JP4739719B2 - Anti-glare film - Google Patents

Description

  The present invention relates to an antiglare film used for various displays (such as a liquid crystal display), a manufacturing method thereof, and a display device including the antiglare film.

  In recent years, various displays such as liquid crystal displays, plasma displays, organic EL (electroluminescence) displays, inorganic EL displays, and FED (field emission displays) have been developed. In particular, liquid crystal displays have made remarkable progress as display devices in television (TV) applications or moving image display applications, and are rapidly spreading. For example, the development of high-speed liquid crystal materials and the improvement of driving methods such as overdrive have overcome the conventional video display that LCDs were not good at, and production technology innovations that responded to larger displays Yes.

  In these displays, in applications such as televisions and monitors that place importance on image quality, and applications such as video cameras that are used outdoors with strong external light, the surface is usually treated to prevent external light. One of the techniques is anti-glare treatment, and for example, the surface of a liquid crystal display is usually subjected to anti-glare treatment. The anti-glare treatment has an effect of blurring the reflected image by scattering the surface reflected light by forming a fine uneven structure on the surface. Therefore, unlike a clear antireflection film, the antiglare layer does not reflect the shape of the viewer or the background, so that the reflected light hardly disturbs the image.

  For example, Japanese Patent Application Laid-Open No. 7-27920 (Patent Document 1) discloses a polyethylene terephthalate film that is attached to a polarizing plate used on the surface of various displays such as word processors, computers, and televisions, particularly a liquid crystal display. A polyethylene terephthalate film that has been antiglare treated by shaping a shaped film having fine irregularities is disclosed. In this document, an ionizing radiation curable resin composition is coated on a polyethylene terephthalate film, and then finely coated on the surface of the coated ionizing radiation curable resin composition in an uncured state. A mat-like shaped film having irregularities is laminated, and then the laminated coating is irradiated with ionizing radiation to completely cure the coating film, and then the mat-shaped shaped film is completely cured. It is described that an antiglare layer having fine irregularities formed on the surface is obtained by peeling from the film.

  Japanese Patent Application Laid-Open No. 11-337734 (Patent Document 2) discloses an antiglare treatment layer having irregularities formed on the surface as a surface treatment layer formed on the surface of a polarizing film suitable as a material for a liquid crystal cell. . According to this document, the anti-glare layer is formed by applying a dispersion of fine particles having a high refractive index in a resin solution by spin coating or after applying only an acrylic resin by spin coating or the like. It is described that the surface is formed directly by mechanically or chemically unevenly forming the surface.

  JP 2001-215307 A (Patent Document 3) discloses an antiglare layer containing transparent fine particles having an average particle diameter of 15 μm in a film having a thickness twice or more the average particle diameter, Among them, an antiglare layer is disclosed in which the transparent fine particles are unevenly distributed on one side in contact with air to form a fine concavo-convex structure.

  However, these anti-glare layers increase the scattering of light on the surface due to the irregularities of the film surface for imparting anti-glare properties, and the scattered light is mixed into a portion that originally looks black, and becomes whitish. That is, in places where the outside light is strong, the screen is generally whitish and lacks a sense of contrast. In particular, in television (TV) applications, a recent home theater boom has become a tailwind, and an image with a strong contrast feeling in which black has been tightened is required.

  Therefore, an increasing number of liquid crystal TVs have a clear surface without being subjected to anti-glare treatment. However, viewers with a clear surface and the reflection of the background became noticeable, which often hindered high-quality images. In particular, in the large-sized display due to the above-mentioned home theater boom, contrast deterioration and reflection are severe, and it is difficult to satisfy both characteristics.

  Such reflection disappears when there is no reflection from the surface, and reflection decreases when the reflection is low. Therefore, as a technique for disposing a low refractive index layer on the surface for the expression of low reflection performance, Japanese Patent Application Laid-Open No. 2001-264508 (Patent Document 4) has an average particle diameter of 1 to 10 μm on a transparent support. Contains antiglare hard coat layer containing particles, inorganic fine particles having an average particle diameter of 0.001 to 0.2 μm, hydrolyzate of photocurable organosilane and / or partial condensate thereof, and fluorine-containing polymer In addition, an antiglare antireflection film in which a low refractive index layer having a refractive index of 1.35 to 1.49 is sequentially formed is disclosed.

  Japanese Patent Laid-Open No. 2001-281411 (Patent Document 5) discloses that an antiglare antireflection film having substantially the same structure as Patent Document 4 has a transmitted image definition of 30 to 70% with an optical comb width of 0.5 mm. An antiglare antireflection film is disclosed.

  However, even with these films, since the intensity distribution of the transmitted scattered light is controlled by the particle size, it is impossible to effectively prevent glare and character blur on the display surface. Moreover, since special fine particles are used, it is disadvantageous in terms of cost.

  On the other hand, in Japanese Patent Application Laid-Open No. 2004-126495 (Patent Document 6), an anti-glare film composed of at least an anti-glare layer, the anti-glare layer having a concavo-convex structure on its surface, and incident light An antiglare film is disclosed that is isotropically transmitted and scattered, has a scattering angle of 0.1 to 10 ° and exhibits a maximum value of scattered light intensity, and has a total light transmittance of 70 to 100%. Has been. In this document, in a method for producing a sheet by evaporating a solvent from a solution in which at least one polymer and at least one curable resin precursor are uniformly dissolved, spinodal decomposition is performed under appropriate conditions, and then the precursor is prepared. Can be formed into a phase separation structure having regularity and a surface uneven structure corresponding to the phase separation structure, and an anti-glare layer having such a phase separation structure is attached to a display device. Then, it is described that a clear image quality with no character blur can be obtained, and at the same time, a good anti-glare effect without whiteness or whitening (white blurring) can be obtained. Furthermore, it is described that when this film is mounted on a high-definition display device, glare on the surface can be effectively removed and a high-performance anti-glare function can be obtained.

However, since this anti-glare film has high transmitted image clarity, when it is mounted on a display such as a liquid crystal display (LCD), the light transmitted through the anti-glare layer is an electrode such as an ITO (indium-titanium-oxide) electrode. Reflected in the screen, and reflection occurs.
JP-A-7-27920 (Claims 1 and 3, paragraph numbers [0001] [0020]) JP 11-337734 A (Claims 1, 4 and 8, paragraph number [0001]) JP 2001-215307 A (Claim 1, paragraph number [0012]) JP 2001-264508 A (Claim 1) JP 2001-281411 A (Claim 1) JP 2004-126495 A (Claims 1, 21, paragraph number [0090])

  Accordingly, an object of the present invention is to provide an antiglare film and a method for producing the same, which can prevent reflection even when mounted on a large display device such as a liquid crystal display.

  Another object of the present invention is to display a high-contrast image that can prevent reflection and glare on the display and reduce whiteness and whitening (white blurring) even under strong external light. It is providing the glare-proof layer and its manufacturing method.

  Still another object of the present invention is to provide an antiglare layer capable of suppressing white floating in a black display image and displaying a strong contrast image with black tightened, and a method for manufacturing the same, even for a large display. It is in.

As a result of intensive studies to achieve the above-mentioned problems, the present inventors have produced a sheet by evaporating a solvent from a solution in which at least one polymer and at least one curable resin precursor are uniformly dissolved. When spinodal decomposition is performed under appropriate conditions, and then the precursor is cured, a phase separation structure having regularity and a surface uneven structure corresponding to the phase structure can be formed, and the phase separation structure having such regularity is provided. When an antiglare layer (antiglare hard coat layer) and a low refractive index resin layer (low refractive index layer) are laminated, the incident light is isotropically transmitted and scattered, and the maximum value of the scattered light intensity is obtained. The scattering angle is 0.1 to 10 °, the total light transmittance is 70 to 100%, and the transmission is measured with a image clarity measuring instrument using an optical comb having a haze of 3 to 15 % and a width of 0.5 mm. Image clarity 0 antiglare film is 50% is obtained, be mounted on a display device such as a liquid crystal display, the glare can be prevented, further, when disposing the low refractive index layer as the outermost layer, a large display However, the present inventors have found that white floating in a black display image can be suppressed and an image with a strong contrast feeling in which black is tightened can be displayed, and the present invention has been completed.

That is, the antiglare film of the present invention is an antiglare film comprising an antiglare layer and a low refractive index resin layer (low refractive index layer) formed on at least one surface of the antiglare layer. The surface has a concavo-convex structure, isotropically transmits incident light and scatters, has a scattering angle of 0.1 to 10 ° indicating the maximum value of scattered light intensity, and transmits all light. with rate is 70% to 100%, a haze of Ri Oh 3 to 15 percent, and the transmission image clarity measured by an image clarity measuring apparatus provided with an optical slit of 0.5mm width is 10 50%.

  The antiglare layer is a layer composed of at least one polymer and at least one curable resin precursor, and includes at least two components (for example, a plurality of polymers, a polymer and a polymer). The curable resin precursor or a plurality of curable resin precursors are phase-separated by spinodal decomposition from the liquid phase, and the precursor is cured. The polymer is composed of a plurality of polymers that can be phase-separated by spinodal decomposition (for example, cellulose derivatives, styrene resins, (meth) acrylic resins, alicyclic olefin resins, polycarbonate resins, polyester resins, etc.). In addition, the curable resin precursor may be compatible with at least one of the plurality of polymers. Of the plurality of polymers, at least one polymer may have a functional group involved in the curing reaction of the curable resin precursor (for example, a polymerizable group such as a (meth) acryloyl group). Examples of the curable resin precursor include epoxy (meth) acrylate, urethane (meth) acrylate, polyester (meth) acrylate, silicone (meth) acrylate, and a polyfunctional monomer having at least two polymerizable unsaturated bonds. Etc. may be comprised. Note that the thermoplastic resin and the curable resin precursor are usually incompatible with each other. Further, the antiglare layer may be provided with hard coat properties (or scratch resistance) by curing of the curable resin precursor, and a regular or periodic phase separation structure may be fixed. The antiglare layer may be cured by, for example, active energy rays (ultraviolet rays, electron beams, etc.), heat, or the like. The antiglare layer may contain a polymer and a cured resin in a ratio of polymer / cured resin = 5/95 to 60/40 (weight ratio). Further, at least one of the plurality of polymers may be a cellulose derivative, and the ratio of the cellulose derivative may be about 5 to 10% by weight in the solid content constituting the antiglare layer.

  The low refractive index layer may be made of a resin having a refractive index of 1.30 to 1.49. The low refractive index layer may contain a fluorine-containing compound. The low refractive index layer may be composed of a curable fluororesin precursor, and the precursor may be cured by at least one selected from active energy rays and heat.

  The antiglare film may be composed of an antiglare layer and a low refractive index layer, and includes a transparent support (such as a transparent polymer film for forming an optical member) and an antiglare layer formed on the support. And a low refractive index layer formed on the antiglare layer.

