Anti-glare film, its manufacturing method and use

Abstract

To provide a display unit including an anti-glare film that has less yellowness and high anti-glare properties.SOLUTION: A display unit is prepared which includes an anti-glare film having a 60-degree gloss of 21% or less, an absolute value of the chromaticity b* of transmitted light of 3 or less, and a haze of 30% or more. The anti-glare film includes a transparent base material layer, and an anti-glare layer formed on at least one face of the transparent base material layer. The anti-glare layer may be a cured product of a curable composition including one or more polymer components and one or more cured resin precursor components. In particular, at least two components selected from the polymer components and the cured resin precursor components may be phase-separated by wet spinodal decomposition.SELECTED DRAWING: None

Description

[Technical Field]

[0001] This invention relates to liquid crystal display devices (LCDs) and organic electroluminescent (EL) displays. Anti-glare films usable in various display devices such as Ray, as well as their manufacturing method and applications. . [Background technology]

[0002] Anti-glare films are used on the display surface of image display devices such as LCDs and OLED displays. It is widely used as a film to prevent reflections of the surrounding scenery and improve visibility. The optical properties required for anti-glare films include high haze, which helps to prevent glare. In addition to its function of improving performance, it has high transparency (total light transmittance) and is biased towards yellow and red. It provides the viewer with a neutral white light rather than a bright color, improving visibility. This can also be mentioned. In order to exhibit such functions, anti-glare films have conventionally used fine particles A mixture of the material and a binder resin or a curable resin is applied to the substrate to form fine irregularities on the surface. A method is known that prevents specular reflection and exhibits anti-glare properties by doing so. However, fine particles In anti-glare films that utilize this technology, the intensity distribution of transmitted and scattered light is controlled by the particle size. Therefore, glare and blurring of text on the display surface cannot be effectively prevented. Furthermore, the fine particles are dispersed The anti-glare film is composed of a matrix material and dispersed fine particles with a refractive index. The larger the difference, the higher the haze value and the greater the light diffusion, but as the internal haze increases, shorter wavelengths Because the light from the sides is scattered over a wide angle, the display device appears yellowish and dull when viewed from the front. Visibility is reduced. Also, because it is prone to backscattering, transparency is reduced.

[0003] Therefore, a method is used to form an uneven surface shape by utilizing the spinodal decomposition of incompatible resin components. The method is also known, and Japanese Patent Publication No. 2014-85371 (Patent Document 1) describes multiple resin compounds An anti-glare film comprising an anti-glare layer having elongated protrusions on its surface formed by phase separation. Furthermore, the aforementioned elongated protrusion has a branched structure and a total length of 100 μm or more. Furthermore, the elongated protrusions on the surface of the anti-glare layer are 1 mm 2 There is at least one anti-glare film per unit. It has been disclosed. This anti-glare film offers an excellent balance between haze and clarity, and is suitable for high-definition displays. Display devices (for example, liquid crystal display devices with a resolution of 200 ppi or higher, or organic EL display devices) Even when installed in locations such as (etc.), it can improve anti-glare properties, highly suppress glare, and also reduce text blurring. It can be controlled.

[0004] However, even with this anti-glare film, improving transparency can sometimes reduce its anti-glare properties. Furthermore, conventional methods require light scattering, which causes high haze, to improve anti-glare properties. There is a need to improve performance, and there is a trade-off between anti-glare properties and transparency (especially suppression of yellowing). They were in a relationship, and it was difficult to balance both.

[0005] Japanese Patent Publication No. 5531388 (Patent Document 2) describes an optical sheet with good contrast. As a method of supplying, the transparent substrate has a functional layer on at least one side, and this functional layer In a method for manufacturing an optical sheet having a diffusion element on its outermost surface and / or inside, a predetermined angle The ratio of the diffuse specular reflectance to the sum of the diffuse reflectances measured is controlled to exceed 0.19. By doing so, a method for stably manufacturing optical sheets with excellent contrast is disclosed. It is.

[0006] However, it was difficult to improve the transparency even with the optical sheet obtained by this method.

Prior Art Documents

Patent Documents

[0007]

Patent Document 1

[0021] )

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0008] Therefore, an object of the present invention is to provide an antiglare film having a small yellowness and high antiglare property, as well as a manufacturing method and uses thereof.

Means for Solving the Problems

[0009] As a result of intensive studies to achieve the above problems, the inventors of the present invention have found that by preparing an antiglare film having an absolute value of the chromaticity b of transmitted light * of 15 or less and a haze of 30% or more, it is possible to improve the antiglare property while suppressing the yellowness, and completed the present invention. That is, the antiglare film of the present invention has an absolute value of the chromaticity b of transmitted light

[0010] of 15 or less, and * also has a haze of 30% or more. The antiglare film may have an absolute value of the chromaticity b of transmitted light of 3 or less * and a 60° gloss of 25% or less. The antiglare film includes a transparent base material layer and an antiglare layer formed on at least one surface of the transparent base material layer, and the antiglare layer is a cured product of a curable composition containing one or more polymer components and one or more cured resin precursor components. ​It may also be a material. At least one selected from the polymer component and the cured resin precursor component. The two components may also be phase-separable by wet spinodal decomposition. - The components may include cellulose esters and / or (meth)acrylics having polymerizable groups. It may also contain a polymer. The curing resin precursor component is a polyfunctional (meth)acrylate. Epoxy (meth)acrylate, polyester (meth)acrylate, urethane (meth (t) At least one selected from acrylates and silicone (meth)acrylates It may contain: The curing resin precursor component contains silica nanoparticles and / or fluorine atoms It may be included.

