JP5038748B2 - Antiglare film and method for producing the same - Google Patents

Description

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

  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 structure or a mat-shaped shaped film having 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, 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.

  Furthermore, in Japanese Patent Application Laid-Open No. 2006-106224 (Patent Document 7), 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 dried. A method for producing an antiglare film that cures a coating film after generating cellular rotational convection is disclosed. In the method described in this document, at least two components of the polymer and the curable resin precursor may have phase separation properties, and the coating surface is raised by cellular rotational convection during the drying process. Thus, a manufacturing method is disclosed in which a regular or periodic uneven shape is formed on the surface. In this method, an anti-glare film is produced by well combining two types of natural self-ordering forces, phase separation and convection, so that the interval is controlled according to the size and arrangement of convection cells and the phase separation. A concave / convex shape having a good shape / height associated with the structure is formed. That is, an antiglare film having a sufficiently controlled shape, arrangement and size can be obtained.

However, in this method, the phase separation of the two components is strong, and the antiglare film obtained by convection has a dense structure with a narrow domain interval and a small number of plane parts (sea parts). The low refractive index layer applied on the antiglare film for the purpose cannot follow the uneven shape on the surface of the antiglare film, and it is difficult to further improve the blackness.
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]) JP 2006-106224 A (Claim 1, FIGS. 1 to 4)

  Accordingly, an object of the present invention is to provide an antiglare film capable of preventing external light from being reflected on a display, suppressing white floating in a black display image, and displaying an image with a strong contrast feeling in which black is tightened. It is providing the anti-glare film using a film | membrane, and its manufacturing method.

  Another object of the present invention is to provide an antiglare film that has high antiglare properties and can suppress iridescence due to interference of reflected light, an antiglare film using this film, and a method for producing the same.

  Still another object of the present invention is to provide an antiglare film that has high followability even when a low refractive index layer is laminated and can improve blackness, an antiglare film using this film, and a method for producing the same. It is in.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventor obtained a non-reactive (meth) acrylic resin, a (meth) acrylic resin having a polymerizable group, and a polyfunctional (meth) acrylate. By using the curing reaction, a string-like convex part is dispersed and formed on the surface in a random direction, and an anti-glare film having a small area ratio of the string-like convex part is prepared. The present invention has been completed by finding that it is possible to prevent the reflection of outside light, suppress white floating in a black display image, and display an image with a strong contrast feeling in which black is tightened.

That is, the antiglare film of the present invention has a poly (meth) acrylic acid ester having a weight average molecular weight of 100,000 to 700,000 , a weight average molecular weight of 1,000 to 50,000 , and a polymerizable group. An antiglare film composed of a cured product of a (meth) acrylic resin and a polyfunctional (meth) acrylate, wherein the (meth) acrylic resin having the polymerizable group is (meth) acrylic acid -(Meth) acrylic resin in which epoxycyclo _C5-8 alkenyl (meth) acrylate is introduced into a part of carboxyl group of (meth) acrylic acid ester copolymer , and the poly (meth) acrylic ester and The (meth) acrylic resin having a polymerizable group is phase-separated by spinodal decomposition, and convection is generated, so that the string-like convex portions are formed on the surface. And the area ratio of the string-like convex portions is 50% or less with respect to the entire surface . The average height of the pre-Symbol cord-like projections, for example, about 0.05 to 10 [mu] m, and an average width of, for example, may be about 0.1 to 30 [mu] m. The said string-like convex part may have the recessed part extended in a length direction .

The present invention includes a poly (meth) acrylic acid ester having a weight average molecular weight of 100,000 to 700,000 , and a (meth) acrylic resin having a weight average molecular weight of 1,000 to 50,000 and having a polymerizable group. And a drying step of applying a solution containing a polyfunctional (meth) acrylate and a solvent having a boiling point of 100 ° C. or higher, generating convection as the solvent evaporates, and a curing step of curing the dried coating film. The manufacturing method of the said anti-glare film | membrane comprised is also included. The solution may further contain solvents having different boiling points. Wherein in the drying step, the poly (meth) acrylic acid ester, together with a (meth) acrylic resin having a polymerizable group is phase-separated by spinodal decomposition, the string-like by the raised surface by the solution generating convection A convex portion may be formed. In the curing step, the coating film may be cured by irradiating at least one selected from active energy rays and heat.

The present invention also includes an antiglare film in which the antiglare film is formed on a transparent support. In this antiglare film, a low refractive index layer may be further formed on the antiglare film. This antiglare film is suitable for display devices such as a liquid crystal display device, a cathode ray tube display device, a plasma display, and a touch panel type input device.

  When the antiglare film of the present invention is applied to various display devices, it is possible to prevent external light from being reflected on the display, to suppress white floating in a black display image, and to display an image with a strong contrast feeling in which black is tightened. it can. Further, the antiglare property is high, and iridescence due to interference of reflected light can be suppressed. Furthermore, even if a low refractive index layer is laminated, followability is high and blackness can be improved.