  In the present invention, an optical member (laminated optical member) in which the antiglare film is laminated on at least one optical path surface (or one surface) of an optical element (such as a polarizing plate) is obtained. In this optical member, the anti-glare film is used in place of the protective film of the optical element (for example, the protective film on both sides of the polarizing plate), so that even if it is mounted on a display device such as a liquid crystal display, the image is reflected. While being able to prevent, high scratch resistance can be imparted to the optical element (polarizing plate or the like). For this reason, the film of this invention is preferably used also for display apparatuses, such as a liquid crystal display device, a plasma display, and a touchscreen type input device.

  The antiglare film of the present invention forms, for example, a phase separation structure from a liquid phase containing at least one polymer, at least one curable resin precursor, and a solvent by spinodal decomposition accompanying evaporation of the solvent, The resin precursor can be cured to form an antiglare layer, and a low refractive index resin layer can be formed on at least one surface of the antiglare layer. Spinodal decomposition from the liquid phase can be performed by evaporating the solvent. The combination forming the phase separation structure may be, for example, a plurality of polymers, a polymer and a curable resin precursor, or a plurality of curable resin precursors. In this method, a thermoplastic resin, a photocurable compound (such as a photopolymerizable monomer or oligomer), a photopolymerization initiator, and a solvent (common solvent) in which the thermoplastic resin and the photocurable compound are soluble are used. You may form a phase-separation structure by spinodal decomposition | disassembly from the composition containing, and may form an anti-glare layer by irradiating light. Also, the thermoplastic resin, a resin that is incompatible with the thermoplastic resin and has a photocurable group, a photocurable compound, a photopolymerization initiator, and the resin and the photocurable compound are soluble. A phase separation structure may be formed by spinodal decomposition from a composition containing an appropriate solvent, and an antiglare layer may be formed by light irradiation. In these methods, at least one antiglare layer may be formed on the transparent support, and a low refractive index resin layer may be formed on the antiglare layer. The present invention also includes an optical member in which the film is laminated on at least one surface of a polarizing plate.

  In the specification, “low reflection antiglare layer” means a laminated structure of an antiglare layer and a low refractive index layer, and “antiglare layer” means an antiglare layer alone.

  In the present invention, the antiglare layer having a phase separation structure utilizing spinodal decomposition and the low refractive index layer control the structure of the antiglare film and impart specific optical characteristics. Even if it is mounted on a large display device, reflection can be prevented. In addition, even under strong external light, it is possible to prevent reflection and glare on the display, and to display an image with high contrast with reduced whiteness and whitening (white blurring). Furthermore, even with a large display, white floating in a black display image can be suppressed, and an image with a strong contrast with black tightened can be displayed.

[Anti-glare film (anti-glare anti-reflection film)]
The antiglare film includes at least an antiglare layer and a low refractive index resin layer (low refractive index layer).

(Anti-glare layer)
The antiglare layer has a phase separation structure, and this phase separation structure is formed by spinodal decomposition (wet spinodal decomposition) from a liquid phase. That is, using the resin composition of the present invention composed of a polymer, a curable resin precursor, and a solvent, the solvent is evaporated from the liquid phase (or a uniform solution or a coating layer thereof) of the resin composition by drying or the like. In the process of removing, phase separation by spinodal decomposition occurs with concentration concentration, and a phase separation structure having a relatively regular interphase distance can be formed. More specifically, the wet spinodal decomposition is usually performed by coating a support with a mixed solution or a resin composition (homogeneous solution) containing at least one polymer, at least one curable resin precursor, and a solvent. This can be done by evaporating the solvent from the layer. Further, the antiglare layer may have a regular or periodic uneven shape formed on the surface thereof by raising the surface of the coating film by the generation of cellular rotational convection in the course of drying.

  When a peelable support is used as the support, after laminating the low refractive index layer on the antiglare layer, the support is peeled off from the antiglare layer, or the antiglare layer is peeled off from the support, By laminating a refractive index layer on the antiglare layer, an antiglare film having a laminated structure composed of an antiglare layer and a low refractive index layer can be obtained. Further, by using a non-peeling support (preferably a transparent support) as the support, an antiglare film having a laminated structure composed of the support, the antiglare layer and the low refractive index layer can be obtained. .

(1) Polymer component As the polymer component, a thermoplastic resin is usually used. Thermoplastic resins include styrene resins, (meth) acrylic resins, organic acid vinyl ester resins, vinyl ether resins, halogen-containing resins, olefin resins (including alicyclic olefin resins), polycarbonate resins, Polyester resin, polyamide resin, thermoplastic polyurethane resin, polysulfone resin (polyethersulfone, polysulfone, etc.), polyphenylene ether resin (2,6-xylenol polymer, etc.), cellulose derivatives (cellulose esters, cellulose carbamate) , Cellulose ethers, etc.), silicone resins (polydimethylsiloxane, polymethylphenylsiloxane, etc.), rubbers or elastomers (diene rubbers such as polybutadiene, polyisoprene, styrene-butadiene copolymers) Acrylonitrile - butadiene copolymer, acrylic rubber, urethane rubber, silicone rubber, etc.), and others. These thermoplastic resins can be used alone or in combination of two or more.

  Styrene resins include styrene monomers alone or copolymers (polystyrene, styrene-α-methylstyrene copolymer, styrene-vinyltoluene copolymer, etc.), styrene monomers and other polymerizable properties. Copolymers with monomers [(meth) acrylic monomers, maleic anhydride, maleimide monomers, dienes, etc.] are included. Examples of the styrene-based copolymer include a styrene-acrylonitrile copolymer (AS resin), a copolymer of styrene and a (meth) acrylic monomer [styrene-methyl methacrylate copolymer, styrene-methacrylic acid. Methyl- (meth) acrylic acid ester copolymer, styrene-methyl methacrylate- (meth) acrylic acid copolymer, etc.], styrene-maleic anhydride copolymer and the like. Preferred styrenic resins include polystyrene, copolymers of styrene and (meth) acrylic monomers [copolymers based on styrene and methyl methacrylate such as styrene-methyl methacrylate copolymer], AS resin, styrene-butadiene copolymer and the like are included.

As the (meth) acrylic resin, a (meth) acrylic monomer alone or a copolymer, a copolymer of a (meth) acrylic monomer and a copolymerizable monomer, or the like can be used. Examples of (meth) acrylic monomers include (meth) acrylic acid; methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, t-butyl (meth) acrylate, ( (Meth) acrylic acid isobutyl, (meth) acrylic acid hexyl, (meth) acrylic acid octyl, (meth) acrylic acid 2-ethylhexyl (meth) acrylic acid C _1-10 alkyl; (meth) acrylic acid phenyl ( (Meth) acrylic acid aryl; hydroxyalkyl (meth) acrylate such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate; glycidyl (meth) acrylate; N, N-dialkylaminoalkyl (meth) acrylate; (meth) acrylonitrile Has an alicyclic hydrocarbon group such as tricyclodecane (Meth) acrylate, and others. Examples of the copolymerizable monomer include the styrene monomer, vinyl ester monomer, maleic anhydride, maleic acid, and fumaric acid. These monomers can be used alone or in combination of two or more.

Examples of the (meth) acrylic resin include poly (meth) acrylic acid esters such as polymethyl methacrylate, methyl methacrylate- (meth) acrylic acid copolymer, methyl methacrylate- (meth) acrylic acid ester copolymer Examples thereof include methyl methacrylate, acrylic acid ester- (meth) acrylic acid copolymer, and (meth) acrylic acid ester-styrene copolymer (MS resin and the like). Preferable (meth) acrylic resins include poly (meth) acrylic acid C _1-6 alkyl such as poly (meth) methyl acrylate, particularly methyl methacrylate as a main component (50 to 100% by weight, preferably 70 to 100%). And a methyl methacrylate-based resin.

  Organic acid vinyl ester resins include vinyl ester monomers alone or copolymers (polyvinyl acetate, polyvinyl propionate, etc.), and vinyl ester monomers and copolymerizable monomers. Examples thereof include a copolymer (ethylene-vinyl acetate copolymer, vinyl acetate-vinyl chloride copolymer, vinyl acetate- (meth) acrylic ester copolymer, etc.) or a derivative thereof. Examples of the vinyl ester resin derivative include polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyvinyl acetal resin, and the like.

Examples of vinyl ether resins include vinyl C _1-10 alkyl ethers such as vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, vinyl t-butyl ether, or copolymers, and vinyl C _1-10 alkyl ethers and copolymers. And a copolymer with a monomer (such as a vinyl alkyl ether-maleic anhydride copolymer).

  Examples of the halogen-containing resin include polyvinyl chloride, polyvinylidene fluoride, vinyl chloride-vinyl acetate copolymer, vinyl chloride- (meth) acrylate ester copolymer, vinylidene chloride- (meth) acrylate ester copolymer, and the like. Can be mentioned.

  Examples of the olefin resin include homopolymers of olefins such as polyethylene and polypropylene, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, ethylene- (meth) acrylic acid copolymer, ethylene- (meta ) Copolymers such as acrylic acid ester copolymers. As the alicyclic olefin-based resin, a cyclic olefin (norbornene, dicyclopentadiene, etc.) alone or a copolymer (for example, a polymer having an alicyclic hydrocarbon group such as sterically rigid tricyclodecane, etc.) And a copolymer of the cyclic olefin and a copolymerizable monomer (such as an ethylene-norbornene copolymer and a propylene-norbornene copolymer). The alicyclic olefin-based resin can be obtained, for example, under the trade name “ARTON” or the trade name “ZEONEX”.

  Polycarbonate resins include aromatic polycarbonates based on bisphenols (such as bisphenol A) and aliphatic polycarbonates such as diethylene glycol bisallyl carbonate.

Polyester resins include aromatic polyesters using aromatic dicarboxylic acids such as terephthalic acid [polyesters such as polyethylene terephthalate and polybutylene terephthalate, homopolyesters such as poly C _2-4 alkylene terephthalate and poly C _2-4 alkylene naphthalate, Examples thereof include a copolyester containing a C _2-4 alkylene arylate unit (C _2-4 alkylene terephthalate and / or C _2-4 alkylene naphthalate unit) as a main component (for example, 50% by weight or more). The copolyesters, poly C _2-4 among constituent units of alkylene arylate, C _2-4 part of the alkylene glycol, polyoxy C _2-4 alkylene glycols, C _6-10 alkylene glycol, alicyclic diols (cyclohexane Dimethanol, hydrogenated bisphenol A and the like, diols having aromatic rings (9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene having a fluorenone side chain, bisphenol A, bisphenol A-alkylene oxide adducts, etc. ) And other copolyesters substituted with asymmetric aromatic dicarboxylic acids such as phthalic acid and isophthalic acid, and copolyesters substituted with aliphatic C _6-12 dicarboxylic acids such as adipic acid It is. Polyester resins also include polyarylate resins, aliphatic polyesters using aliphatic dicarboxylic acids such as adipic acid, and homopolymers or copolymers of lactones such as ε-caprolactone. A preferred polyester resin is usually amorphous such as an amorphous copolyester (for example, C _2-4 alkylene arylate copolyester).

