JP4739720B2 - Method for producing antiglare film - Google Patents

Description

  The present invention relates to a method for producing an antiglare film used for various high-definition image displays used for image display of computers, word processors, televisions and the like.

  In recent years, in displays such as cathode ray tube display (CRT) displays, liquid crystal displays, plasma displays, touch panel input devices, organic or inorganic EL (electroluminescence) displays, FEDs (field emission displays), etc. When an external light source is reflected on the display surface, the reflected light interferes with the screen. That is, since visibility is remarkably inferior due to such reflection, various displays are provided with an anti-glare layer on the display surface for diffusing reflected light to some extent.

  As an antiglare layer, for example, Japanese Patent Laid-Open No. 6-18706 (Patent Document 1) essentially includes a resin bead having a refractive index of 1.40 to 1.60 and an ionizing radiation curable resin composition on a transparent substrate. An anti-scratch anti-glare film in which an anti-glare layer is formed is disclosed. In JP-A-10-20103 (Patent Document 2), at least a base film and transparent particles having an average particle diameter of 0.5 to 1.5 μm are contained in an amount of 20 to 30 with respect to 100 parts by weight of the curable resin. An antiglare film which is a laminated film with an antiglare layer containing parts by weight is disclosed. Further, in Japanese Patent No. 3314965 (Patent Document 3), an anti-glare layer having fine irregularities on the surface composed of an ionizing radiation curable resin composition is formed on a transparent substrate. A scratch-resistant antiglare film containing an organic filler is disclosed. In addition, an antiglare layer of a type that forms an uneven shape on the surface of the antiglare layer by agglomeration of particles such as cohesive silica is also known.

  However, since these anti-glare layers all have a concavo-convex shape on the surface by a filler or the like, the concavo-convex shape on the surface cannot be precisely controlled in the manufacturing process. In addition, since the manufacturing stability is low, it is difficult to determine the shape, position, interval, size, and the like of the uneven shape on the surface. As a result, the uneven shape on the surface is random in position, size, shape, size, frequency, etc., and the antiglare property of the manufactured antiglare layer varies greatly. In addition, as an antiglare layer, there is a type in which a film having a concavo-convex shape is laminated on the surface of the layer and the concavo-convex shape is transferred.

  Further, JP-A-6-16851 (Patent Document 4) essentially discloses an ionizing radiation curable resin composition formed on a transparent substrate with a mat-shaped molding film having fine irregularities on the surface. An anti-scratch anti-glare film in which an anti-glare layer is formed is disclosed. Japanese Patent Application Laid-Open No. 2000-206317 (Patent Document 5) discloses an antiglare film in which an antiglare layer made of at least an ionizing radiation curable resin is laminated on one or both surfaces of a transparent substrate film. Thus, an antiglare film is disclosed in which an irregular shape having periodicity is provided on the surface of the antiglare layer. In these production methods, controlled surface irregularities can be formed by using a shaped film having a regular ordered structure or a mat-like shaped film with a controlled surface irregularity shape.

  However, since it is difficult to produce such a mat-shaped shaped film itself, mass productivity is low. It is also known that when such a regular arrangement is made artificially, the reflected light inevitably causes interference and iridescence.

  On the other hand, in Japanese Patent Application Laid-Open No. 2004-126495 (Patent Document 6), an antiglare film composed of at least an antiglare layer, the antiglare layer has a concavo-convex structure on its surface, Disclosed is an antiglare film 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%. ing. This document describes a regular phase separation structure and a surface corresponding to the phase separation structure from a liquid phase containing a plurality of polymers, a polymer, a curable resin precursor, and a solvent by spinodal decomposition accompanying the evaporation of the solvent. A manufacturing method for forming the concavo-convex structure is disclosed. In this method, since the antiglare layer is produced using the natural self-ordering ability well, the artificially formed minute uneven shape is formed even though the surface shape and arrangement are sufficiently controlled. Unlike, it is difficult to cause iridescence due to interference of reflected light.