  The antiglare film of the present invention can be produced by using convection (convection cell) associated with phase separation of a plurality of polymers, and more specifically, (meth) acrylic resin (“non-reactive (meth) acrylic resin”). And (meth) acrylic resin having a polymerizable group ("reactive (meth) acrylic resin having a polymerizable group", or simply "reactive (meth) acrylic resin"). In some cases), a polyfunctional (meth) acrylate, and a solution containing a solvent having a boiling point of 100 ° C. or higher, a drying step for generating convection as the solvent evaporates, and the dried coating film is cured. It can be manufactured through a curing process. 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.

((Meth) acrylic resin)
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 The alicyclic hydrocarbon group such as tricyclodecane The (meth) acrylate etc. which have can be illustrated. 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.

  The weight average molecular weight of the (meth) acrylic resin is, for example, 30,000 to 1,000,000, preferably 100,000 to 700,000, more preferably 200,000 to 500,000 (particularly 300,000 to About 500,000). When the molecular weight is within this range, the balance between the solubility in the dope solution and the film strength after curing is improved. In particular, if the molecular weight is too small, compatibility with the (meth) acrylic resin having a functional group involved in the curing reaction is improved, and it becomes difficult to form a domain structure due to phase separation and convection.

  The glass transition temperature of the (meth) acrylic resin is, for example, in the range of −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.). You can choose.

  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.).

((Meth) acrylic resin having a polymerizable group)
As the polymerizable group, a functional group involved in the curing reaction (a functional group capable of reacting with a polyfunctional (meth) acrylate described later) can be used. Such a polymerizable group may be included in the main chain of the (meth) acrylic resin, or may be included in the side chain. The polymerizable group may be introduced into the main chain by copolymerization or cocondensation, but is usually introduced into the side chain. Such polymerizable groups include condensable or reactive functional groups (for example, hydroxyl group, acid anhydride group, carboxyl group, amino group or imino group, epoxy group, glycidyl group, isocyanate group, etc.), radical polymerizable Functional groups (for example, C _2-6 alkenyl groups such as vinyl, propenyl, isopropenyl, butenyl, allyl, C _2-6 alkynyl groups such as ethynyl, propynyl, butynyl, C _2-6 alkenylidene groups such as vinylidene, or these And a functional group having a radical polymerizable functional group (such as a (meth) acryloyl group). Of these functional groups, radically polymerizable functional groups are preferred.

  The (meth) acrylic resin having a polymerizable group in the side chain has, for example, a (meth) acrylic resin having a reactive group (such as the functional group exemplified in the above-mentioned condensable or reactive functional group). The compound (ii) is obtained by reacting the resin (i), a reactive group with respect to the reactive group of the (meth) acrylic resin, and the compound (polymerizable compound) (ii) having the polymerizable group. It can be produced by introducing a polymerizable group into a (meth) acrylic resin.

  As the (meth) acrylic resin (i) having a reactive group, a thermoplastic resin having a carboxyl group or an acid anhydride group thereof [for example, (meth) acrylic resin (methyl methacrylate- (meth) acrylic acid) (Meth) acrylic acid- (meth) acrylic acid ester copolymer, methyl methacrylate-acrylic acid ester- (meth) acrylic acid copolymer, etc.) such as a copolymer, (meth) acrylic resin having a hydroxyl group [(Meth) acrylic acid ester- (meth) acrylic acid hydroxyalkyl ester copolymer, etc.], (meth) acrylic resin having an epoxy group [for example, (meth) acrylic resin having a glycidyl group, etc.] it can. 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. Said (meth) acrylic-type resin (i) can be used individually or in combination of 2 or more types.

  As the reactive group of the polymerizable compound (ii), a reactive group with respect to the reactive group of the (meth) acrylic resin (i), for example, the condensability or reaction exemplified in the section of the functional group of the polymer. And functional groups similar to the functional group.

Examples of the polymerizable compound (ii) include an epoxy group-containing polymerizable compound [for example, epoxy group-containing (meth) acrylate (epoxy C ₃₋ such as glycidyl (meth) acrylate, 1,2-epoxybutyl (meth) acrylate), etc. ₈ alkyl (meth) acrylate; epoxycyclo C _5-8 alkenyl (meth) acrylate such as epoxycyclohexenyl (meth) acrylate), allyl glycidyl ether etc.], a compound having a hydroxyl group [hydroxyl group-containing (meth) acrylate, for example, hydroxy _{C 2-4} alkyl (meth) acrylates such as hydroxyethyl (meth) acrylate; and _{C 2-6} alkylene glycol mono (meth) acrylates such as ethylene glycol mono (meth) acrylate], organic amino group That the polymerizable compound [e.g., 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 (meth) acrylate, vinyl isocyanate, etc.], a polymerizable compound having a carboxyl group or its acid anhydride group [for example, unsaturated carboxylic acid such as (meth) acrylic acid or maleic anhydride, or its anhydride, etc. ] Can be illustrated. These polymerizable compounds (ii) can be used alone or in combination of two or more.