  Examples of polyamide resins include aliphatic polyamides such as nylon 46, nylon 6, nylon 66, nylon 610, nylon 612, nylon 11 and nylon 12, dicarboxylic acids (for example, terephthalic acid, isophthalic acid, adipic acid, etc.) and diamines ( Examples thereof include polyamides obtained from hexamethylenediamine and metaxylylenediamine). The polyamide-based resin may be a lactam homopolymer or copolymer such as ε-caprolactam, and is not limited to homopolyamide but may be copolyamide.

Among cellulose derivatives, cellulose esters include, for example, aliphatic organic acid esters (cellulose acetate such as cellulose diacetate and cellulose triacetate; cellulose propionate, cellulose butyrate, cellulose acetate propionate, and cellulose acetate butyrate). C _1-6 organic acid esters), aromatic organic acid esters (C _7-12 aromatic carboxylic acid esters such as cellulose phthalate and cellulose benzoate), and inorganic acid esters (eg, cellulose phosphate, cellulose sulfate, etc.) Examples thereof include mixed acid esters such as acetic acid and cellulose nitrate ester. Cellulose derivatives include cellulose carbamates (for example, cellulose phenyl carbamate), cellulose ethers (for example, cyanoethyl cellulose; hydroxy C _2-4 alkyl cellulose such as hydroxyethyl cellulose and hydroxypropyl cellulose; C _1- such as methyl cellulose and ethyl cellulose; ₆ alkylcellulose; carboxymethylcellulose or a salt thereof, benzylcellulose, acetylalkylcellulose, etc.).

  Preferred thermoplastic resins include, for example, styrene resins, (meth) acrylic resins, vinyl acetate resins, vinyl ether resins, halogen-containing resins, alicyclic olefin resins, polycarbonate resins, polyester resins, and polyamide resins. Examples thereof include resins, cellulose derivatives, silicone resins, and rubbers or elastomers. As the thermoplastic resin, a resin that is amorphous and is soluble in an organic solvent (particularly, a common solvent capable of dissolving a plurality of polymers and curable compounds) is usually used. In particular, resins with high moldability or film formability, transparency and weather resistance, such as styrene resins, (meth) acrylic resins, alicyclic olefin resins, polyester resins, cellulose derivatives (cellulose esters, etc.) Etc. are preferable. In particular, in the present invention, a cellulose derivative is preferable as the thermoplastic resin. Cellulose derivatives are semi-synthetic polymers and have very good phase separation properties because they have different dissolution behavior from other resins and curable resin precursors.

As the polymer (thermoplastic resin), a polymer having a functional group involved in the curing reaction (functional group capable of reacting with the curable precursor) can also be used. Such a polymer may have a functional group in the main chain or in a side chain. The functional group may be introduced into the main chain by copolymerization or cocondensation, but is usually introduced into the side chain. Such functional groups include condensable or reactive functional groups (for example, hydroxyl groups, acid anhydride groups, carboxyl groups, amino groups or imino groups, epoxy groups, glycidyl groups, isocyanate groups, etc.), polymerizable functional groups. (For example, C _2-6 alkenyl groups such as vinyl, propenyl, isopropenyl, butenyl and allyl, C _2-6 alkynyl groups such as ethynyl, propynyl and butynyl, C _2-6 alkenylidene groups such as vinylidene, or polymerization thereof And a functional group having a functional functional group (such as a (meth) acryloyl group). Among these functional groups, a polymerizable functional group is preferable.

  The thermoplastic resin having a polymerizable functional group in the side chain is, for example, a thermoplastic resin (i) having a reactive group (such as a functional group similar to the functional group exemplified in the section of the condensable or reactive functional group). , Reacting a reactive group for the reactive group of this thermoplastic resin with a compound (polymerizable compound) (ii) having a polymerizable functional group, and then reacting the polymerizable functional group of compound (ii) with the thermoplastic resin It can manufacture by introduce | transducing into.

Examples of the thermoplastic resin (i) having a reactive group include a thermoplastic resin having a carboxyl group or its acid anhydride group [for example, (meth) acrylic resin (methyl methacrylate- (meth) acrylic acid copolymer). (Meth) acrylic acid- (meth) acrylic acid ester copolymer, methyl methacrylate-acrylic acid ester- (meth) acrylic acid copolymer, etc.), polyester-based resin having a terminal carboxyl group or polyamide-based resin, etc. ], A thermoplastic resin having a hydroxyl group [for example, a (meth) acrylic resin (such as a (meth) acrylic acid ester- (meth) acrylic acid hydroxyalkyl ester copolymer), a polyester-based resin having a terminal hydroxyl group or a polyurethane Resin, cellulose derivatives (hydroxyethylcellulose, hydroxyp Pills hydroxy C _2-4 alkyl cellulose such as cellulose), polyamide resins (N- methylolacrylamide copolymer)], a thermoplastic resin having an amino group (e.g., a polyamide resin having a terminal amino group), Examples thereof include a thermoplastic resin having an epoxy group (for example, a (meth) acrylic resin or a polyester resin having an epoxy group (such as a glycidyl group)). In addition, as the thermoplastic resin (i) having the reactive group, the reactive group may be added to a thermoplastic resin such as a styrene resin, an olefin resin, or an alicyclic olefin resin by copolymerization or graft polymerization. The introduced resin may be used. Of these thermoplastic resins (i), a thermoplastic resin having a carboxyl group or its acid anhydride group, a hydroxyl group or a glycidyl group (particularly a carboxyl group or its acid anhydride group) as a reactive group is preferred. In addition, it is preferable that the said copolymer contains 50 mol% or more of (meth) acrylic acid among the said (meth) acrylic-type resin. The thermoplastic resins (i) can be used alone or in combination of two or more.

  The reactive group of the polymerizable compound (ii) is a group reactive to the reactive group of the thermoplastic resin (i), for example, the condensable or reactive functional group exemplified in the section of the functional group of the polymer. And the same functional group.

Examples of the polymerizable compound (ii) include an epoxy group-containing polymerizable compound [for example, an epoxy group-containing (meth) acrylate (epoxy C ₃₋ such as glycidyl (meth) acrylate, 1,2-epoxybutyl (meth) acrylate), etc. ₈ alkyl (meth) acrylates; epoxycycloC _5-8 alkenyl (meth) acrylates such as epoxycyclohexenyl (meth) acrylate), allyl glycidyl ethers etc.], compounds having hydroxyl groups [hydroxyl group-containing (meth) acrylates, For example, hydroxy C _2-4 alkyl (meth) acrylates such as hydroxypropyl (meth) acrylate; C _2-6 alkylene glycol mono (meth) acrylates such as ethylene glycol mono (meth) acrylate, etc.], polymerizable having an amino group Compound For example, an amino group-containing (meth) acrylate (C _3-6 alkenyl amines such as allylamine; 4-aminostyrene, etc. aminostyrene such as di-aminostyrene), a polymerizable compound having an isocyanate group [for example, (poly) urethane ( And a polymerizable compound having a carboxyl group or an acid anhydride group thereof (for example, an unsaturated carboxylic acid such as (meth) acrylic acid or maleic anhydride or an anhydride thereof). These polymerizable compounds (ii) can be used alone or in combination of two or more.

  Examples of the combination of the reactive group of the thermoplastic resin (i) and the reactive group of the polymerizable compound (ii) include the following combinations.

(i-1) Reactive group of thermoplastic resin (i): carboxyl group or acid anhydride group thereof Reactive group of polymerizable compound (ii): epoxy group, hydroxyl group, amino group, isocyanate group
(i-2) Reactive group of thermoplastic resin (i): hydroxyl group Reactive group of polymerizable compound (ii): carboxyl group or its acid anhydride group, isocyanate group
(i-3) Reactive group of thermoplastic resin (i): amino group Reactive group of polymerizable compound (ii): carboxyl or its acid anhydride group, epoxy group, isocyanate group
(i-4) Reactive group of thermoplastic resin (i): epoxy group Reactive group of polymerizable compound (ii): carboxyl group or its acid anhydride group, amino group.

  Among the polymerizable compounds (ii), an epoxy group-containing polymerizable compound (such as an epoxy group-containing (meth) acrylate) is particularly preferable.

  The functional group-containing polymer, for example, a polymer in which a polymerizable unsaturated group is introduced into a part of the carboxyl group of the (meth) acrylic resin can be obtained from Daicel Chemical Industries, Ltd. as “Cyclomer P”, for example. . Cyclomer P is produced by reacting the epoxy group of 3,4-epoxycyclohexenylmethyl acrylate with a part of the carboxyl group of the (meth) acrylic acid- (meth) acrylic ester copolymer to form a side chain. It is a (meth) acrylic polymer into which a photopolymerizable unsaturated group is introduced.

  The introduction amount of the functional group (particularly polymerizable group) involved in the curing reaction for the thermoplastic resin is 0.001 to 10 mol, preferably 0.01 to 5 mol, more preferably 0 with respect to 1 kg of the thermoplastic resin. About 0.02 to 3 moles.

These polymers can be used in appropriate combinations. That is, the polymer may be composed of a plurality of polymers. The plurality of polymers may be phase separable by liquid phase spinodal decomposition. The plurality of polymers may be incompatible with each other. When combining a plurality of polymers, the combination of the first resin and the second resin is not particularly limited, but suitable as a plurality of polymers incompatible with each other near the processing temperature, for example, two polymers incompatible with each other Can be used in combination. For example, when the first polymer is a cellulose derivative (for example, cellulose esters such as cellulose acetate propionate), the second polymer is a styrene resin (polystyrene, styrene-acrylonitrile copolymer, etc.), (meta ) Acrylic resins, alicyclic olefin resins (such as polymers containing norbornene), polycarbonate resins, polyester resins (such as the poly C _2-4 alkylene arylate copolyester) Good. Further, for example, when the first polymer is a styrene resin (polystyrene, styrene-acrylonitrile copolymer, etc.), the second polymer is a cellulose derivative (eg, cellulose esters such as cellulose acetate propionate), (Meth) acrylic resins (polymethyl methacrylate, etc.), alicyclic olefin resins (polymers containing norbornene as a monomer), polycarbonate resins, polyester resins (the poly C _2-4 alkylene arylates) Copolyester etc.) may be used. In the combination of a plurality of resins, at least cellulose esters (for example, cellulose C _2-4 aliphatic carboxylic acid esters such as cellulose diacetate, cellulose triacetate, cellulose acetate propionate, and cellulose acetate butyrate) may be used. .