However, even in this method, it is difficult to control the phase separation, and the size of the phase separation structure changes greatly due to slight changes in the raw material lot, polymer composition, etc., making it difficult to stably produce an antiglare sheet. It is.
JP-A-6-18706 (Claim 1) JP 10-20103 A (Claim 1) Japanese Patent No. 3314965 (Claim 1) JP-A-6-16851 (Claim 1) JP 2000-206317 A (Claim 1) JP 2004-126495 A (Claims 1, 21, paragraph number [0090])

  Accordingly, an object of the present invention is to provide a method capable of efficiently and stably producing an antiglare film capable of preventing reflection.

  Another object of the present invention is to provide a method capable of easily producing an antiglare film having high antiglare property and capable of suppressing iridescence due to interference of reflected light with high productivity.

  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. It has been found that an antiglare film capable of preventing reflection can be efficiently and stably produced by generating a cellular rotating convection (convection cell) using a solvent having a boiling point of 100 ° C. or higher, and has completed the present invention.

  That is, in the method for producing an antiglare film according to the present invention, a solution containing at least one polymer, at least one curable resin precursor, and a solvent having a boiling point of 100 ° C. or more is applied, and a cellular state is formed during the drying process. After generating rotational convection, the coating is cured. In this production method, the solvent may be composed of at least two types of solvents having different boiling points. Further, at least two components of the polymer and the curable resin precursor may have phase separation properties. In the drying process of the method, the coating film surface may be raised by cellular rotational convection to form a regular or periodic uneven shape on the surface. In addition, an uneven shape may be formed on the surface by cellular rotational convection and a phase separation structure may be formed. In the curing step of the above method, the coating film may be cured by irradiation with active energy rays or heat. In the method, a composition containing a thermoplastic resin, a photocurable compound, a photopolymerization initiator, and a solvent soluble in the thermoplastic resin and the photocurable compound is applied, and a cellular state is formed during the drying process. While forming uneven | corrugated shape on the surface by rotation convection, after forming a phase-separation structure, you may harden a coating film by irradiating light.

  In the above method, the polymer is a plurality of polymers that are phase-separable from each other (for example, a cellulose derivative, a styrene resin, a (meth) acrylic resin, an alicyclic olefin resin, a polycarbonate resin, a polyester resin, etc.). While being configured, 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 (such as a polymerizable group such as a (meth) acryloyl group) involved in the curing reaction of the curable resin precursor. Note that the thermoplastic resin and the curable resin precursor are usually incompatible with each other.

  In the present invention, on a transparent support, a solution containing at least one polymer, at least one curable resin precursor, and a solvent having a boiling point of 100 ° C. or more is applied, and in the course of drying, cellular rotational convection is performed. A method for producing an antiglare film in which the coating film is cured to form an antiglare film after the generation of the above is also included. In this method, the transparent support may be composed of a transparent polymer film for forming an optical member. Further, a resin layer having a low refractive index (for example, a resin having a low refractive index of 1.30 to 1.47) may be formed on the antiglare film.

  The antiglare film obtained by the above production method is also included in the present invention. The antiglare film may have a regular or periodic concavo-convex shape fixed on the surface by curing of the curable resin precursor. Further, scratch resistance may be imparted by curing the curable resin precursor.

  The present invention also includes an antiglare film obtained by the above production method. This antiglare film is suitable for use in a display device such as a liquid crystal display device, a cathode ray tube display device, a plasma display, or a touch panel type input device.

  In the present invention, an antiglare film capable of preventing reflection can be produced efficiently and stably. Furthermore, an antiglare film that has high antiglare properties and can suppress iridescence due to interference of reflected light can be easily produced with high productivity.

[Production method of antiglare film]
The antiglare film of the present invention is applied with a solution containing at least one polymer, at least one curable resin precursor, and a solvent having a boiling point of 100 ° C. or higher, and is rotated by a cellular rotational convection (convection cell) in the course of drying. ) And then the coating film is cured. More specifically, it can be carried out usually by coating the solution on a support and evaporating the solvent from the coating layer. When a peelable support is used as the support, the coating film may be peeled from the support to form an antiglare film.