  In addition, as a combination of the reactive group of (meth) acrylic-type resin (i) and the reactive group of polymeric compound (ii), the following combinations etc. are mentioned, for example.

(i-1) Reactive group of (meth) acrylic 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 (meth) acrylic resin (i): hydroxyl group Reactive group of polymerizable compound (ii): carboxyl group or its acid anhydride group, isocyanate group
(i-3) Reactive group of (meth) acrylic resin (i): amino group Reactive group of polymerizable compound (ii): carboxyl group or its acid anhydride group, epoxy group, isocyanate group
(i-4) Reactive group of (meth) acrylic 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 polymerizable 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, is obtained from Daicel Chemical Industries, Ltd. as “Cyclomer P”, for example. it can. 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 polymerizable group with respect to the (meth) acrylic resin is 0.001 to 10 mol, preferably 0.01 to 5 mol, more preferably 0.02 to 3 with respect to 1 kg of the (meth) acrylic resin. It is about a mole.

  When the polymerizable group is introduced into the side chain, the proportion of the (meth) acrylic unit having a polymerizable group (unit corresponding to the monomer) is, for example, 10 to 90 mol%, preferably, among all units. It is about 20 to 60 mol%, more preferably about 30 to 50 mol%.

  The weight average molecular weight (total molecular weight including the polymerizable group) of the reactive (meth) acrylic resin having such a polymerizable group is, for example, 1,000 to 100,000, preferably 5,000 to 50, 000, more preferably about 10,000 to 30,000. When the molecular weight is within this range, the balance between the solubility in the dope solution and the curing reactivity is improved.

  Irregular shapes on the surface raised by convection (for example, irregularities on the surface raised by a phase-separated structure arranged and controlled by the convection domain) are finally caused by actinic rays (ultraviolet rays, electron beams, etc.) or heat. Cure to form a cured resin. Therefore, scratch resistance can be imparted to the antiglare film, and durability can be improved.

  The ratio (weight ratio) between the non-reactive (meth) acrylic resin and the reactive (meth) acrylic resin having a polymerizable group is, for example, the former / the latter = 1/99 to 90/10, preferably 3. / 97 to 70/30, more preferably about 5/95 to 50/50 (particularly 10/90 to 40/60).

  In the present invention, the two types of (meth) acrylic resins are incompatible with each other and have weak phase separation properties, and are incompatible with each other near the processing temperature. With such a combination, convection can be generated with a weak phase separation action, and the area of the flat portion on the film surface can be increased. Since the (meth) acrylic resin has rigidity and high light resistance, it has very high durability as an antiglare film.

  In addition to the two incompatible polymers, other polymers such as styrene resins and organic acid vinyl esters can be used as the polymer for forming the phase separation structure, as long as the effects of the present invention are not impaired. Resin, vinyl ether resin, halogen-containing resin, olefin resin (including alicyclic olefin resin), polycarbonate resin, polyester resin, polyamide resin, thermoplastic polyurethane resin, polysulfone resin (polyethersulfone, Polysulfone, etc.), polyphenylene ether resins (2,6-xylenol polymers, etc.), cellulose derivatives (cellulose esters, cellulose carbamates, cellulose ethers, etc.), silicone resins (polydimethylsiloxane, polymethylphenylsiloxane, etc.) , Rubber or Elastomers (polybutadiene, diene rubbers such as polyisoprene, styrene - butadiene copolymer, acrylonitrile - butadiene copolymer, acrylic rubber, urethane rubber, silicone rubber, etc.) may be included, such as.

(Multifunctional (meth) acrylate)
The polyfunctional (meth) acrylate is a compound having a functional group that reacts with heat or active energy rays (such as ultraviolet rays or EB (electron beam)), and has the polymerizable group by heat or active energy rays. A resin (particularly a cured or crosslinked resin) can be formed by curing or crosslinking with a (meth) acrylic resin.

  The functional group of the polyfunctional (meth) acrylate may be an epoxy group, isocyanate group, alkoxysilyl group, silanol group, polymerizable group (vinyl group, allyl group, (meth) acryloyl group, etc.), etc. , Photocurable groups that can be cured in a short time (especially ultraviolet curable groups), for example, radically polymerizable groups (such as vinyl groups, allyl groups, (meth) acryloyl groups) and photosensitive groups (such as cinnamoyl groups), A radical polymerizable group is particularly preferable.