  In addition, a plurality of polymers do not phase-separate each other in the drying process for evaporating the solvent, and the phase separation of the plurality of polymers functioning as an antiglare layer is a uniform solution using a good solvent for both components. In the process of gradually evaporating the solvent, it can be easily determined by visually confirming whether or not the residual solid content becomes cloudy.

  In addition, the phase separation structure produced | generated by spinodal decomposition | disassembly is finally hardened | cured with actinic light (an ultraviolet ray, an electron beam, etc.), heat, etc., and forms cured resin. The antiglare layer forms a hard coat layer by final curing. Therefore, scratch resistance can be imparted to the antiglare layer, and durability can be improved.

  From the viewpoint of scratch resistance after curing, at least one of a plurality of polymers, for example, one of the incompatible polymers (when combining the first resin and the second resin, Both polymers are preferably polymers having functional groups in the side chain capable of reacting with the curable resin precursor.

  The ratio (weight ratio) between the first polymer and the second polymer is, for example, the former / the latter = 1/99 to 99/1, preferably 5/95 to 95/5, more preferably 10/90 to 90. Can be selected from the range of about / 10, and is usually about 20/80 to 80/20, particularly about 30/70 to 70/30. In particular, when a cellulose derivative is used as the first polymer, the ratio (weight ratio) between the first polymer and the second polymer is, for example, the former / the latter = 1/99 to 30/70, preferably 5/95. It is about -28/72, More preferably, it is about 10 / 90-27 / 73 (especially 15 / 85-25 / 75) grade. When the ratio of the cellulose derivative is within this range, an antiglare film having low haze and suppressed transmitted image clarity can be formed.

  In addition, as a polymer for forming a phase-separated structure, the said thermoplastic resin and another polymer other than the said two incompatible polymers may be contained.

  The glass transition temperature of the polymer can be selected from the range of, for example, −100 ° C. to 250 ° C., preferably −50 ° C. to 230 ° C., more preferably about 0 to 200 ° C. (for example, about 50 to 180 ° C.).

  From the viewpoint of surface hardness, the glass transition temperature is advantageously 50 ° C. or higher (for example, about 70 to 200 ° C.), preferably 100 ° C. or higher (for example, about 100 to 170 ° C.). The weight average molecular weight of a polymer can be selected from the range of about 1,000,000 or less, preferably about 1,000 to 500,000, for example.

(2) Curable resin precursor The curable resin precursor is a compound having a functional group that reacts with heat or active energy rays (such as ultraviolet rays or electron beams) and is cured or crosslinked with heat or active energy rays. Thus, various curable compounds capable of forming a resin (particularly a cured or crosslinked resin) can be used.

  Examples of the resin precursor include a thermosetting compound or a resin [an epoxy group, an isocyanate group, an alkoxysilyl group, a silanol group, a polymerizable group (such as a vinyl group, an allyl group, a (meth) acryloyl group). Molecular weight compounds (or prepolymers such as low molecular weight resins such as epoxy resins, unsaturated polyester resins, urethane resins, silicone resins, etc.)], photocurable compounds that can be cured by actinic rays (such as ultraviolet rays) ( Examples thereof include UV curable compounds such as photocurable monomers, oligomers, and prepolymers, and the like. The photocurable compound may be an EB (electron beam) curable compound. Note that a photocurable compound such as a photocurable monomer, an oligomer, or a photocurable resin that may have a low molecular weight may be simply referred to as a “photocurable resin”. A curable resin precursor can be used individually or in combination of 2 or more types.

  The photocurable compound usually has a photocurable group, for example, a polymerizable group (vinyl group, allyl group, (meth) acryloyl group, etc.) or a photosensitive group (cinnamoyl group, etc.). A photocurable compound having a functional group (for example, a monomer, an oligomer (or a resin, particularly a low molecular weight resin)) is preferable. A photocurable compound can be used individually or in combination of 2 or more types.

Among the photocurable compounds having a polymerizable group, examples of the monomer include monofunctional monomers [(meth) acrylic monomers such as (meth) acrylic acid esters, for example, alkyl (meth) Acrylate (C _1-6 alkyl (meth) acrylate such as methyl (meth) acrylate), cycloalkyl (meth) acrylate, (meth) acrylate having a bridged cyclic hydrocarbon group (isobornyl (meth) acrylate, adamantyl (meth) ) Acrylate, etc.), glycidyl (meth) acrylate, vinyl esters such as vinyl acetate, vinyl monomers such as vinyl pyrrolidone, etc.], multifunctional monomers having at least two polymerizable unsaturated bonds [ethylene glycol di (Meth) acrylate, propylene glycol di (meth) acrylate, butanedio Alkylene glycol di (meth) acrylates such as rudi (meth) acrylate, neopentyl glycol di (meth) acrylate, hexanediol di (meth) acrylate; diethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, polyoxy (Poly) oxyalkylene glycol di (meth) acrylates such as tetramethylene glycol di (meth) acrylate; dicyclomethane dimethanol di (meth) acrylates and diammers having bridged cyclic hydrocarbon groups such as adamantane di (meth) acrylates (Meth) acrylate; trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol Rutetora (meth) acrylate, a polyfunctional monomer having 3 to 6 degree of polymerizable unsaturated bonds, such as dipentaerythritol penta (meth) acrylate] can be exemplified.

  Among the photocurable compounds having a polymerizable group, as an oligomer or resin, (meth) acrylate, epoxy (meth) acrylate (bisphenol A type epoxy (meth) acrylate, novolak type epoxy (bisphenol A-alkylene oxide adduct)) Meth) acrylate), polyester (meth) acrylate (for example, aliphatic polyester type (meth) acrylate, aromatic polyester type (meth) acrylate, etc.), (poly) urethane (meth) acrylate (polyester type urethane (meth) acrylate) And polyether type urethane (meth) acrylate), silicone (meth) acrylate and the like.

  Preferred curable resin precursors are photocurable compounds that can be cured in a short time, for example, ultraviolet curable compounds (monomers, oligomers, resins that may be low molecular weight, etc.), and EB curable compounds. In particular, practically advantageous resin precursors are ultraviolet curable monomers and ultraviolet curable resins. Further, in order to improve resistance such as scratch resistance, the photocurable resin is a compound having 2 or more (preferably about 2 to 6, more preferably about 2 to 4) polymerizable unsaturated bonds in the molecule. Is preferred.

  The molecular weight of the curable resin precursor is about 5000 or less, preferably about 2000 or less, more preferably about 1000 or less in consideration of compatibility with the polymer.

  The curable resin precursor may be used in combination with a curing agent depending on the type. For example, the thermosetting resin precursor may be used in combination with a curing agent such as amines and polyvalent carboxylic acids, and the photocurable resin precursor may be used in combination with a photopolymerization initiator.

  Examples of the photopolymerization initiator include conventional components such as acetophenones or propiophenones, benzyls, benzoins, benzophenones, thioxanthones, acylphosphine oxides, and the like.

  The content of the curing agent such as a photocuring agent is 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, more preferably 1 to 8 parts by weight (100 parts by weight based on 100 parts by weight of the curable resin precursor. In particular, it is about 1 to 5 parts by weight, and may be about 3 to 8 parts by weight.

  Furthermore, the curable resin precursor may contain a curing accelerator or a crosslinking agent. For example, the photocurable resin precursor may be combined with a photocuring accelerator such as a tertiary amine (such as a dialkylaminobenzoic acid ester) or a phosphine photopolymerization accelerator.

  In the present invention, it is preferable that at least two components of at least one polymer and at least one curable resin precursor are used in a combination in which phase separation occurs near the processing temperature. Examples of combinations for phase separation include (a) a combination in which a plurality of polymers are incompatible with each other, (b) a combination in which a polymer and a curable resin precursor are incompatible and phase separated, c) A combination of a plurality of curable resin precursors incompatible with each other and phase separated. Of these combinations, (a) a combination of a plurality of polymers, or (b) a combination of a polymer and a curable resin precursor, and (a) a combination of a plurality of polymers is particularly preferable. When the compatibility of both of the phases to be separated is high, both do not effectively separate in the drying process for evaporating the solvent, and the function as an antiglare layer is reduced.

  The thermoplastic resin and the curable resin precursor (or curable resin) are usually incompatible with each other. When the polymer and the curable resin precursor are incompatible and phase-separated, a plurality of polymers may be used as the polymer. When a plurality of polymers are used, it is sufficient that at least one polymer is incompatible with the resin precursor (or cured resin), and other polymers may be compatible with the resin precursor.

  Further, it may be a combination of two thermoplastic resins that are incompatible with each other and a curable compound (in particular, a monomer or oligomer having a plurality of curable functional groups). Furthermore, from the viewpoint of scratch resistance after curing, one of the incompatible thermoplastic resins (especially both polymers) is involved in the curing of the functional group (participating in the curing of the curable resin precursor). A thermoplastic resin having a functional group).

  When the polymer is composed of a plurality of incompatible polymers and phase-separated, the curable resin precursor is a combination in which at least one of the incompatible polymers is compatible with each other near the processing temperature. Used in. That is, when a plurality of incompatible polymers are constituted by, for example, a first resin and a second resin, the curable resin precursor is at least one of the first resin and the second resin. It may be compatible with one resin, and may be compatible with both polymer components. When compatible with both polymer components, at least two phases of a mixture mainly composed of the first resin and the curable resin precursor and a mixture mainly composed of the second resin and the curable resin precursor You may phase-separate.

  When the compatibility of a plurality of selected polymers is high, the polymers are not effectively separated in the drying process for evaporating the solvent, and the function as an antiglare layer is reduced.

  The plurality of polymers incompatible with the curable monomer are used in a combination in which at least one component polymer and the curable monomer are compatible with each other near the processing temperature. That is, when a plurality of polymers that are incompatible with each other, for example, composed of polymer A and polymer B, the curable monomer may be compatible with at least either polymer A or polymer B, preferably both polymers It may be compatible with the components. When compatible with both polymer components, it is phase-separated into at least two phases of a mixture mainly composed of polymer A and curable monomer and a mixture mainly composed of polymer B and curable monomer.

  In addition, a plurality of polymer phase separation properties and a phase separation property between a polymer and a curable monomer are obtained by preparing a uniform solution using good solvents for both components and gradually evaporating the solvent. It can be easily determined by visually confirming whether or not the liquid becomes cloudy.

  Furthermore, the refractive index of the polymer and the cured or crosslinked resin produced by curing the resin precursor are usually different from each other. Further, the refractive indexes of the plurality of polymers (first resin and second resin) are also different from each other. The difference in refractive index between the polymer and the cured or crosslinked resin and the difference in refractive index between the plurality of polymers (first resin and second resin) are, for example, 0.001 to 0.2, preferably 0.05 to It may be about 0.15.