(Cellular rotational convection)
In this invention, after apply | coating the said solution, the coating-film surface is raised by a cellular rotation convection, and regular or periodic uneven | corrugated shape is formed in the surface. In general, rotational convection is caused by a difference in temperature between the upper layer and the lower layer of the coating film that exceeds the limit as a result of the evaporation and drying of the solvent and the vicinity of the surface of the coating film being cooled by the heat of evaporation. Such convection is referred to as Benard convection. Benard-type convection is also called Benard-Rayleigh convection because it was discovered by Benard and theorized by Rayleigh. The critical temperature difference ΔT is determined by the thickness d of the coating film, the kinematic viscosity coefficient ν of the coating film (solution), the temperature conductivity κ of the coating film, the volume expansion coefficient α of the coating film, and the gravitational acceleration g. Convection occurs when the Rayleigh number Ra defined by the following equation exceeds a specific critical value.

Ra = (α · g · ΔT · d ³ ) / (κ · ν)
The convection generated in this manner regularly repeats ascending and descending movements, and regularly or periodically uneven shapes are arranged in a cellular manner on the film surface. It is known that the aspect ratio (application direction / thickness direction) of the cells is about 2/1 to 3/1.

  The method of cellular rotational convection is not particularly limited, and may be other convection, for example, Marangoni convection (density difference convection) due to non-uniform distribution of surface tension.

(Combination of convection and phase separation)
In the present invention, the rotational convection is generated in this way, and the surface irregularity shape caused by the convection flow and the solid content concentration difference is formed. With such convection, two components (polymer and The components may be phase separated using a solution containing at least two components of the curable resin precursor) to form a phase separated structure. Although the detailed mechanism in the combined use of convection and phase separation has not been elucidated, it can be estimated as follows.

  By using convection and phase separation in combination, convection cells are first generated after application. Next, phase separation occurs in each convection cell, and the phase separation structure grows with time, but the growth of phase separation stops at the convection cell wall. As a result, the convection cell is controlled to have an interval corresponding to the size and arrangement of the convection cells, and a concavo-convex shape having a good shape and height associated with the phase separation structure is formed. That is, an antiglare film having a sufficiently controlled shape, arrangement and size can be obtained.

(solvent)
In the present invention, the convection and phase separation can be performed by evaporating the solvent in the solution containing the polymer and the curable resin precursor. In particular, among the components contained in the solution, the solvent is indispensable for stably generating convection. This is because it has the effect of lowering the temperature of the coating film surface by the heat of vaporization accompanying evaporation, and also has the fluidity effect to allow the generated convection to flow smoothly.

  The solvent can be selected according to the type and solubility of the polymer and the curable resin precursor to be used. In the case of a mixed solvent, at least one type is a solid component (a plurality of polymers and curable resin precursors, a reaction initiator, and other additions). Any solvent can be used as long as it can uniformly dissolve the agent. Examples of such solvents 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, etc.), cellosolves (methyl cellosolve, ethyl cellosolve, etc.), cellosolve acetates, sulfoxides (dimethylsulfoxide, etc.), amides (dimethylformamide, dimethylacetamide, etc.) Etc. can be exemplified. These solvents can be used alone or in combination of two or more.

  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. This document discloses a method for forming an uneven shape on the surface of an antiglare film by phase separation in spinodal decomposition, but does not describe cellular rotational convection.

  In the present invention, in order to generate such a convection cell, it is preferable to use a solvent having a boiling point of 100 ° C. or higher at normal pressure. Furthermore, in order to generate a convection cell, it is preferable that the solvent is composed of at least two types of solvents having different boiling points. Moreover, the boiling point of a high boiling point solvent is 100 degreeC or more, Usually, it is about 100-200 degreeC, Preferably it is 105-150 degreeC, More preferably, it is about 110-130 degreeC. In particular, from the viewpoint of using a convection cell and phase separation in combination, it is preferable to use a combination of at least one solvent having a boiling point of 100 ° C. or higher and at least one solvent having a boiling point of less than 100 ° C. When such a mixed solvent is used, the low boiling point solvent generates a temperature difference between the upper layer and the lower layer due to evaporation, and the high boiling point solvent remains in the coating film and maintains fluidity.