  The polyfunctional (meth) acrylate has at least two (preferably 2 to 6, more preferably about 2 to 4) polymerizable unsaturated bonds, such as alkylene glycol di (meth) acrylate [for example, , Ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, hexanediol di (meth) acrylate, etc.], bridged cyclic hydrocarbon group (E.g., (poly) oxyalkylene glycol di (meth) acrylates such as diethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, and polyoxytetramethylene glycol di (meth) acrylate) Tricyclodecane dimethanol di (meth) acrylate, adamantane di (meth) acrylate, etc.], polyfunctional monomer having about 3 to 6 polymerizable unsaturated bonds [e.g., trimethylolpropane tri (meth) acrylate , Trimethylolethane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like. Furthermore, the polyfunctional (meth) acrylate may be an oligomer or a resin as long as it has two or more polymerizable unsaturated bonds, for example, a (meth) acrylate of a bisphenol A-alkylene oxide adduct, Epoxy (meth) acrylate (bisphenol A type epoxy (meth) acrylate, novolac type epoxy (meth) acrylate, etc.), 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, polyether type urethane (meth) acrylate, etc.), silicone (meth) acrylate, and the like. These polyfunctional (meth) acrylates can be used alone or in combination of two or more. Among these polyfunctional (meth) acrylates, polyfunctional monomers having about 3 to 6 polymerizable unsaturated bonds, particularly dipentaerythritol tetra to hexa (dipentaerythritol hexa (meth) acrylate) and the like ( (Meth) acrylate is preferred.

  The molecular weight of the polyfunctional (meth) acrylate is about 5000 or less, preferably about 2000 or less, and more preferably about 1000 or less in consideration of compatibility with the polymer.

  The polyfunctional (meth) acrylate may be used in combination with a curing agent depending on the type. For example, the polyfunctional (meth) acrylate may be used in combination with a curing agent such as amines or polyvalent carboxylic acids, or 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.

  Content of hardening | curing agents, such as a photocuring agent, is 0.1-20 weight part with respect to 100 weight part of polyfunctionality (meth) acrylate, Preferably it is 0.5-10 weight part, More preferably, it is 1-8 weight part. Part (particularly 1 to 5 parts by weight), and may be about 3 to 8 parts by weight.

  The polyfunctional (meth) acrylate may contain a curing accelerator or a crosslinking agent. For example, the polyfunctional (meth) acrylate may be combined with a photocuring accelerator such as a tertiary amine (such as a dialkylaminobenzoic acid ester) or a phosphine photopolymerization accelerator.

Furthermore, the polyfunctional (meth) acrylate is a monofunctional vinyl compound [(meth) acrylic monomer such as (meth) acrylic acid ester, such as alkyl (meth) acrylate (methyl (meth) acrylate, etc. C _1-6 alkyl (meth) acrylate), cycloalkyl (meth) acrylate, (meth) acrylate having a bridged cyclic hydrocarbon group (such as isobornyl (meth) acrylate, adamantyl (meth) acrylate), glycidyl (meth) Acrylate; vinyl ester such as vinyl acetate, vinyl monomer such as vinyl pyrrolidone, etc.].

(Convection)
In this invention, after apply | coating the solution containing the said 2 types of (meth) acrylic-type resin and polyfunctionality (meth) acrylate, the coating-film surface is raised by convection, and a string-like convex part is on the film | membrane surface. It is formed by being dispersed in random directions. In general, convection is caused by a temperature difference exceeding the limit between the upper layer and the lower layer of the coating film as a result of the evaporation 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 convex shapes having substantially regular or periodic intervals on the film surface are arranged as random string domains. It is known that the aspect ratio (application direction / thickness direction) of this domain is about 2/1 to 3/1.

  Further, the method of convection is not particularly limited, and other convection may be used. For example, Marangoni convection (density difference convection) due to nonuniform distribution of surface tension may be used. Marangoni convection is a flow having a surface tension difference Δσ as a driving force. Since the surface tension generally varies greatly depending on the temperature and concentration, if there is a temperature / concentration gradient on the surface of the coated thin film, a Marangoni flow is generated from a point with a low surface tension to a point with a high surface tension. On the other hand, the increase in the viscous resistance accompanying the solvent evaporation due to drying acts to suppress the Marangoni flow. The critical condition for generating Marangoni convection can be expressed by the Marangoni number Ma, which is the ratio of surface tension to viscous force, and is given by the following equation according to temperature T, thermal diffusivity α of coating solution, film thickness h, and viscosity μ. It is known that vortex convection occurs when the Marangoni number exceeds a certain critical value Mac, and often appears at the beginning of drying when the film thickness is large and the viscosity is low.

