulose acetate propionate: Eastman "CAP-482-20" Acetylation degree = 2.5%, propionyl degree = 46%, polystyrene equivalent number average molecular weight 7 5000 Silicone acrylate: Daicel Allnex "EB1360" Silicone hard coating material: "AS-201S" manufactured by Tokushiki Co., Ltd. Urethane acrylate A: "U-15HA" manufactured by Shin-Nakamura Chemical Co., Ltd. Urethane acrylate B: "AU-230" manufactured by Tokushiki Co., Ltd. Dipentaerythritol hexaacrylate: "DPH" manufactured by Daicel Allnex Co., Ltd. A” Nanosilica-containing acrylic UV-curable compound: Momentive Performance Materials "XR39-C6210" manufactured by Reals Japan LLC Silica-containing acrylic UV-curable compound: Aica Kogyo Co., Ltd. "Z-757-4RL" " Acrylic UV-curable compound: Aica Kogyo Co., Ltd. "Z-757-4CL" PMMA beads A: SSX-115 manufactured by Sekisui Chemical Co., Ltd. PMMA beads B: SSX-105 manufactured by Sekisui Chemical Co., Ltd. Cross-linked styrene beads: "SX-130H" manufactured by Soken Chemical & Engineering Co., Ltd. Fluorine-based compound A having a polymerizable group: Shin-Etsu Chemical Co., Ltd. "KY-1203" Fluorine-based compound B having a polymerizable group: "Ftergent 602A" manufactured by Neos Co., Ltd. Photoinitiator A: "Irgacure 184" manufactured by BASF Japan Ltd. Photoinitiator B: "Irgacure 907" manufactured by BASF Japan Ltd. Polyethylene terephthalate (PET) film: "Diafoil" manufactured by Mitsubishi Plastics, Inc. Cellulose triacetate (TAC) film: Fujifilm Corporation's "Fujitac T" G60UL".

[0099] [Coat layer thickness] Using an optical film thickness meter, measurements were taken at 10 random locations, and the average value was calculated.

[0100] [Transparent hue (b * )] In accordance with JIS Z8781, a spectrophotometer (Hitachi High-Tech Science Corporation's "U- 3010).

[0101] Diffuse Reflection Intensity The back side of the anti-glare film (the side without the uneven structure, the side opposite to the viewer side) is covered with a transparent adhesive. The sample was attached to a flat black acrylic plate with no irregularities or warping via a tape to prepare an evaluation sample. The evaluation sample was placed on the measuring device, and the surface of the evaluation sample facing the antiglare film was The light beam was incident at an angle of 45 degrees from the normal to the surface. is defined as the direction of diffuse specular reflection, and the reflection intensity in the direction of diffuse specular reflection is defined as R. The light incident on the anti-glare film surface of the sample and diffusely reflected was measured at an angle of -45 degrees to the direction of diffuse specular reflection. The diffuse reflection intensity is measured by scanning the receiver at 1 degree intervals in the range of 1 degree to +45 degrees. The sum of these was defined as V. The diffuse reflection intensity was measured by the equipment manufactured by Murakami Co., Ltd. We used the "GP-200" manufactured by Color Research Institute.

[0102] [Hayes] Using a haze meter (Nippon Denshoku Co., Ltd. "NDH-5000W"), 136, and the measurement was performed by placing the surface with the uneven structure facing the photodetector.

[0103] [60° gloss] Gloss meter (IG-320 manufactured by Horiba Manufacturing Co., Ltd.) conforming to JIS K7105 ) was used to measure at an angle of 60 degrees.

[0104] [Anti-glare] The anti-glare film was attached to a commercially available black acrylic plate with optical glue, and illuminated with a three-wavelength fluorescent lamp. The reflected image was visually observed and evaluated according to the following criteria.

[0105] ◎: Fluorescent lights are completely invisible ○: The outline of the fluorescent light is blurred △: The shape of the fluorescent light is visible, but the glare is reduced.

[0106] [Color] The anti-glare film was held in front of a three-wavelength fluorescent lamp, and the color of the transmitted light was visually observed. It was evaluated according to the following criteria.

[0107] ○: When the film is observed through a fluorescent lamp, it appears colorless and transparent. △: Looks slightly yellow or bluish ×: Visibly yellow or blue.