Examples of the solvent having a boiling point of 100 ° C. or higher at normal pressure include, for example, alcohols (C _4-8 alkyl alcohols such as butanol, pentyl alcohol, hexyl alcohol, etc.), alkoxy alcohols (C _1-6 such as methoxypropanol, butoxyethanol, etc.). Alkoxy C _2-6 alkyl alcohol), alkylene glycols (C _2-4 alkylene glycol such as ethylene glycol and propylene glycol), ketones (cyclohexanone, etc.) and the like. These solvents can be used alone or in combination of two or more. Of these, C _4-8 alkyl alcohols such as butanol, C _1-6 alkoxy C _2-6 alkyl alcohols such as methoxypropanol and butoxyethanol, and C _2-4 oxyalkylene glycols such as ethylene glycol are preferable.

  The ratio of solvents having different boiling points is not particularly limited, but when a solvent having a boiling point of 100 ° C. or higher and a solvent having a boiling point of less than 100 ° C. are used in combination (when two or more types are used in combination, the total weight ratio), for example The former / the latter = 10/90 to 70/30, preferably 10/90 to 50/50, more preferably 15/85 to 40/60 (particularly about 20/80 to 40/60).

  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 triacetyl cellulose film is used as a transparent support, an antiglare film can be formed without impairing the properties of the film by using, for example, tetrahydrofuran, methyl ethyl ketone, isopropanol, toluene or the like as a solvent for a mixed solution or a coating solution. Can be formed.

(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). Of these functional groups, a polymerizable group is preferable.

  The thermoplastic resin having a polymerizable 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); A reactive group with respect to a reactive group of this thermoplastic resin is reacted with a compound having a polymerizable functional group (polymerizable compound) (ii), and the polymerizable functional group of compound (ii) is converted into a thermoplastic resin. It can manufacture by introducing.

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 can be phase-separated from each other (in the absence of a solvent) and can be phase-separated in the liquid phase before the solvent has completely evaporated. 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 styrenic resin (polystyrene, styrene-acrylonitrile copolymer, etc.), the second polymer is a cellulose derivative (for example, cellulose esters such as cellulose acetate propionate), (meta ) Acrylic resins (such as polymethyl methacrylate), alicyclic olefin resins (such as polymers containing norbornene), polycarbonate resins, polyester resins (the poly C _2-4 alkylene arylate copolyester) Etc.). 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.), (Meth) acrylic resins, alicyclic olefin resins (such as polymers having norbornene as a monomer), polycarbonate resins, polyester resins (such as the poly C _2-4 alkylene arylate copolyesters). May be. 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. .

  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.

  Surface irregularities raised by rotating convection (for example, irregularities on the surface raised by a phase-separated structure that is arranged and controlled by convection cells) are finally generated by actinic rays (ultraviolet rays, electron beams, etc.) or heat. To form a cured resin. Therefore, scratch resistance can be imparted to the antiglare film, 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.

  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.

(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 or the like (particularly cured or crosslinked). Various curable compounds capable of forming (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 film 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.

  As the phase separation progresses, a co-continuous phase structure is formed, and when the phase separation further progresses, the continuous phase becomes discontinuous due to its surface tension, resulting in a droplet phase structure (spherical, true spherical, discoid or ellipsoidal) Sea island structure of independent phase). 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 film 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 co-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 film 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.

  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.

(Viscosity and concentration of solution)
According to the present invention, if the solution viscosity when convection occurs is too low, the solution viscosity is preferably reasonably high and the convection does not stagnate in order to maintain the uneven shape of the surface raised by convection. In order to flow, it is preferable that the viscosity of the solution is moderately low. In order to obtain such a viscosity of the solution, the solid content concentration of the solution is, for example, about 5 to 50% by weight, preferably about 10 to 40% by weight, and more preferably about 15 to 35% by weight.