  In spinodal decomposition, a co-continuous phase structure is formed with the progress of phase separation, and when the phase separation further proceeds, the continuous phase becomes discontinuous by its surface tension, resulting in a droplet phase structure (spherical, true spherical, disc-like) Or an island-like sea-island structure such as an ellipsoidal shape. Therefore, an intermediate structure between the co-continuous phase structure and the droplet phase structure (phase structure in the process of transition from the co-continuous phase to the droplet phase) can be formed depending on the degree of phase separation. In the present invention, the phase separation structure of the antiglare layer may be a sea-island structure (droplet phase structure or a phase structure in which one phase is independent or isolated), a co-continuous phase structure (or network structure), An intermediate structure in which a continuous phase structure and a droplet phase structure are mixed may be used. With these phase separation structures, fine irregularities can be formed on the surface of the antiglare layer after solvent drying.

  In the phase separation structure, a droplet phase structure having at least island-like domains is advantageous from the viewpoint of forming a surface uneven structure and increasing the surface hardness. When the phase separation structure composed of the polymer and the precursor (or cured resin) is a sea-island structure, the polymer component may form a sea phase, but from the viewpoint of surface hardness, the polymer component is an island. Preferably, a domain is formed. By forming island-like domains, fine irregularities can be formed on the surface of the antiglare layer after drying.

  Furthermore, the average distance between the domains of the phase separation structure is usually substantially regular or periodic. For example, the average interphase distance between domains may be, for example, about 30 to 300 μm, preferably about 40 to 250 μm, and more preferably about 50 to 200 μm.

  The ratio (weight ratio) between the polymer and the curable resin precursor is not particularly limited, and can be selected, for example, from the range of the former / the latter = 5/95 to 95/5, and preferably 5 from the viewpoint of surface hardness. / 95 to about 60/40, more preferably about 10/90 to 50/50, particularly about 10/90 to 40/60. In particular, when a cellulose derivative is used for all or part of the polymer, the ratio (weight ratio) between the polymer and the curable resin precursor is, for example, the former / the latter = 10/90 to 80/20, preferably 20/80. It is about -70/30, More preferably, it is about 30 / 70-50 / 50.

  In the antiglare film, the thickness of the antiglare layer may be, for example, about 0.3 to 20 μm, preferably about 1 to 15 μm (for example, 1 to 10 μm), and usually 2 to 10 μm (particularly 3 to 3 μm). 7 μm). In addition, when not using it by laminating | stacking with a support body, you may select the thickness of an anti-glare layer from the range of about 1-100 micrometers, for example, Preferably about 3-50 micrometers.

(Low refractive index layer)
The low refractive index layer is made of a low refractive index resin. By laminating the low refractive index layer on at least one surface of the antiglare layer, when the low refractive index layer is disposed on the outermost surface of an optical member or the like, light from the outside (external light source) Etc.) can be effectively prevented from reflecting on the surface of the antiglare film.

  The refractive index of the low refractive index resin is, for example, about 1.30 to 1.49, preferably about 1.36 to 1.49, and more preferably about 1.38 to 1.48.

  Examples of the low refractive index resin include fluorine resins such as methylpentene resin, diethylene glycol bis (allyl carbonate) resin, polyvinylidene fluoride (PVDF), and polyvinyl fluoride (PVF). In addition, the low refractive index layer usually preferably contains a fluorine-containing compound. When a fluorine-containing compound is used, the refractive index of the low refractive index layer can be reduced as desired.

  The fluorine-containing compound has a fluorine atom and a functional group (such as a curable group such as a crosslinkable group or a polymerizable group) that reacts with heat, active energy rays (such as ultraviolet rays or electron beams), and the like. And a fluorine-containing resin precursor that can be cured or crosslinked by an active energy ray or the like to form a fluorine-containing resin (particularly a cured or crosslinked resin).

  Examples of such fluorine-containing resin precursors include fluorine atom-containing thermosetting compounds or resins [with fluorine atoms, reactive groups (epoxy groups, isocyanate groups, carboxyl groups, hydroxyl groups, etc.), polymerizable groups (vinyl). Group, allyl group, (meth) acryloyl group, etc.)], fluorine atom-containing photocurable compound or resin (photocurable fluorine-containing monomer or oligomer, etc.) curable by actinic rays (such as ultraviolet rays) Examples thereof include ultraviolet curable compounds.

  As the thermosetting compound or resin, for example, a low molecular weight resin obtained using at least a fluorine-containing monomer, for example, a fluorine-containing polyol (particularly a diol) is used instead of a part or all of the polyol component as a constituent monomer. Epoxy-based fluorine-containing resin obtained in the same manner; similarly, unsaturation obtained by using a fluorine atom-containing polyol and / or a fluorine atom-containing polycarboxylic acid component instead of part or all of the polyol and / or polycarboxylic acid component Polyester-based fluorine-containing resin: A urethane-based fluorine-containing resin obtained by using a fluorine atom-containing polyol and / or a polyisocyanate component instead of a part or all of the polyol and / or polyisocyanate component can be exemplified. These thermosetting compounds or resins can be used alone or in combination of two or more.

  Examples of the photocurable compound include monomers and oligomers (or resins, particularly low molecular weight resins), and examples of the monomers include, for example, a monofunctional monomer as exemplified in the section of the antiglare layer. Fluorine atom-containing monomers corresponding to isomers and polyfunctional monomers [fluorine atom-containing (meth) acrylic monomers such as fluorinated alkyl esters of (meth) acrylic acid, vinyl-based monomers such as fluoroolefins, etc. And monofunctional monomers such as dimers; di (meth) acrylates of fluorinated alkylene glycols such as 1-fluoro-1,2-di (meth) acryloyloxyethylene]. Moreover, as an oligomer or resin, the fluorine atom containing oligomer or resin corresponding to the oligomer or resin illustrated by the term of the said glare-proof layer can be used. These photocurable compounds can be used alone or in combination of two or more.

  The curable precursor of the fluorine-containing resin can be obtained, for example, in the form of a solution (coating liquid), and such a coating liquid is, for example, “TT1006A” and “JN7215” manufactured by Nippon Synthetic Rubber Co., Ltd. It can be obtained as “Defenser TR-330” manufactured by Nippon Ink Chemical Co., Ltd.

  The thickness of the low refractive index layer is, for example, 0.05 to 2 μm, preferably 0.1 to 1 μm (for example, 0.1 to 0.5 μm), and more preferably about 0.1 to 0.3 μm.

  As described above, the antiglare film may be composed of an antiglare layer and a low refractive index layer, and is composed of a support and an antiglare layer and a low refractive index layer that are sequentially formed on the support. May be. As the support, a light-transmitting support, for example, a transparent support such as a synthetic resin film is used. Moreover, the support body which has a light transmittance may be comprised with the transparent polymer film for forming an optical member.

  In general, when the surface of the antiglare layer is coated with a low refractive index layer, the haze is reduced by about 1 to 10% and the transmission sharpness tends to be increased by about 1 to 10% compared to the antiglare layer alone before coating. For this reason, in order to adjust the haze and transmission clarity of the final low-reflection antiglare layer within the scope of the present invention, the haze of the antiglare layer alone is prepared in advance so that the antiglare layer alone It is necessary to adjust so that the transmission definition of the image becomes lower.

(Transparent support)
Examples of the transparent support (or base sheet) include resin sheets in addition to glass and ceramics. As resin which comprises a transparent support body, resin similar to the said glare-proof layer can be used. Preferred transparent supports include transparent polymer films such as cellulose derivatives [cellulose triacetate (TAC), cellulose acetate such as cellulose diacetate, etc.], polyester resins [polyethylene terephthalate (PET), polybutylene terephthalate (PBT), Polyarylate resin, etc.], Polysulfone resin [Polysulfone, Polyethersulfone (PES), etc.], Polyetherketone resin [Polyetherketone (PEK), Polyetheretherketone (PEEK), etc.], Polycarbonate resin (PC ), Polyolefin resins (polyethylene, polypropylene, etc.), cyclic polyolefin resins (ARTON, ZEONEX, etc.), halogen-containing resins (poly Etc. fluoride), (meth) acrylic resins, styrene-based resin (polystyrene), vinyl acetate or vinyl alcohol resin (polyvinyl alcohol, etc.), and the film formed in the like. The transparent support may be uniaxially or biaxially stretched, but is preferably optically isotropic. A preferred transparent support is a low birefringence support sheet or film. Examples of the optically isotropic transparent support include unstretched sheets or films, such as polyesters (PET, PBT, etc.), cellulose esters, particularly cellulose acetates (cellulose diacetate, cellulose triacetate, etc.). Examples thereof include sheets or films formed of cellulose acetate C _3-4 organic acid esters such as acetate, cellulose acetate propionate, and cellulose acetate butyrate. The thickness of the support having a two-dimensional structure can be selected from the range of, for example, about 5 to 2000 μm, preferably about 15 to 1000 μm, and more preferably about 20 to 500 μm.

[Optical member]
The low-reflection antiglare layer has not only high antiglare properties but also high light scattering properties. In particular, it is possible to increase the scattering intensity in a specific angle range while transmitting and scattering the transmitted light isotropically. Furthermore, the clarity of the transmitted image is high. Further, external light reflection can be efficiently prevented on the surface of the low refractive index layer. Therefore, the antiglare film of the present invention is suitable for uses such as an optical member, and the support can be composed of a transparent polymer film for forming various optical members. The antiglare film obtained in combination with the transparent polymer film may be used as an optical member as it is, and various optical elements disposed in the optical path of an optical element (for example, a polarizing plate, a retardation plate, a light guide plate, etc.) An optical member may be formed in combination with an element. That is, the antiglare film may be disposed or laminated on at least one optical path surface of the optical element. For example, an anti-glare film may be laminated on at least one surface of the retardation plate, and an anti-glare film may be disposed or laminated on the exit surface of the light guide plate.

  An antiglare film in which scratch resistance is imparted to the low reflection antiglare layer can also function as a protective film. Therefore, the antiglare film of the present invention is a laminate (optical member) using an antiglare film instead of at least one of the two protective films of the polarizing plate, that is, at least the polarizing plate. It is suitable for use as a laminate (optical member) in which an antiglare film is laminated on one surface.

  In the antiglare film of the present invention, a large amount of fine concavo-convex structure corresponding to the phase separation structure is formed on the surface of the antiglare layer. Therefore, glare can be suppressed while preventing reflection of an outside scene due to surface reflection, and antiglare properties can be improved. Furthermore, since a low refractive index layer is overcoated on such an antiglare layer, it covers fine irregularities (for example, irregularities with an elevation difference of about 1 μm or less), and as a result, the reflectivity due to the lower refractive index of the surface. Combined with the reduction, the whitening of the display can be reduced. In addition, the white floating of a display can be evaluated visually by bonding an anti-glare film to a black board through a transparent adhesive, for example.