[0108] [Example 1] 15.0 parts by weight of acrylic polymer having a polymerizable group, cellulose acetate propionate 3 parts by weight of silicate, 150 parts by weight of nanosilica-containing acrylic ultraviolet curing compound, silicone 1 part by weight of acrylate was mixed with 101 parts by weight of methyl ethyl ketone and 24 parts by weight of 1-butanol. The resulting solution was prepared by dissolving the compound in a mixed solvent of the compound and the part.

[0109] This solution was cast onto a PET film using a wire bar (#20), and then The substrate was left in an oven at 0°C for 1 minute to evaporate the solvent, forming a coating layer with a thickness of about 9 µm.

[0110] Then, ultraviolet light was irradiated onto the coating layer from a high-pressure mercury lamp for about 5 seconds (accumulated light intensity of about 10 0mJ / cm 2 The coating layer was then subjected to ultraviolet curing treatment to obtain an antiglare film.

[0111] [Example 2] 12.5 parts by weight of acrylic polymer having polymerizable groups, cellulose acetate propionate 4 parts by weight of acrylate, 150 parts by weight of nanosilica-containing acrylic UV-curable compound, silicone 1 part by weight of acrylate, 81 parts by weight of methyl ethyl ketone, and 24 parts by weight of 1-butanol The compound was dissolved in a mixed solvent containing 13 parts by weight of 1-methoxy-2-propanol to prepare a solution.

[0112] This solution was cast onto a PET film using a wire bar (#20), and then The substrate was left in an oven at 0°C for 1 minute to evaporate the solvent, forming a coating layer with a thickness of about 9 µm.

[0113] Then, the coating layer was irradiated with ultraviolet light from a high-pressure mercury lamp for about 5 seconds. After curing, an antiglare film was obtained.

[0114] [Example 3] 45.6 parts by weight of acrylic polymer having polymerizable groups, cellulose acetate propionate 2.3 parts by weight of urethane acrylate A, 70.7 parts by weight of dipentaerythritol 8.2 parts by weight of hydroxyacrylate, 0.6 parts by weight of silicone acrylate, 0.1 parts by weight of fluorine-based compound B, 1 part by weight of photoinitiator A, and 1 part by weight of photoinitiator B were mixed in a methyl 128 parts by weight of ethyl ketone, 25 parts by weight of 1-butanol, and 31 parts by weight of cyclohexanone The solution was prepared by dissolving the compound in a mixed solvent of the above.

[0115] This solution was cast onto a TAC film using a wire bar (#16), and then The substrate was left in an oven at 37°C for 1 minute to evaporate the solvent, forming a coating layer with a thickness of about 7 µm.

[0116] Then, the coating layer was irradiated with ultraviolet light from a high-pressure mercury lamp for about 5 seconds. After curing, an antiglare film was obtained.

[0117] [Example 4] 12.5 parts by weight of acrylic polymer having polymerizable groups, cellulose acetate propionate 5.5 parts by weight of nanosilica-containing acrylic ultraviolet-curable compound 149 parts by weight of polymerizable 0.1 parts by weight of fluorine-based compound B having a 1-bromo group was mixed with 129 parts by weight of methyl ethyl ketone. Dissolved in a mixed solvent of 24 parts by weight of ethanol and 13 parts by weight of 1-methoxy-2-propanol , a solution was prepared.

[0118] This solution was cast onto a PET film using a wire bar (#14), and then The substrate was left in an oven at 0°C for 1 minute to evaporate the solvent, forming a coating layer with a thickness of about 5 µm.

[0119] Then, the coating layer was irradiated with ultraviolet light from a high-pressure mercury lamp for about 5 seconds. After curing, an antiglare film was obtained.

[0120] [Example 5] 36.9 parts by weight of acrylic polymer having polymerizable groups, cellulose acetate propionate 3.0 parts by weight of urethane acrylate A, 55.0 parts by weight of silicone acrylate 0.7 parts by weight, dipentaerythritol hexaacrylate 22.9 parts by weight, 0.1 parts by weight of fluorine-based compound A, 1 part by weight of photoinitiator A, and 1 part by weight of photoinitiator B were mixed together in a methyl The solution was dissolved in a mixed solvent of 144 parts by weight of ethyl ethyl ketone and 21 parts by weight of 1-butanol. Prepared.