(Coating thickness)
In order to generate a cellular convection of a desired size, the coating thickness of the solution is, for example, about 20 to 200 μm, preferably about 20 to 100 μm, and more preferably about 20 to 50 μm. Utilizing the aspect ratio of convection cells of 2 to 3, for example, when the distance between protrusions of the concavo-convex shape is about 50 μm, the solution is applied on the transparent support with an application thickness of about 20 to 50 μm. In this case, a part of the low boiling point solvent in the solution evaporates to reduce the thickness of the coating film, and at the same time, a temperature difference occurs between the upper layer and the lower layer of the coating film, and a cellular rotation having a size of about 50 μm. Convection can be generated.

(Drying temperature)
After casting or coating the solution, the solvent at a temperature lower than the boiling point of the solvent (for example, 1 to 120 ° C., preferably 5 to 80 ° C., particularly about 10 to 60 ° C. lower than the boiling point of the high boiling solvent). It is preferred to induce cellular rotational convection and phase separation by evaporating. For example, it may be dried at a temperature of about 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.

In particular, in order to generate a cellular rotating convection, after casting or coating is applied on a support, rather than dried immediately put into dry燥機such ovens, a predetermined time (e.g., 1 second to 1 minute, preferably 3 to 30 seconds, more preferably about 5 to 20 seconds), left at room temperature or room temperature (for example, about 0 to 40 ° C., preferably about 5 to 30 ° C.), and then placed in a dryer. It is preferable to input. Further, the amount of dry air is not particularly limited, but if the air amount is too strong, it is dried and solidified before sufficient rotational convection is generated, and therefore it is 50 m / min or less (for example, 1 to 50 m / min, preferably 1 to It is preferable to dry with an air volume of 30 m / min, more preferably about 1 to 10 m / min. The angle at which the drying air is applied to the antiglare film is not particularly limited, and may be parallel to or perpendicular to the antiglare film, for example.

(Curing treatment)
After the solution is dried, the coating film is cured or crosslinked by heat or active energy rays (such as ultraviolet rays or electron beams). The curing method can be selected according to the type of the curable resin precursor, but a method of curing by irradiation with light such as ultraviolet rays or electron beams is usually 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.

[Anti-glare film]
The antiglare film thus obtained has irregularities formed on its surface at relatively controlled intervals according to the arrangement of convective cells. Furthermore, the dot-like or linear convex part (micro-bulge area | region) raised by the upward flow may be formed in the position corresponded to the center part of a convection cell. Furthermore, the point-like convex part by about 1 to several (for example, 1-3) phase-separation structure may be formed in one convection cell. In one convection cell, about 1 to 2 ascending currents or minute protrusions due to a phase separation structure are formed, so that the protrusion intervals of the cell cells become more uniform, and a uniform uneven shape is formed. Particularly preferred.

  The uneven shape formed by cellular rotational convection usually has substantially regularity or periodicity. For example, the average convex distance Sm may be about 20 to 300 μm, preferably about 25 to 250 μm, and more preferably about 30 to 200 μm. The average convex distance Sm can be controlled by, for example, the thickness of the coating film when convection occurs.

  The total light transmittance of the antiglare film 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, 90). ~ 99%).

  The haze of the antiglare film is, for example, about 1 to 50%, preferably 2 to 40%, and more preferably about 5 to 35%. Moreover, when a low refractive index resin layer (low refractive index layer) described later is coated on the antiglare film, the haze is generally about 1 to 10% lower than the haze of the antiglare alone. . The haze when the antiglare film and the low refractive index layer are combined is, for example, 1 to 30%, preferably 2 to 25%, more preferably about 2 to 20%, and usually about 7 to 18%. It is. In the case of forming a low refractive index layer, it is preferable to adjust the haze of the antiglare film in consideration of a decrease in haze.

  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 can be selected from a range of about 10 to 100% when an optical comb having a width of 0.5 mm is used, but is preferably 10% or more and less than 70%, and more preferably 10%. About 60%.