  Further, as described above, in the phase separation structure, the average interphase distance of the domains is substantially regular or periodic. Therefore, the light that enters and passes through the antiglare film exhibits a scattered light maximum at a specific angle away from the straight transmitted light due to Bragg reflection corresponding to the interphase average distance (or the periodicity of the surface uneven structure). That is, the antiglare film of the present invention isotropically transmits incident light and scatters or diffuses, but scattered light (transmitted scattered light) is a scattering angle shifted from the scattering center [for example, 0.1 to 0.1]. 10 °, preferably 1-10 ° (eg 3-9 °), more preferably 1-8 ° (eg 4-8 °), in particular 1.5-8 ° (eg 1.5-5). °), usually about 2 to 5 °]. Therefore, the adverse effect of the scattered light due to the surface irregularities on the profile of the straight transmitted light is extremely small, and the problem of glare that could not be solved by the conventional fine particle dispersed antiglare sheet can be avoided.

  The maximum value of the scattered light intensity may be separated into peaks in the angular distribution profile of the scattered light intensity, and even if it is a shoulder-like peak or a flat peak, it can be regarded as having a maximum value. .

  In addition, as shown in FIG. 1, the angular distribution of the light which permeate | transmitted the glare-proof film uses the measuring device provided with the laser light source 1 such as a He-Ne laser, and the optical receiver 4 installed in the goniometer. It can be measured. In this example, the sample 3 can be irradiated with laser light from the laser light source 1 via the ND filter 2, and the scattered light from the sample can be changed at a scattering angle θ with respect to the optical path of the laser light. And it detects with the detector (light receiver) 4 provided with the photoelectron amplifier tube, and measures the relationship between scattering intensity and scattering angle (theta). As such an apparatus, an automatic laser light scattering measuring apparatus (manufactured by Nippon Kagaku Engineering Co., Ltd.) can be used.

  The total light transmittance of the antiglare film of the present invention is, for example, 70 to 100%, preferably 80 to 100%, more preferably 85 to 100% (for example, 85 to 95%), particularly 90 to 100% ( For example, it is about 92 to 99%).

  The haze of the antiglare film of the present invention is 1 to 30%, preferably 2 to 25%, more preferably 2 to 20% (for example, 3 to 15%), particularly 3 to 10% (for example, 5 to 5%). 10%).

  The haze and total light transmittance can be measured using a NDH-300A haze meter manufactured by Nippon Denshoku Industries Co., Ltd. in accordance with JIS K7105.

  The transmitted image definition of the antiglare film of the present invention is 10% or more and less than 70%, preferably 10 to 50%, more preferably 10 to 40% when an optical comb having a width of 0.5 mm is used. In particular, it is about 10 to 30%).

  The transmitted image definition is a scale for quantifying blur and distortion of light transmitted through a film. The transmitted image definition is measured through an optical comb that moves the transmitted light from the film, and a value is calculated based on the amount of light in the bright and dark portions of the optical comb. That is, when the film blurs the transmitted light, the image of the slit formed on the optical comb becomes thick, so that the amount of light at the transmissive part is 100% or less, while the light leaks at the non-transmissive part, 0%. That's it. The value C of the transmitted image definition is defined by the following equation from the maximum transmitted light value M of the transparent portion and the minimum transmitted light value m of the opaque portion of the optical comb.

C (%) = [(M−m) / (M + m)] × 100
That is, as the value of C approaches 100%, the image blur due to the antiglare film is smaller [reference: Suga, Mitamura, painting technology, July 1985 issue].

  As a measuring device for measuring the transmitted image definition, Suga Test Instruments Co., Ltd. image clarity measuring instrument ICM-1DP can be used. As the optical comb, an optical comb having a width of 0.125 to 2 mm can be used.

  When the transmitted image definition is in the above range, the outline of the reflection can be sufficiently blurred, so that a good antiglare property can be imparted. In particular, the antiglare film having such transmitted image definition is suitable for a liquid crystal display such as a high definition LCD. When the transmitted image definition is too high, strong external light is transmitted through the low-reflection anti-glare layer and from the specular reflective layer in the liquid crystal cell (for example, the glass surface of the upper electrode and the conductive surface of the upper electrode inside the cell). The light is reflected without being scattered, and the reflected light is transmitted without being scattered so much. Therefore, with an antiglare film having a transmitted image definition of 70% or more, it is not possible to achieve the reflection prevention required for a liquid crystal display, particularly a large display. On the other hand, if the transmitted sharpness is too small, the reflection can be prevented, but the sharpness of the image is lowered.

  However, even if the transmitted image definition is less than 70%, the haze, which is a measure of the haze of the film, needs to be in the above range. That is, since the haze and the transmitted image definition are in the above-described range, even if the haze and the transmitted image definition are mounted on a large display device such as a liquid crystal display, it is possible to prevent reflection.

  JP-A-2004-126495 discloses a method for producing a sheet by evaporating a solvent from a solution in which at least one polymer and at least one curable resin precursor are uniformly dissolved, as in the present invention. Discloses a method for producing an antiglare layer by decomposing spinodal under appropriate conditions and then curing the precursor. Although this document discloses an antiglare film composed of a single antiglare layer and having a transmitted image definition of 70% or more, it specifically describes an antiglare film having a transmitted image definition of less than 70% and a method for producing the same. Is not disclosed.

The antiglare film having such transmitted image definition and haze can be prepared by selecting the type and ratio of the polymer. For example, first, a cellulose derivative (especially an aliphatic C _1-6 organic acid ester such as cellulose acetate propionate) is used as a polymer for performing stable liquid-liquid phase separation, and the blending ratio of the cellulose derivative is prevented. It suppresses to 5 to 10% by weight (preferably 6 to 10% by weight, more preferably 7 to 10% by weight) of the solid content forming the glare layer, and forms an antiglare layer by liquid-liquid phase separation, and is low It can be prepared by coating a refractive index layer. In particular, in blending cellulose derivatives, polymers having functional groups involved in the curing reaction (such as (meth) acrylic resins having epoxy groups) and curable resin precursors (such as polyfunctional (meth) acrylic monomers) ) And a cellulose derivative (particularly, an aliphatic C _1-6 organic acid ester such as cellulose acetate propionate) (weight ratio), for example, curable component / cellulose derivative = 90 / It is preferably 10 to 95/5, preferably 90/10 to 94/6, and more preferably about 90/10 to 93/7. Although the mechanism is not yet elucidated, by adjusting the blending ratio of the cellulose derivative, the surface of the antiglare layer is filled with uneven shapes derived from a phase separation structure that is gentle and has a relatively large period. This surface shape is basically maintained even after the low refractive index layer is coated, and it is estimated that the transmission sharpness is lowered.

  In the wet spinodal decomposition, the solvent can be selected according to the type and solubility of the polymer and curable resin precursor, and at least the solid content (a plurality of polymers and curable resin precursors, reaction initiators, other additives) is selected. Any solvent that can be uniformly dissolved may be used. Examples of such a solvent include ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), ethers (dioxane, tetrahydrofuran, etc.), aliphatic hydrocarbons (hexane, etc.), alicyclic hydrocarbons ( Cyclohexane etc.), aromatic hydrocarbons (toluene, xylene etc.), halogenated carbons (dichloromethane, dichloroethane etc.), esters (methyl acetate, ethyl acetate, butyl acetate etc.), water, alcohols (ethanol, isopropanol, Butanol, cyclohexanol, methoxypropanol, putoxyethanol, etc.), cellosolves (methyl cellosolve, ethyl cellosolve, etc.), alkylene glycols (ethylene glycol, propylene glycol, etc.), cellosolve Tate, sulfoxides (dimethyl sulfoxide, etc.), amides (dimethylformamide, dimethylacetamide, etc.), and others. The solvent may be a mixed solvent.

  The antiglare film of the present invention forms a phase separation structure from a liquid phase (or liquid composition) containing the polymer, a curable resin precursor, and a solvent by spinodal decomposition accompanying evaporation of the solvent, It can be produced by curing the curable resin precursor to form an antiglare layer, and forming a low refractive index layer on the antiglare layer.

  The phase separation structure is usually obtained by applying or casting a mixed solution (particularly a liquid composition such as a uniform solution) containing the polymer, a curable resin precursor, and a solvent to a peelable or non-peelable support, It can be formed by evaporating the solvent from the coating. The obtained phase separation structure has a regular or periodic average interphase distance.

  The antiglare layer can be formed by forming at least the curable resin precursor using heat, active light, or the like after forming the phase separation structure. In a preferred embodiment, as the mixed liquid, a composition containing the thermoplastic resin, a photocurable compound, a photopolymerization initiator, and a solvent that can dissolve the thermoplastic resin and the photocurable compound can be used. The antiglare layer is formed by curing the photocuring component of the phase separation structure formed by spinodal decomposition by light irradiation. In another preferred embodiment, a composition containing a plurality of incompatible polymers, a photocurable compound, a photopolymerization initiator, and a solvent can be used as the mixed solution, which is formed by spinodal decomposition. The antiglare layer is formed by curing the photocuring component of the phase separation structure by light irradiation.

  The concentration of the solute (polymer and curable resin precursor, reaction initiator, other additives) in the mixed solution can be selected within a range where phase separation occurs and a range where casting properties and coating properties are not impaired. It is about 80% by weight, preferably 5 to 60% by weight, more preferably about 15 to 40% by weight (particularly 20 to 40% by weight).

  In addition, when the said liquid mixture is apply | coated to a transparent support body, a transparent support body may melt | dissolve or swell depending on the kind of solvent. For example, when a coating liquid (uniform solution) containing a plurality of resins is applied to a triacetyl cellulose film, the coated surface of the triacetyl cellulose film may be eluted, eroded, or swollen depending on the type of solvent. In such a case, an optically isotropic solvent-resistant coating layer may be formed by previously applying a solvent-resistant coating agent on the application surface of a transparent support (such as a triacetyl cellulose film). Such coating layers include, for example, AS resins, polyester resins, thermoplastic resins such as polyvinyl alcohol resins (polyvinyl alcohol, ethylene-vinyl alcohol copolymer, etc.), epoxy resins, silicone resins, and UV curable types. It can be formed using a curable resin such as a resin.

  Moreover, when apply | coating a liquid mixture or a coating liquid to a transparent support body, according to the kind of transparent support body, you may select the solvent which does not melt | dissolve, erode, or swell a transparent support body. For example, when a triacetylcellulose film is used as a transparent support, an antiglare layer can be formed without impairing the properties of the film by using, for example, tetrahydrofuran, methyl ethyl ketone, isopropanol, toluene, etc. as the solvent of the mixed solution or coating solution. it can.