Ma = Δσh / (αμ)
(Combination of convection and phase separation)
In the present invention, convection is generated in this way, and a surface irregularity shape caused by the convection flow and the solid content concentration difference is formed. In addition to such convection, two types of (meth) acrylic resins and polyfunctionality are formed. Using a solution containing (meth) acrylate, at least two of these components may be phase-separated 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, a convection domain is first generated after application. Next, phase separation occurs in each convection domain, and the structure of the phase separation grows with time, but the growth of phase separation stops at the domain wall of the convection. As a result, the spacing according to the size and arrangement of the convection domains is controlled, 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 a solvent in a solution containing two kinds of (meth) acrylic resins and a polyfunctional (meth) acrylate. 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 (meth) acrylic resin and polyfunctional (meth) acrylate to be used. In the case of a mixed solvent, at least one type is a solid component (two types of (meth) acrylic resins). And a polyfunctional (meth) acrylate, a reaction initiator, other additives) may be used as long as the solvent can be uniformly dissolved. 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 (benzene etc.), halogenated carbons (dichloromethane, dichloroethane etc.), esters (methyl acetate, ethyl acetate etc.), water, alcohols (ethanol, isopropanol, butanol, cyclohexanol etc.) ), Cellosolves (methyl cellosolve, ethyl cellosolve, etc.), cellosolve acetates, amides (dimethylformamide, dimethylacetamide, etc.) and the like. 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 convection.

  In the present invention, in order to generate such a convection domain, 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. Further, when two types of solvents having different boiling points are used, the boiling point of the high boiling point solvent is 100 ° C. or higher, usually about 100 to 200 ° C., preferably 105 to 150 ° C., more preferably 110 to 130 ° C. Degree. 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 aromatic hydrocarbons (toluene, xylene, etc.), alcohols (C _4-8 alkyl alcohols, such as butanol, pentyl alcohol, hexyl alcohol), alkoxy alcohols. (C _1-6 alkoxy C _2-6 alkyl alcohol such as methoxypropanol and butoxyethanol), alkylene glycols (C _2-4 alkylene glycol such as ethylene glycol and propylene glycol), ketones (cyclohexanone etc.), sulfoxide (Dimethyl sulfoxide 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, C _2-4 alkylene glycols such as ethylene glycol, and the like are preferable.

  Preferred combinations include, for example, a combination of a solvent having a boiling point of 100 ° C. or higher (alcohol such as butanol, alkoxy alcohol such as methoxypropanol) and a solvent having a boiling point lower than 100 ° C. (ketone such as methyl ethyl ketone). Can be mentioned.

  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.

In the present invention, at least two components of the two (meth) acrylate resins and the polyfunctional (meth) acrylate are phase-separated from each other near the processing temperature. If the compatibility of both of the phases to be separated is too low, the convection domain generated in the process of solvent evaporation has a narrow and dense structure, making it difficult to uniformly apply a low refractive index layer on the antiglare film It becomes. Note that the non-reactive (meth) acrylic resin and the polyfunctional (meth) acrylate are usually completely incompatible with each other or weakly compatible with each other .

  The polyfunctional (meth) acrylate is compatible with the reactive (meth) acrylate-based resin having a polymerizable group in the vicinity of the processing temperature. Further, when the polyfunctional (meth) acrylate is compatible with the non-reactive (meth) acrylic resin, the reactive (meth) acrylic resin having the polymerizable group and the polyfunctional (meth) acrylate are the main components. The mixture may be phase-separated into at least two phases of a mixture composed mainly of a non-reactive (meth) acrylic resin and a polyfunctional (meth) acrylate. Also in this case, when the compatibility between the two types of (meth) acrylic resins is too low, the space between the convection domains generated in the process of evaporating the solvent becomes a narrow and dense structure, and the low refractive index on the antiglare film It becomes difficult to uniformly coat the rate layer.

  When two types of (meth) acrylic resins are incompatible with each other, at least one component (meth) acrylic resin and multifunctional (meth) acrylate are used in a combination compatible with each other near the processing temperature. The That is, the polyfunctional (meth) acrylate may be compatible with at least one of the (meth) acrylic resins, and may preferably be compatible with both (meth) acrylic resins. When compatible with both (meth) acrylic resins, mixtures based on non-reactive (meth) acrylic resins and polyfunctional (meth) acrylates, reactive (meth) acrylic resins and polyfunctional Phase-separated into at least two phases with a mixture mainly composed of a soluble (meth) acrylate.

  In addition, the polymer phase separation between (meth) acrylic resins and the phase separation between (meth) acrylic resin and polyfunctional (meth) acrylate can be obtained by using a good solvent for both components. In the process of preparing and gradually evaporating the solvent, it can be easily determined by visually confirming whether or not the residual solid content becomes cloudy.

  Furthermore, the refractive index of a non-reactive (meth) acrylic resin and a cured or crosslinked resin produced by curing a reactive (meth) acrylic resin and a polyfunctional (meth) acrylate are usually different from each other. Further, the refractive indexes of the non-reactive (meth) acrylic resin and the reactive (meth) acrylic resin are also different from each other. The difference in refractive index between the non-reactive (meth) acrylic resin and the cured or crosslinked resin, and the difference in refractive index between the non-reactive (meth) acrylic resin and the reactive (meth) acrylic resin are, for example, 0 It may be about 0.001 to 0.2, preferably about 0.05 to 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 non-reactive (meth) acrylic resin and the cured or cross-linked resin is a sea-island structure, the non-reactive (meth) acrylic resin component forms a sea phase. However, from the viewpoint of surface hardness, it is preferable that the non-reactive (meth) acrylic resin component forms island-like domains. By forming island-like domains, fine irregularities can be formed on the surface of the antiglare layer after drying.