  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 portion is 100% or less, while the light leaks at the non-transmissive portion, so 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.

  As the roughness of the antiglare film, the average line average roughness Ra is about 0.05 to 0.25 μm, preferably 0.05 to 0.2 μm, more preferably about 0.07 to 0.15 μm. It is. Moreover, when the low-refractive-index layer is coated on the anti-glare film, the value after coating the low-refractive-index layer is preferably within this range.

  The thickness of the antiglare film may be, for example, about 0.3 to 20 μm, preferably about 1 to 15 μm (for example, 1 to 10 μm), in order to impart an appropriate hard coat property and uneven surface shape. Usually, it is about 6 to 10 μm (particularly 7 to 10 μm). When the antiglare film is used alone without being combined with the support, the thickness of the antiglare film is, for example, 1 to 100 μm, preferably 2 to 70 μm, and more preferably about 3 to 50 μm. Good.

[Anti-glare film]
By using a non-peelable support (preferably a transparent support) as a support for the antiglare film, a laminate comprising a support and an antiglare film formed on the support is used. An antiglare film having a structure can be obtained. Further, a low refractive index layer (thin film layer) can be further formed on the antiglare film of the antiglare film. Further, after laminating the low refractive index layer on the antiglare film, the support is peeled off from the antiglare film, or after the antiglare film is peeled off from the support, the low refractive index layer is applied to the antiglare layer. By laminating, an antiglare film having a laminated structure composed of an antiglare layer and a low refractive index layer can also be obtained. 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.

(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.

(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.

[Optical member]
The antiglare film has a concavo-convex shape in which each convex portion is uniformly controlled by cellular rotational convection, and thus has a homogeneous and high-grade antiglare property. Furthermore, it has high scratch resistance (hard coat property) and can control the intensity distribution of transmitted scattered light. 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 excellent, and there is little blurring of characters on the display surface. In addition, when the low refractive index layer is formed, external light reflection can be efficiently prevented on the surface thereof. 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.

  The antiglare film imparted with scratch resistance 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.

[Display device]
The antiglare film and the antiglare film of the present invention can be used for various display devices such as liquid crystal display (LCD) devices, plasma displays, and display devices 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 requiring anti-glare properties and light scattering properties, for example, display devices such as the optical members 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.

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, solvent: 1-methoxy-2-propanol (MMPG) (boiling point 119 ° C.)] 5.65 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) 0.9 parts by weight, polyfunctional acrylic UV 6.3 parts by weight of curing monomer (Daicel UCB Co., Ltd., DPHA), photoinitiator (Ciba Specialty Chemicals) Manufactured by Irgacure 184) 0.5 parts by weight of methyl ethyl ketone (MEK) (boiling point 80 ° C.) 20.1 parts by weight, 1-butanol (BuOH) (boiling point 113 ° C.) 5.4 parts by weight, 1-methoxy-2-propanol (Boiling point: 119 ° C.) Dissolved in 1.89 parts by weight. Cellulose acetate propionate and acrylic resin are incompatible, and this solution exhibits phase separation properties as well as concentration. This solution was cast on a triacetylcellulose film using a wire bar # 24, and then allowed to stand at room temperature for 10 seconds. Immediately after that, the solution was placed in an explosion-proof oven at 70 ° C. and a wind speed of 3 m / min and held for 5 seconds. Then, a convection cell accompanying solvent evaporation was generated. This coating film was further dried in an oven for 2 minutes to generate a phase separation structure in the convection cell and to form a coating layer having a surface irregularity of about 9 μm in thickness. 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 produce an antiglare film having hard coat properties and a surface uneven structure.

Example 2
Using the wire bar # 5, a thermosetting fluorine-containing compound coating solution (manufactured by Nissan Chemical Co., Ltd., LR204-6, solid content 1% by weight) as a low refractive index layer on the antiglare film of Example 1 After coating, drying, and thermosetting at 90 ° C. for 5 minutes, a low reflection antiglare film was produced.