  Phase casting by spinodal decomposition can be induced by evaporating the solvent after casting or coating the mixed solution. The solvent evaporation temperature (phase separation temperature) is not particularly limited, but the difference between the boiling point of the solvent and the evaporation temperature is, for example, within 120 ° C, preferably within 100 ° C (eg, within 70 ° C), more preferably It is preferable to select within a range of 60 ° C. or less (for example, 50 ° C. or less). Further, the solvent may be evaporated at a temperature lower than the boiling point of the solvent (for example, a temperature 1 to 120 ° C., preferably 5 to 50 ° C., particularly 10 to 50 ° C. lower than the boiling point of the solvent). The evaporation of the solvent is usually drying, for example, at a temperature of 30 to 200 ° C. (for example, 30 to 100 ° C.), preferably 40 to 120 ° C., more preferably about 40 to 80 ° C., depending on the boiling point of the solvent. This can be done by drying.

  By such spinodal decomposition accompanied by evaporation of the solvent, regularity or periodicity can be imparted to the average distance between the domains of the phase separation structure. Then, the phase separation structure formed by spinodal decomposition can be immediately fixed by curing the precursor. Curing of the precursor can be performed by heating, light irradiation, or a combination of these methods depending on the type of the curable resin precursor. As long as it has the said phase-separation structure, a heating temperature can be selected from an appropriate range, for example, about 50-150 degreeC, and may be selected from the temperature range similar to the said layer separation temperature.

  The light irradiation can be selected according to the type of the photocuring component or the like, and usually ultraviolet rays, electron beams, etc. can be used. A general-purpose exposure source is usually an ultraviolet irradiation device. Note that light irradiation may be performed in an inert gas atmosphere if necessary.

  The method for forming the low refractive index layer is not particularly limited as long as at least a layer composed of the resin material can be formed on the antiglare layer. Usually, the low refractive index component is formed on the antiglare layer. The low refractive index layer can be formed by applying or casting a coating solution containing, and curing the coating film with heat or active light.

  In addition to the low refractive index component (fluorine-containing compound, etc.), the coating liquid is usually an organic solvent [for example, the same as the solvent exemplified in the item of the antiglare layer depending on the type of the low refractive index resin. In addition to the organic solvent], a reactive diluent (such as a (meth) acrylic monomer such as a polyfunctional (meth) acrylate) may be included. Such a solvent may be removed by evaporation along with the coating film, and when the solvent is a reactive diluent, it may be cured by polymerization as the fluorine-containing resin precursor is cured. . The coating liquid further contains a curing agent [a thermal polymerization initiator such as an organic peroxide; a photopolymerization initiator (such as a ketone polymerization initiator such as 1-hydroxy-cyclohexyl-phenyl-ketone)]. May be. Further, the coating solution may contain a crosslinking agent or the like.

  The concentration of the solid content (low refractive index component, compound capable of curing reaction, and other additives) in the coating solution for the low refractive index layer can be selected within a range that does not impair the coating properties. % By weight, preferably 0.5 to 10% by weight, more preferably about 1 to 5% by weight.

[Display device]
The anti-glare film of the present invention is particularly suitably used for television (TV) applications, which are used for television (TV) applications having a strong contrast feeling in which black is tightened. Further, it can be used for various display devices such as a liquid crystal display (LCD) device, a plasma display, and a display device with a touch panel. These display devices include the antiglare film and the optical member (particularly, a laminate of a polarizing plate and an antiglare film) as optical elements. In particular, since it can be prevented from being reflected even when mounted on a large-sized liquid crystal display device such as a high-definition or high-definition liquid crystal display, it can be preferably used for a liquid crystal display device.

  The liquid crystal display device may be a reflective liquid crystal display device that illuminates a display unit including a liquid crystal cell using external light, and a transmissive type that includes a backlight unit for illuminating the display unit. It may be a liquid crystal display device. In the reflective liquid crystal display device, incident light from outside can be taken in through the display unit, and the transmitted light that has passed through the display unit can be reflected by the reflecting member to illuminate the display unit. In the reflective liquid crystal display device, the antiglare film and the optical member (particularly, a laminate of a polarizing plate and an antiglare film) can be disposed in the optical path ahead of the reflective member. For example, the antiglare film or the optical member can be disposed or laminated between the reflecting member and the display unit, on the front surface of the display unit, or the like.

  In a transmissive liquid crystal display device, a backlight unit causes light from a light source (a tubular light source such as a cold cathode tube or a point light source such as a light-emitting diode) to enter from one side and exit from a front emission surface. A light guide plate (for example, a light guide plate having a wedge-shaped cross section) may be provided. If necessary, a prism sheet may be provided on the front side of the light guide plate. In general, a reflection member for reflecting light from the light source toward the emission surface is disposed on the back surface of the light guide plate. In such a transmissive liquid crystal display device, the antiglare film and the optical member can usually be disposed or laminated in the optical path ahead from the light source. For example, the antiglare film or the optical member can be disposed or laminated between the light guide plate and the display unit, on the front surface of the display unit, or the like.

  INDUSTRIAL APPLICABILITY The present invention is useful as an optical element for various applications that require anti-glare properties and light scattering properties, such as the optical member and liquid crystal display devices (particularly high-definition or high-definition display devices). is there.

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

Reference example 1
Acrylic resin having a polymerizable unsaturated group in the side chain [compound in which 3,4-epoxycyclohexenylmethyl acrylate is added to a part of the carboxyl group of (meth) acrylic acid- (meth) acrylic ester copolymer) Manufactured by Daicel Chemical Industries, Ltd., Cyclomer P (ACA) 320M, solid content 49.6% by weight] 5.25 parts by weight, cellulose acetate propionate (degree of acetylation = 2.5%, degree of propionylation = 46%, polystyrene-equivalent number average molecular weight 75000; manufactured by Eastman Co., CAP-482-20) 0.9 part by weight, polyfunctional acrylic UV curing monomer (manufactured by Daicel-UCB Co., Ltd., DPHA) 6.3 Parts by weight, 0.5 parts by weight of a photoinitiator (manufactured by Ciba Specialty Chemicals, Irgacure 184) and methyl ethyl ketone (MEK) 20.1 parts by weight, 5.4 parts by weight of 1-butanol was dissolved in 1-methoxy-2-propanol (MMPG) 1.86 parts by weight. This solution was cast on a triacetylcellulose film using a wire bar # 24, and then left in an explosion-proof oven at 80 ° C. for 2 minutes to evaporate the solvent and form a coat layer having a thickness of about 9 μm. . Then, the coating layer was subjected to UV curing treatment by irradiating ultraviolet rays from a metal halide lamp (manufactured by Eye Graphics Co., Ltd.) for about 30 seconds to form an antiglare layer having hard coat properties and a surface uneven structure. As a low refractive index layer, a thermosetting fluorine-containing compound coating liquid (manufactured by Nissan Chemical Co., Ltd., LR204-6, 1 wt% solid content) is applied using wire bar # 5, dried, and then at 90 ° C. Heat cured for 5 minutes.

Example 1
Acrylic resin having a polymerizable unsaturated group in the side chain [compound in which 3,4-epoxycyclohexenylmethyl acrylate is added to a part of the carboxyl group of (meth) acrylic acid- (meth) acrylic ester copolymer) Manufactured by Daicel Chemical Industries, Ltd., Cyclomer P (ACA) 320M, solid content 49.6% by weight] 6.05 parts by weight, cellulose acetate propionate (degree of acetylation = 2.5%, degree of propionylation = 46%, polystyrene-equivalent number average molecular weight 75000; manufactured by Eastman Co., CAP-482-20) 0.8 part by weight, polyfunctional acrylic UV curing monomer (manufactured by Daicel-UCB Co., Ltd., DPHA) 6.2 Part by weight, 0.5 part by weight of photoinitiator (Ciba Specialty Chemicals, Irgacure 184) dissolved in 26.5 parts by weight of MEK It was. This solution is cast on a triacetylcellulose film using a wire bar # 24 and then left in an explosion-proof oven at 60 ° C. for 1.5 minutes to evaporate the solvent and form a coat layer having a thickness of about 9 μm. I let you. Then, the coating layer was subjected to UV curing treatment by irradiating ultraviolet rays from a metal halide lamp (manufactured by Eye Graphics Co., Ltd.) for about 30 seconds to form an antiglare layer having hard coat properties and a surface uneven structure. As a low refractive index layer, a thermosetting fluorine-containing compound coating liquid (manufactured by Nissan Chemical Co., Ltd., LR204-6, 1 wt% solid content) is applied using wire bar # 5, dried, and then at 90 ° C. Heat cured for 5 minutes.

Comparative Example 1
Acrylic resin having a polymerizable unsaturated group in the side chain [compound in which 3,4-epoxycyclohexenylmethyl acrylate is added to a part of the carboxyl group of (meth) acrylic acid- (meth) acrylic ester copolymer) Manufactured by Daicel Chemical Industries, Ltd., Cyclomer P (ACA) 320M, solid content 49.6% by weight] 5.65 parts by weight, cellulose acetate propionate (degree of acetylation = 2.5%, degree of propionylation = 46%, polystyrene conversion number average molecular weight 75000; Eastman, CAP-482-20) 1.2 parts by weight, polyfunctional acrylic UV curable monomer (Daicel UCB Co., Ltd., DPHA) 6 parts by weight , 0.53 parts by weight of a photoinitiator (Ciba Specialty Chemicals, Irgacure 184) was added to 37.15 tetrahydrofuran. It was dissolved in the amount section. This solution was cast on a triacetylcellulose film (Fuji Photo Film Co., Ltd., TD-80) using a wire bar # 24, and then left in an explosion-proof oven at 80 ° C. for 3 minutes to evaporate the solvent. Thus, a coat layer having a thickness of about 7 μm was formed. Then, the coating layer was subjected to UV curing treatment by irradiating ultraviolet rays from a metal halide lamp (manufactured by Eye Graphics Co., Ltd.) for about 30 seconds to form an antiglare layer having hard coat properties and a surface uneven structure. As a low refractive index layer, a thermosetting fluorine-containing compound coating liquid (manufactured by Nissan Chemical Co., Ltd., LR204-6, 1 wt% solid content) is applied using wire bar # 5, dried, and then at 90 ° C. Heat cured for 5 minutes.