  The total amount of non-reactive (meth) acrylic resin and reactive (meth) acrylic resin (amount of polymer component) and the ratio (weight ratio) of polyfunctional (meth) acrylate are not particularly limited, For example, the former / the latter = 5/95 to 95/5, preferably 10/90 to 90/10, and more preferably about 20/80 to 80/20 (particularly 30/70 to 70/30).

  The ratio of the reactive (meth) acrylic resin having a polymerizable group and the polyfunctional (meth) acrylate is not particularly limited. For example, the number of moles of the reactive groups is equimolar (for example, 0 .5 to 1.5 times mol, preferably 0.8 to 1.2 times mol). Furthermore, the ratio of the total amount (curable resin precursor component) of the reactive (meth) acrylic resin having the polymerizable group and the polyfunctional (meth) acrylate and the non-reactive (meth) acrylic resin is There is no particular limitation, and the former / the latter may be selected from the range of about 99.9 / 0.1 to 10/90, for example, about 99/1 to 30/70 (particularly about 98/2 to 50/50). It may be. Moreover, the ratio of all the components (solid content) of a non-reactive (meth) acrylic resin is 1 to 60 weight%, for example, Preferably it is 3 to 30 weight%, More preferably, it is about 4 to 15 weight%. .

(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 50% by weight, and more preferably about 15 to 40% by weight.

(Coating thickness)
In order to generate a convection domain having a desired size, the coating thickness of the solution is, for example, about 20 to 200 μm, preferably 20 to 100 μm, and more preferably about 20 to 50 μm. For example, when the convex-concave distance of the concave-convex shape (particularly, the distance of the concave portion as a flat portion between the convex portion) is about 50 μm, the solution is applied on the transparent support with a coating thickness of about 20-50 μm When the coating is applied, a part of the low boiling point solvent in the solution evaporates, so that the coating thickness becomes thin and at the same time a temperature difference occurs between the upper layer and the lower layer of the coating, and the convection has a size of about 50 μm. 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 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 convection, it is not applied to a dryer such as an oven immediately after being applied on a support and cast or applied, and then dried, for a certain time (for example, 1 second to 1). For 3 minutes, preferably 3 to 30 seconds, more preferably about 5 to 20 seconds), at room temperature or room temperature (for example, 0 to 40 ° C., preferably about 5 to 30 ° C.), and then put into the dryer. preferable. 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 convection is generated, so it is 50 m / min or less (for example, 1 to 50 m / min, preferably 1 to 30 m). / Minute, more preferably about 1 to 10 m / minute). The angle at which the drying air is applied to the antiglare film is not particularly limited, and may be, for example, parallel to or perpendicular to the antiglare film.

(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 component, 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.

(Characteristics of antiglare film)
The antiglare film thus obtained has a string-like (or linear) shape on its surface at a relatively controlled interval according to the arrangement of the convection domains by convection accompanying phase separation of a plurality of polymers. The convex portions are formed in a distributed manner in a random direction. The shape of each string-like convex part (two-dimensional shape of the film surface) is usually a straight line or a string shape having a curved part partially or entirely. An intersecting shape may be formed. Such string-like convex portions are evenly dispersed on the surface of the film and have a partially continuous structure as described above. Therefore, the surface of the film has a two-dimensional network structure (as if it is a mask It can be observed as forming a mesh pattern of melon skin. In addition, such a string-like convex part should just form the net-like structure, and forms the structure where the continuous part and the non-continuous part were mixed normally.

  The average height of the string-like convex portions is, for example, about 0.05 to 10 μm, preferably 0.1 to 5 μm, and more preferably about 0.3 to 3 μm (particularly 0.5 to 2 μm). The average width of the string-like convex portions is, for example, about 0.1 to 30 μm, preferably 1 to 20 μm, and more preferably about 3 to 15 μm (particularly 5 to 10 μm). If both the height and width of the string-like convex portion are too large, the followability to the low refractive index layer is lowered, and conversely, if it is too small, the antiglare performance is lowered.

  In the present invention, since a specific (meth) acrylic resin is selected and phase separation and convection are generated, the bulge region due to convection becomes such a string-like convex portion, and the area occupied on the film surface is also reduced. . Specifically, the area ratio of the string-like convex portion is 50% or less (for example, 1 to 50%) with respect to the entire surface, preferably 10 to 48%, more preferably 20 to 45% (particularly 30). ~ 45%). Since the area of the string-like convex part is in such a low range on the film surface, the antiglare film of the present invention has a large area of the flat part formed as the concave part, and the low refractive index layer of the antiglare film The follow-up performance with respect to is improved. In the present invention, the area of the string-like convex part is calculated not based on the surface area of the three-dimensional string-like convex part but based on the two-dimensional area observed in the micrograph.