[0121] This solution was cast onto a TAC film using a wire bar (#18), and then The substrate was left in an oven at 37°C for 1 minute to evaporate the solvent, forming a coating layer with a thickness of approximately 8 µm.

[0122] Then, the coating layer was irradiated with ultraviolet light from a high-pressure mercury lamp for about 5 seconds. After curing, an antiglare film was obtained.

[0123] [Example 6] 50 parts by weight of acrylic polymer having polymerizable groups, cellulose acetate propionate 4 parts by weight, urethane acrylate A 76 parts by weight, silicone acrylate 1 part by weight, 1 part by weight of initiator A and 1 part by weight of photoinitiator B were mixed with 176 parts by weight of methyl ethyl ketone and 1-butanol The resulting solution was dissolved in a mixed solvent of 28 parts by weight of alcohol.

[0124] This solution was cast onto a TAC film using a wire bar (#18), and then The substrate was left in an oven at 37°C for 1 minute to evaporate the solvent, forming a coating layer with a thickness of approximately 8 µm.

[0125] Then, the coating layer was irradiated with ultraviolet light from a high-pressure mercury lamp for about 5 seconds. After curing, an antiglare film was obtained.

[0126] [Example 7] 3 parts by weight of cellulose acetate propionate, 97 parts by weight of urethane acrylate A, 90 parts by weight of PMMA beads B, 1 part by weight of photoinitiator A, and 1 part by weight of photoinitiator B were mixed in a methylethyl alcohol. A solution was prepared by dissolving the compound in a mixed solvent of 277 parts by weight of methyl ketone and 23 parts by weight of 1-butanol. Ta.

[0127] This solution was cast onto a PET film using a wire bar (#6), and then heated at 80°C. The substrate was left in an oven at 100°C for 1 minute to evaporate the solvent, thereby forming a coating layer with a thickness of about 1 μm.

[0128] Then, the coating layer was irradiated with ultraviolet light from a high-pressure mercury lamp for about 5 seconds. After curing, an antiglare film was obtained.

[0129] [Reference example 1] 50 parts by mass of silica-containing acrylic UV-curable compound and acrylic UV-curable compound This solution was mixed with 150 parts by mass of cellulose acetate and 150 parts by mass of cellulose acetate. After casting the mixture on a PET film, it was left in an oven at 80°C for 1 minute to evaporate the solvent. A coating layer with a thickness of about 7 μm was formed.

[0130] Then, the coating layer is irradiated with ultraviolet light from an ultraviolet lamp for about 5 seconds to perform an ultraviolet curing process. An antiglare film was obtained.

[0131] [Reference example 2] Urethane acrylate B 39 parts by weight, silicone hard coating material 15.7 parts by weight, P 0.3 parts by weight of MMA beads A, 6.1 parts by weight of cross-linked styrene beads, 3 parts by weight of methyl ethyl ketone A solution was prepared by dissolving in 8 parts by weight.

[0132] This solution was cast onto a PET film using a wire bar (#14), and then 100 The sample was left in a 100°C oven for 1 minute to evaporate the solvent and form a coating layer with a thickness of approximately 6 μm. .

[0133] Then, the coating layer was irradiated with ultraviolet light from a high-pressure mercury lamp for about 5 seconds. After curing, an antiglare film was obtained.

[0134] Table 1 shows the evaluation results of the antiglare films obtained in the examples and reference examples.

[0135] [Table 1]

[0136] As is clear from the results in Table 1, the antiglare films of the examples have high antiglare properties and good color (invisible light). The color transparency was also excellent. [Industrial Applicability]

[0137] The antiglare film of the present invention can be used in various display devices, such as LCDs, cathode ray tube displays, organic or Inorganic EL displays, field emission displays (FEDs), surface field displays (SFDs) Display (SED), rear projection TV display, plasma display It can be used as an anti-glare film for display devices such as display devices with touch panels. do.