Comparative Example 2
Acrylic resin having a polymerizable unsaturated group in the side chain [compound in which 3,4-epoxycyclohexenylmethyl acrylate is added to a part of the carboxyl group of (meth) acrylic acid- (meth) acrylic ester copolymer) Manufactured by Daicel Chemical Industries, Ltd., Cyclomer P (ACA) 320M, solid content 49.6% by weight] 5.25 parts by weight, cellulose acetate propionate (degree of acetylation = 2.5%, degree of propionylation = 46%, polystyrene-equivalent number average molecular weight 75000; manufactured by Eastman Co., CAP-482-20) 1.1 parts by weight, polyfunctional acrylic UV curing monomer (manufactured by Daicel UCB Co., Ltd., DPHA) 6.3 weights Parts, 0.62 parts by weight of photoinitiator (Ciba Specialty Chemicals, Irgacure 184) were added to 37. It was dissolved in 6 parts by weight. This solution was cast on a triacetylcellulose film (manufactured by Fuji Photo Film Co., Ltd., TD-80) using wire bar # 24, and then left in an explosion-proof oven for 3 minutes to evaporate the solvent and thicken the solution. A coating layer having a thickness of about 7 μm was formed. Then, the coating layer was subjected to UV curing treatment by irradiating ultraviolet rays from a metal halide lamp (manufactured by Eye Graphics Co., Ltd.) for about 30 seconds to form an antiglare layer having hard coat properties and a surface uneven structure. As a low refractive index layer, a thermosetting fluorine-containing compound coating liquid (manufactured by Nissan Chemical Co., Ltd., LR204-6, 1 wt% solid content) is applied using wire bar # 5, dried, and then at 90 ° C. Heat cured for 5 minutes.

Comparative Example 3
Acrylic resin having a polymerizable unsaturated group in the side chain [compound in which 3,4-epoxycyclohexenylmethyl acrylate is added to a part of the carboxyl group of (meth) acrylic acid- (meth) acrylic ester copolymer) Manufactured by Daicel Chemical Industries, Ltd., Cyclomer P (ACA) 320M, solid content 49.6% by weight] 5.24 parts by weight, cellulose acetate propionate (degree of acetylation = 2.5%, degree of propionylation = 46%, polystyrene-equivalent number average molecular weight 75000; manufactured by Eastman, CAP-482-20) 1.1 parts by weight, polyfunctional urethane acrylate UV curing monomer (manufactured by Daicel UCB, EB8301) 6.3 Parts by weight, 0.62 parts by weight of photoinitiator (Ciba Specialty Chemicals, Irgacure 184) It was dissolved in Rofuran 37.36 parts by weight. This solution was cast on a triacetylcellulose film (manufactured by Fuji Photo Film Co., Ltd., TD-80) using wire bar # 24, and then left in an explosion-proof oven for 3 minutes to evaporate the solvent and thicken the solution. A coating layer having a thickness of about 7 μm was formed. Then, the coating layer was subjected to UV curing treatment by irradiating ultraviolet rays from a metal halide lamp (manufactured by Eye Graphics Co., Ltd.) for about 30 seconds to form an antiglare layer having hard coat properties and a surface uneven structure. As a low refractive index layer, a thermosetting fluorine-containing compound coating liquid (manufactured by Nissan Chemical Co., Ltd., LR204-6, 1 wt% solid content) is applied using wire bar # 5, dried, and then at 90 ° C. Heat cured for 5 minutes.

Comparative Example 4
20 parts by weight of a polyfunctional acrylic UV curable monomer (manufactured by Daicel UCB Co., Ltd., DPHA), 1.6 parts by weight of acrylic-styrene copolymer beads having an average particle size of 3.5 μm as transparent fine particles, a photoinitiator ( A dispersion was prepared by mixing 1 part by weight of Ciba Specialty Chemicals, Irgacure 184) with 30 parts by weight of a mixed solvent of tetrahydrofuran / toluene = 7/3 (weight ratio). This dispersion was applied so as to have a dry thickness of 3 μm, and irradiated with ultraviolet rays from a metal halide lamp (manufactured by Eye Graphics Co., Ltd.) for about 30 seconds to perform UV curing treatment. As a low refractive index layer, a thermosetting fluorine-containing compound coating liquid (manufactured by Nissan Chemical Co., Ltd., LR204-6, 1 wt% solid content) is applied using wire bar # 5, dried, and then at 90 ° C. Heat cured for 5 minutes.

Reference Example 1 was observed by anti-glare and anti-reflection film of the transmission optical microscope of Example 1及 beauty Comparative Examples 1-4, Reference Example 1, the coating layer of Example 1及 beauty Comparative Examples 1 to 3 liquid It had a drop-like phase separation structure.

When the angular distribution of the transmitted light was measured for the reference example 1, the example 1, and the comparative examples 1 to 4 using the apparatus shown in FIG. 1, the examples 1 and 2 were in the vicinity of the scattering angle = 2 °. In the films 1 to 3, the scattering light maximum was observed at a scattering angle of around 5 °, and at a scattering angle separated from the linearly transmitted light (scattering angle = 0 °). In Comparative Example 4, the maximum in scattering was not recognized.

Reference Example 1, the transmission image clarity of the anti-glare film obtained in Example 1及 beauty Comparative Examples 1-4, total light transmittance, the result of measuring the haze are shown in Table 1.

Reflection of reflected light, white floating (sink of black display), and image contrast are low reflection anti-glare layers obtained in Examples and Comparative Examples, respectively, with a front luminance of 450 cd / m ² and a contrast of 400 to 1, 20 respectively. The sample was mounted on the surface of a VA (vertical alignment) type LCD panel having a resolution of 60 ppi and visually evaluated according to the following criteria.

(Reflection)
○: No reflection Δ: There is a slight reflection ×: The reflection is intense.

(White float)
A: The black display appears clear. B: The black display appears slightly white. Δ: The black display appears white. ×: The black display appears white.

(Image contrast)
◎: Visible clearly ○: Visible almost clearly △: Visible ×: Difficult to see

As is clear from the results in Table 1, the antiglare and antireflection films of Reference Example 1 and Example 1 have no reflection, whitening, and high image contrast. On the other hand, the films of Comparative Examples 1 to 3 have a strong reflection, and the film of Comparative Example 4 has a strong white floating and a low image contrast. Therefore, the antiglare film of the present invention is a film suitable for forming a high contrast image on a large liquid crystal display.

FIG. 1 is a schematic diagram showing an apparatus for measuring the angular distribution of transmitted light.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Laser light source 2 ... ND filter 3 ... Sample 4 ... Detector

Claims (24)

At least one polymer and at least one curable resin precursor, and at least two components of the polymer and the precursor are phase-separated by spinodal decomposition from a liquid phase, and the precursor is and cured to have anti-glare layer, an the anti-glare anti-glare composed of at least one of the low refractive index of the resin layer formed on a surface of the layer film has an uneven structure on the surface The incident light is isotropically transmitted and scattered, the scattering angle showing the maximum value of the scattered light intensity is 0.1 to 10 °, the total light transmittance is 70 to 100%, and the haze is An antiglare film having a transmitted image sharpness of 10 to 50% as measured with a image clarity measuring device using an optical comb having a width of 3 to 15 % and a width of 0.5 mm. A plurality of polymer between the polymer and curable resin precursor, or a plurality of curable resin precursors with each other, anti-glare film according to claim 1 wherein the phase-separated by spinodal decomposition. Polymer, while being constituted by a phase-separable multiple polymer by spinodal decomposition, the curable resin precursor, among the plurality of polymers, anti-glare film according to claim 1, further comprising at least one polymer compatible . The anti-glare film according to claim 3 , wherein at least one of the plurality of polymers has a functional group involved in the curing reaction of the curable resin precursor. The anti-glare film according to claim 2 , wherein at least one of the plurality of polymers has a (meth) acryloyl group. A plurality of polymers phase-separated by spinodal decomposition are a cellulose derivative and at least one resin selected from styrene resins, (meth) acrylic resins, alicyclic olefin resins, polycarbonate resins, and polyester resins. The anti-glare film according to claim 4 , wherein the anti-glare film is configured and at least one of the polymers has a polymerizable group. The curable resin precursor is selected from epoxy (meth) acrylate, urethane (meth) acrylate, polyester (meth) acrylate, silicone (meth) acrylate, and polyfunctional monomer having at least two polymerizable unsaturated bonds The antiglare film according to claim 1 , wherein the antiglare film is composed of at least one kind. Anti-glare film according to claim 1, wherein the scratch resistance antiglare layer is provided by curing the curable resin precursor. Curing of the curable resin precursor, anti-glare film according to claim 1, wherein the regular or periodic phase separation structure in the anti-glare layer is immobilized.   The antiglare film according to claim 1, wherein the antiglare layer is cured by at least one selected from active energy rays and heat.   The anti-glare film according to claim 1, wherein the anti-glare layer contains a polymer and a cured resin in a ratio of polymer / cured resin = 5/95 to 60/40 (weight ratio). The antiglare film according to claim 2 , wherein at least one of the plurality of polymers is a cellulose derivative, and a ratio of the cellulose derivative is 5 to 10% by weight in a solid content constituting the antiglare layer.   The anti-glare film according to claim 1, wherein the resin layer having a low refractive index is composed of a resin having a refractive index of 1.30 to 1.49.   The anti-glare film according to claim 1, wherein the resin layer having a low refractive index contains a fluorine-containing compound.   The antiglare film according to claim 1, wherein the resin layer having a low refractive index is composed of a curable fluororesin precursor, and the precursor is cured by at least one selected from active energy rays and heat. .   The anti-glare film according to claim 1, wherein an anti-glare layer and a low refractive index resin layer are sequentially formed on the transparent support. The antiglare film according to claim 16 , wherein the transparent support is composed of a transparent polymer film for forming an optical member.   The anti-glare film according to claim 1, which is used for at least one kind of display device selected from a liquid crystal display device, a plasma display, and a touch panel type input device.   An anti-glare layer is formed by forming a phase separation structure from a liquid phase containing at least one polymer, at least one curable resin precursor, and a solvent, by spinodal decomposition accompanying evaporation of the solvent, and curing the resin precursor. The method for producing an antiglare film according to claim 1, wherein a resin layer having a low refractive index is formed on at least one surface of the antiglare layer. The manufacturing method according to claim 19 , wherein a plurality of polymers, a polymer and a curable resin precursor, or a plurality of curable resin precursors form a phase separation structure by spinodal decomposition. A phase separation structure is formed by spinodal decomposition from a composition containing a thermoplastic resin, a photocurable compound, a photopolymerization initiator, and a solvent soluble in the thermoplastic resin and the photocurable compound, and is irradiated with light. The manufacturing method of Claim 19 which forms an anti-glare layer by doing. A thermoplastic resin, a resin that is incompatible with the thermoplastic resin and has a photocurable group, a photocurable compound, a photopolymerization initiator, and a solvent that dissolves the resin and the photocurable compound The manufacturing method of Claim 19 which forms a phase-separation structure by spinodal decomposition | disassembly from the composition containing these, and forms an anti-glare layer by irradiating light. The production method according to claim 19 , wherein at least one antiglare layer is formed on the transparent support, and a low refractive index resin layer is formed on the antiglare layer.   An optical member in which the film according to claim 1 is laminated on at least one surface of a polarizing plate.

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