  Furthermore, the said string-like convex part may have a recessed part in the convex part surface. The shape and number of the recesses are not particularly limited, but usually a string-like recess corresponding to the shape of the string-like projection is formed. That is, the string-shaped recess may be formed along the length direction of the string-shaped protrusion, and both side portions of the string-shaped protrusion may be formed so as to extend like a bank along the length direction. The reason why such a concave portion is formed is not clear, but it is formed together with the ridges of the string-like convex portions accompanying the phase separation and convection, and such concave portions make the intervals between the convex portions of the domains more uniform and uniform. It is particularly preferable because a concavo-convex shape having an appropriate interval can be formed. In addition, the recessed part does not need to be formed according to the shape of a string-like convex part, for example, the dotted | punctate recessed part may be formed.

  The average depth of the recesses is, for example, about 0.001 to 5 μm, preferably about 0.005 to 3 μm, and more preferably about 0.01 to 2 μm (particularly 0.1 to 1 μm).

  The uneven shape formed by convection usually has substantially regularity or periodicity in the interval. For example, the average convex distance Sm may be about 10 to 300 μm, preferably 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, 0.5 to 50%, preferably 1 to 40%, and more preferably about 2 to 35%. Further, as will be described later on the antiglare film (when a low refractive index layer is coated, the haze is generally about 1 to 10% lower than that of the antiglare single haze. The haze when combined with the refractive index layer is, for example, 0.5 to 30%, preferably 1 to 25%, more preferably about 1 to 20%, and usually about 1 to 10%. In the case of forming the 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 90%, and more preferably 20 About 80%.

  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 center line average roughness Ra is about 0.01 to 0.25 μm, preferably 0.01 to 0.2 μm, more preferably about 0.02 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 25 μm, preferably about 1 to 20 μm (for example, 1 to 18 μm), in order to impart an appropriate hard coat property and uneven surface shape. Usually, it is about 6 to 15 μm (particularly 8 to 15 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 | permeability 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 material of the low refractive index layer is not particularly limited, and may be composed of a resin component, inorganic or organic particles, a combination thereof, or the like, but is generally composed 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 1.20 to 1.49, preferably 1.25 to 1.47, and more preferably about 1.30 to 1.45.

  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 resin 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 Dainippon Ink & Chemicals, Inc.

  The thickness of the low refractive index layer is, for example, about 0.04 to 2 μm, preferably about 0.06 to 0.5 μm, and more preferably about 0.08 to 0.3 μm.

[Optical member]
The antiglare film has a concavo-convex shape in which the size of each convex portion and the distance between the convex portions are controlled substantially uniformly by convection, and thus has a uniform 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 [weight average molecular weight: 25,000, a part of carboxyl group of (meth) acrylic acid- (meth) acrylic acid ester copolymer, 3,4-epoxycyclohexane Compound to which hexenylmethyl acrylate is added; 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, polymethyl methacrylate (PMMA) (weight average molecular weight 480000; manufactured by Mitsubishi Rayon Co., Ltd., BR88) 0.9 parts by weight, polyfunctional acrylic UV curing monomer (dipentaerythritol hexaacrylate; Daicel・ 6.3 parts by weight, manufactured by UCB Co., Ltd., DPHA), photoinitiator (Ciba Specialty Chemical) 0.5 parts by weight of Irgacure 184), 20.1 parts by weight of methyl ethyl ketone (MEK) (boiling point 80 ° C.), 5.4 parts by weight of 1-butanol (BuOH) (boiling point 113 ° C.), 1-methoxy-2- Dissolved in 1.89 parts by weight of propanol (boiling point 119 ° C.). In addition, PMMA and the acrylic resin which has a polymerizable unsaturated group do not show perfect compatibility, but this solution shows weak phase-separation property with 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 wt%, solvent: 1-methoxy-2-propanol (boiling point 119 ° C.)] 5.24 parts by weight, polymethyl methacrylate (PMMA) (weight average molecular weight 480000; manufactured by Mitsubishi Rayon Co., Ltd., BR88) 0.9 parts by weight, polyfunctional acrylic UV curable monomer (manufactured by Daicel UCB Co., Ltd., DPHA), 6.5 parts by weight, 0.5 part by weight of a photoinitiator (Ciba Specialty Chemicals, Irgacure 184) is 36.8 parts by weight of MEK (boiling point 80 ° C.), Nord was dissolved in (boiling point 113 ° C.) 7.73 parts by weight. In addition, PMMA and the acrylic resin which has a polymerizable unsaturated group do not show perfect compatibility, but this solution shows weak phase-separation property with 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
For the anti-glare film of Example 3, a thermosetting fluorine-containing compound coating solution (manufactured by Nissan Chemical Industries, LR204-6, solid content 1% by weight) is used as a low refractive index layer using wire bar # 5. After coating, drying, and thermosetting at 90 ° C. for 5 minutes, a low reflection antiglare film was produced.