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, solvent: 1-methoxy-2-propanol (boiling point 119 ° C.)] 5.24 parts by weight, cellulose acetate propio Nate (degree of acetylation = 2.5%, degree of propionylation = 46%, polystyrene-equivalent number average molecular weight 75000; manufactured by Eastman, CAP-482-20) 0.9 parts by weight, polyfunctional acrylic UV curing monomer ( 6.5 parts by weight of Daicel UCB Co., Ltd., DPHA), photoinitiator (Ciba Specialty Chemicals, Irga) Interview A 184) 0.5 parts by weight of MEK (boiling point 80 ° C.) 36.8 parts by weight, was dissolved in 7.73 parts by weight of 1-butanol (boiling point 113 ° C.). Cellulose acetate propionate and acrylic resin are incompatible, and this solution exhibits phase separation properties as well as concentration. This solution was cast on a triacetyl cellulose film using a wire bar # 34, left at room temperature for 10 seconds, and then immediately put in an explosion-proof oven at 60 ° C. and a wind speed of 3 m / min and held for 5 seconds. Then, a convection cell accompanying solvent evaporation was generated. This coating film was further dried in an oven for 2 minutes to generate a phase separation structure in the convection cell and to form a coating layer having a concavo-convex shape on the surface and 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, thereby producing a hard coat property and an antiglare film having an uneven structure on the surface.

Example 4
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) 2X0M, solid content 40% by weight, solvent: 1-methoxy-2-propanol (boiling point 119 ° C.)] 5.75 parts by weight, ethyl cellulose (ethoxy group content) = 49%; Hercules, N-4) 1.2 parts by weight, polyfunctional acrylic UV curing monomer (manufactured by Daicel UCB, DPHA) 3.5 parts by weight, polyfunctional acrylic urethane oligomer (Negami Kogyo Co., Ltd., UN-3320HS) 3 parts by weight, photoinitiator (Ciba Specialty Chemicals, Irgacure 184) 0 5 parts by weight of MEK (boiling point 80 ° C.) 16.25 parts by weight, was dissolved in 4.55 parts by weight of 1-butanol (boiling point 113 ° C.). In addition, ethylcellulose and an acrylic resin are incompatible, and this solution exhibits phase separation properties as well as concentration. This solution was cast on a triacetylcellulose film using a wire bar # 24, and then allowed to stand at room temperature for 10 seconds. Immediately after that, the solution was placed in an explosion-proof oven at 70 ° C. and a wind speed of 3 m / min and held for 5 seconds. Then, a convection cell accompanying solvent evaporation was generated. This coating film was further dried in an oven for 2 minutes to generate a phase separation structure in the convection cell and to form a coating layer having a concavo-convex shape on the surface and 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 produce an antiglare film having hard coat properties and a surface uneven structure.

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], 5.25 parts by weight, cellulose acetate propionate (degree of acetylation = 2.5%, degree of propionylation = 46%, polystyrene-equivalent number average molecular weight) 75,000; 1.1 parts by weight manufactured by Eastman, CAP-482-20), 6.3 parts by weight of a polyfunctional acrylic UV curing monomer (manufactured by Daicel UCB Co., Ltd., DPHA), photoinitiator (Ciba Special) 0.62 parts by weight of Tea Chemicals, Irgacure 184) was dissolved in 37.36 parts by weight of tetrahydrofuran. 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 a hard coat property and an antiglare film having a concavo-convex structure on the surface.

  Table 1 shows the results of measuring the total light transmittance, haze, and transmitted image definition in the antiglare films of the antiglare films obtained in Examples 1 to 4 and Comparative Example 1.

About the performance of the anti-glare films obtained in Examples 1 to 4 and Comparative Example 1, the anti-glare property, white floating (sink of black display), and image contrast were obtained in a light environment illuminated by outside light. The obtained antiglare films were mounted on the surface of a VA (vertical alignment) type LCD panel having a front luminance of 450 cd / m ² , a contrast of 400 to 1, 20 type, and a resolution of 60 ppi, respectively, and visually evaluated according to the following criteria.