[0138] Furthermore, the antiglare film of the present invention can be adapted to screens of various sizes and is suitable for small or portable screens. Screen display devices (e.g., car navigation displays, game devices, smartphones) displays for smartphones, tablet PCs, and other devices with touch panels), Medium-sized screen display devices (e.g., notebook or laptop PCs and desktop PCs, televisions, etc.), large-screen display devices (e.g., digital signage) These can be selected appropriately depending on the resolution, but Because it is possible to achieve both brightness and anti-glare properties, it is suitable for use in displays such as medium-sized and large-sized screens. It can be suitably used for installation.

[0139] Furthermore, films with anti-glare layers containing cured resin precursors have excellent scratch resistance, making them suitable for LCDs. and aftermarket protective films for OLED displays It can also be used as.

Claims

1. R / V is the ratio of the diffuse specular reflection intensity R to the total diffuse reflection intensity V (In the formula, the diffuse specular reflection intensity R is the diffuse reflection intensity measured at an aperture angle of 1 degree using a goniophotometer in the diffuse specular reflection direction when visible light is irradiated at an angle of 45 degrees from the normal to the surface of the anti-glare film to be measured, and the sum of the diffuse reflection intensities V is the sum of the diffuse reflection intensities measured at an aperture angle of 1 degree using a goniophotometer in 1-degree increments from -45 degrees to +45 degrees, including 0 degree, with respect to the diffuse specular reflection direction when visible light is irradiated at an angle of 45 degrees from the normal to the surface of the anti-glare film to be measured.) is 0.01 to 0.03, the haze is 44% or more, the 60-degree gloss is 0.2 to 10%, and the chromaticity b of the transmitted light is ＊ An antiglare film having an absolute value of 2 or less.

2. 2. The antiglare film according to claim 1, comprising a transparent substrate layer and an antiglare layer formed on at least one surface of the transparent substrate layer, wherein the antiglare layer is a cured product of a curable composition containing one or more polymer components and one or more curable resin precursor components.

3. 3. The antiglare film according to claim 2, wherein at least two components selected from the polymer component and the curable resin precursor component are phase-separable by wet spinodal decomposition.

4. 4. The antiglare film according to claim 2, wherein the polymer component comprises a cellulose ester and / or a (meth)acrylic polymer which may have a polymerizable group.

5. The antiglare film according to any one of claims 2 to 4, wherein the curable resin precursor component comprises at least one selected from the group consisting of polyfunctional (meth)acrylate, epoxy (meth)acrylate, polyester (meth)acrylate, urethane (meth)acrylate, and silicone (meth)acrylate.

6. The antiglare film according to any one of claims 2 to 5, which satisfies at least one of the following requirements (1) and (2): (1) The curable resin precursor component contains silica nanoparticles (2) The curable resin precursor component is a precursor component containing a fluorine atom.

7. The method for producing an antiglare film according to any one of claims 2 to 6, further comprising a curing step of curing the curable composition with heat or active energy rays.

8. 8. The method for producing an antiglare film according to claim 7, further comprising a phase separation step of applying a curable composition containing one or more polymer components and one or more curable resin precursor components onto a support and drying the applied composition to phase separate at least two components selected from the polymer components and the curable resin precursor components by wet spinodal decomposition, and a curing step of curing the phase-separated curable composition with heat or active energy rays.

9. A display device comprising the antiglare film according to any one of claims 1 to 6.

10. 10. The display device according to claim 9, which is an organic EL display or a liquid crystal display device.

11. R / V is the ratio of the diffuse specular reflection intensity R to the sum V of the diffuse reflection intensities (wherein the formula is the diffuse specular reflection intensity R measured at an aperture angle of 1 degree using a goniophotometer in the diffuse specular reflection direction when visible light is irradiated at an angle of 45 degrees from the normal to the surface of the anti-glare film to be measured, and the sum V of the diffuse reflection intensities is the sum of the diffuse reflection intensities measured at an aperture angle of 1 degree using a goniophotometer at 1 degree intervals from -45 degrees to +45 degrees, including 0 degree, with respect to the diffuse specular reflection direction when visible light is irradiated at an angle of 45 degrees from the normal to the surface of the anti-glare film to be measured), haze, 60-degree gloss, and chromaticity b of transmitted light ＊ to the ranges of 0.01 to 0.03, 44% or more, 0.2 to 10%, and 2 or less, respectively, thereby improving the antiglare properties and transparency of the antiglare film.

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