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, 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. In addition, the acrylic resin which has a cellulose unsaturated propionate and a polymerizable unsaturated group is incompatible, and this solution shows phase-separation property with 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.

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

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 wt%, solvent: 1-methoxy-2-propanol (boiling point 119 ° C.)] 5.24 parts by weight, polymethyl methacrylate (PMMA) (weight average molecular weight 25000; manufactured by Mitsubishi Rayon Co., Ltd., BR87) 0.9 part by weight, polyfunctional acrylic UV curing monomer (manufactured by Daicel-UCB, Inc., DPHA) 6.5 parts by weight, 0.5 part by weight of a photoinitiator (Ciba Specialty Chemicals, Irgacure 184) is 36.8 parts by weight of MEK (boiling point 80 ° C.), 1-butane Lumpur was dissolved in (boiling point 113 ° C.) 7.73 parts by weight. The low molecular weight PMMA and the acrylic resin having a polymerizable unsaturated group exhibit complete compatibility, and no phase separation is induced by concentration in this solution. 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.

  Table 1 shows the results of measuring the total light transmittance, haze, and transmitted image clarity in the antiglare films of the antiglare films obtained in Examples 1 to 4 and Comparative Examples 1 to 3.

About the performance of the anti-glare films obtained in Examples 1 to 4 and Comparative Examples 1 to 3, the anti-glare property, white floating (sink of black display), and image contrast are in the light environment illuminated by outside light. The antiglare films obtained were each 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, and visually evaluated according to the following criteria: did.

(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, in the film of Comparative Example 1, the black display looks white and the contrast of the image is low. Further, the film of Comparative Example 2 has a high haze value and low image definition. Furthermore, the film of Comparative Example 3 is intensely reflected and has low antiglare properties.

  Furthermore, the black film is bonded to the back side of the antiglare films obtained in Examples 2 and 4 and Comparative Example 2, and observed with a laser reflection microscope. 1 to 3 are photographs of an objective lens magnification of 5 times with a laser reflection microscope having surface irregularities in the antiglare films obtained in Examples 2, 4 and Comparative Example 2, respectively.

  As is apparent from the photographs of FIGS. 1 and 2, the films of Examples 2 and 4 are formed by dispersing the string-like convex portions closed on the film surface in random directions, so that the irregular shape is formed by convection. It can be confirmed that it is formed.

  On the other hand, as is clear from the photograph of FIG. 3, the film of Comparative Example 2 has a dense structure in which the domain spacing is narrow and the plane portion (sea portion) is small.

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

Claims (10)

Poly (meth) acrylic acid ester having a weight average molecular weight of 100,000 to 700,000 , a (meth) acrylic resin having a weight average molecular weight of 1,000 to 50,000 and having a polymerizable group, and polyfunctionality An antiglare film composed of a cured product with (meth) acrylate,
The (meth) acrylic resin having a polymerizable group introduces epoxycyclo C _5-8 alkenyl (meth) acrylate into a part of the carboxyl group of the (meth) acrylic acid- (meth) acrylic ester copolymer. (Meth) acrylic resin,
The poly (meth) acrylic acid ester and the (meth) acrylic resin having a polymerizable group are phase-separated by spinodal decomposition, and convection is generated, whereby string-like convex portions are dispersed in a random direction on the surface. Formed,
And the anti-glare film | membrane whose area ratio of the said string-like convex part is 50% or less with respect to the whole surface.   The antiglare film according to claim 1, wherein the average height of the string-like convex portions is 0.05 to 10 µm and the average width is 0.1 to 30 µm.   The antiglare film according to claim 1, wherein the string-like convex part has a concave part extending in the length direction. Poly (meth) acrylic acid ester having a weight average molecular weight of 100,000 to 700,000 , a (meth) acrylic resin having a weight average molecular weight of 1,000 to 50,000 and having a polymerizable group, and polyfunctionality Claims comprising: a drying step of applying a solution containing (meth) acrylate and a solvent having a boiling point of 100 ° C or higher and generating convection as the solvent evaporates; and a curing step of curing the dried coating film. The manufacturing method of the anti-glare film | membrane in any one of 1-3 . The production method according to claim 4 , wherein the solution further contains solvents having different boiling points. In the drying process, the poly (meth) acrylic acid ester and the (meth) acrylic resin having a polymerizable group are phase-separated by spinodal decomposition, and the surface is raised by generating convection to form a string-like convex. The manufacturing method of Claim 4 which forms a part. The manufacturing method according to claim 4 , wherein in the curing step, the coating film is cured by irradiating at least one selected from active energy rays and heat.   An antiglare film, wherein the antiglare film according to claim 1 is formed on a transparent support. The antiglare film according to claim 8 , wherein a low refractive index layer is further formed on the antiglare film. The anti-glare film according to claim 8, which is used in at least one display device selected from a liquid crystal display device, a cathode ray tube display device, a plasma display, and a touch panel type input device.