(Anti-glare)
○: 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 apparent from the results in Table 1, the antiglare films of Examples 1 to 4 have no whitening and have high antiglare properties and image contrast. On the other hand, the film of Comparative Example 1 has low antiglare properties and image contrast.

  Furthermore, the black film was bonded to the back side of the anti-glare film obtained in Examples 2-4, and the photograph which copied the uneven | corrugated shape of the surface by observing with a laser reflection microscope is shown. 1 and 2 are photographs of objective lens magnification 5 × and 10 ×, respectively, obtained by a laser reflection microscope having an uneven surface shape in the antiglare film obtained in Example 2. FIG. FIG. 3 is a laser reflection micrograph (objective lens magnification: 10 times) of the uneven surface of the antiglare film obtained in Example 3. Further, FIG. 4 is a laser reflection micrograph (objective lens magnification: 10 times) of the surface irregularity shape in the antiglare film obtained in Example 4.

  As apparent from the photographs of FIGS. 1 to 4, since a dot-like or streak-like protrusion appears at the center of the concavo-convex shape, it can be seen that the concavo-convex shape is formed by the cellular rotating convection cell.

FIG. 1 is a laser reflection micrograph (magnification 5 times) of an uneven surface shape of the antiglare film obtained in Example 2. FIG. 2 is a laser reflection micrograph (magnification 10 times) of the surface irregularity shape in the antiglare film obtained in Example 2. FIG. 3 is a laser reflection micrograph (magnification 10 times) of the surface irregularity shape in the antiglare film obtained in Example 3. FIG. 4 is a laser reflection micrograph (magnification 10 times) of the surface irregularity shape in the antiglare film obtained in Example 4.

Claims (13)

  A solution containing at least one polymer, at least one curable resin precursor, a solvent having a boiling point of 100 ° C. or higher, and another solvent having a different boiling point from this solvent is coated on the support to obtain the highest boiling point. By producing at a temperature lower than the boiling point of the solvent having a cellular rotational convection during the drying process, the coating film is cured to form an antiglare film. A method for producing an antiglare film in which at least two components of the polymer and the curable resin precursor are mutually phase-separable.   The manufacturing method according to claim 1, wherein the coating film surface is raised by cellular rotational convection to form a regular or periodic uneven shape on the surface.   The manufacturing method according to claim 1, wherein an uneven shape is formed on the surface by cellular rotational convection and a phase separation structure is formed.   The production method according to claim 1, wherein the coating film is cured by irradiating at least one selected from active energy rays and heat.   A composition comprising a thermoplastic resin, a photocurable compound, a photopolymerization initiator, and a solvent soluble in the thermoplastic resin and the photocurable compound is applied, and the surface is rotated by cellular rotational convection during the drying process. The manufacturing method of Claim 1 which hardens a coating film by light-irradiating after forming an uneven | corrugated shape in this and forming a phase-separation structure.   The manufacturing method according to claim 1, wherein the polymer is composed of a plurality of polymers that can be phase-separated from each other, and the curable resin precursor is compatible with at least one of the plurality of polymers.   The production method according to claim 6, wherein at least one of the plurality of polymers has a functional group involved in the curing reaction of the curable resin precursor.   The production method according to claim 6, wherein at least one of the plurality of polymers has a (meth) acryloyl group.   A plurality of mutually phase-separable polymers are composed of a cellulose derivative and at least one resin selected from a styrene resin, a (meth) acrylic resin, an alicyclic olefin resin, a polycarbonate resin, and a polyester resin. The method according to claim 6, wherein at least one of the polymers has a polymerizable group.   The production method according to claim 1, wherein the support is a transparent support.   The manufacturing method of Claim 10 with which the transparent support body is comprised with the transparent polymer film for forming an optical member.   The manufacturing method according to claim 1, wherein a resin layer having a low refractive index is further formed on the antiglare film.   The manufacturing method according to claim 12, wherein the resin layer having a low refractive index is made of a resin having a low refractive index of 1.30 to 1.47.