[0011] The present invention includes a curing step in which a curable composition is cured with heat or active energy rays. The method for manufacturing anti-glare films is also included. This manufacturing method involves placing one or more polymers on a support. - A curable composition containing one or more curable resin precursor components is applied and dried. Furthermore, at least two components selected from polymer components and curing resin precursor components are used in a wet environment. The process may further include a phase separation step in which phase separation is performed by spinodal decomposition. The process was a curing process in which the phase-separated curable composition was cured with heat or active energy rays. That's fine.

[0012] The present invention also includes a display device equipped with the anti-glare film. This display device uses organic E It may also be an L-display or a liquid crystal display.

[0013] The present invention relates to the chromaticity b of transmitted light. * The absolute value and haze of the following values ​​should be 15 or less and 30% or less, respectively. This also includes methods to adjust within the above range to improve the anti-glare properties and transparency of the anti-glare film.

[0014] In addition, in this specification and the claims, (meth)acrylate includes both methacrylic acid esters and acrylic acid esters. [Advantages of the Invention]

[0015] In the present invention, since the absolute value of the chromaticity b of the transmitted light of the antiglare film * is 15 or less and the haze is 30% or more, it is possible to achieve both color tone and antiglare property. In particular, the yellowness can also be reduced, and while suppressing the yellowish taste, the antiglare property can be improved. [Embodiments for Carrying Out the Invention]

[0016] [Optical Properties of Antiglare Film] The antiglare film of the present invention has the absolute value of the chromaticity b of the transmitted light * and the haze adjusted to specific ranges, so that it is possible to achieve both antiglare property and transparency (especially suppression of yellowish taste).

[0017] The antiglare film of the present invention preferably has the absolute value of the chromaticity (transmission hue) b of the transmitted light * of 15 or less (for example, 0 to 15), but may be, for example, 10 or less (for example, 5 or less), preferably 3 or less, more [[ID=4l]]preferably 2 or less, and particularly may be 1 or less (for example, 0.1 to 1). When the chromaticity b * exceeds 15, the yellowish or bluish taste increases and it looks dull, and the transparency decreases.

[0018] In addition, in this specification and the claims, the transmission hue b * can be measured in accordance with JIS Z8781 using a spectrophotometer ("U-3010" manufactured by Hitachi High-Technologies Corporation). It can be measured.

[0019] The anti-glare film of the present invention only needs to have a haze of 30% or more (for example, 30-100%). However, in order to improve anti-glare properties, for example, 40% or more (for example, 40-99%), preferably 50-98% (e.g., 70-97%), more preferably 80-96% (especially 85-95%). It is approximately %). If the haze is too low, there is a risk of reduced anti-glare properties.

[0020] The total light transmittance of the anti-glare film of the present invention is, for example, 70% or more (for example, 70-100%). Preferably 80-99.9%, more preferably 85-99% (especially 90-98%) It is a matter of degree. If the total light transmittance is too low, there is a risk that transparency will decrease.

[0021] In this specification and in the claims, haze and total light transmittance are defined as JIS K In accordance with 7105, a haze meter (NDH-5000W, manufactured by Nippon Denshoku Industries Co., Ltd.) is used. It can be measured using [this method].

[0022] [Anti-glare layer] The anti-glare film of the present invention only needs to include an anti-glare layer for exhibiting the optical properties described above. The material and structure are not limited, but they are usually formed from a transparent material with a fine, uneven surface. This uneven surface design suppresses reflections of the surrounding scenery, thereby improving glare resistance. It's possible.

[0023] The anti-glare layer surface (if the anti-glare film is formed as an anti-glare layer alone, at least one of them) The 60° gloss of the surface may be 90% or less, for example, 0-25%, preferably 0. 1-20% (e.g., 0.2-10%), more preferably 0.3-5% (especially 0.5-1%) It is approximately %). If the 60° gloss is too high, there is a risk that the anti-glare effect will decrease.

[0024] In this specification and in the claims, 60° gross is in accordance with JIS K8741. This can be measured using a gross meter ("IG-320" manufactured by Horiba, Ltd.).

[0025] The anti-glare film of the present invention may be formed by the anti-glare layer alone, or it may consist of a transparent substrate layer and this transparent It may also include an anti-glare layer formed on at least one surface of the light-colored base material layer.

[0026] The anti-glare layer only needs to be made of a transparent material, and can be made of either organic or inorganic material. It may be formed, but from the standpoint of productivity and handling, it is preferable to form it using a composition containing resin components. A formed anti-glare layer is preferred. As mentioned above, the surface of the anti-glare layer usually has an uneven shape. Furthermore, this uneven shape is not particularly limited and can be formed by physical processing or transfer using a mold. The uneven shape may be formed, but from the standpoint of productivity, etc., it is formed with a composition containing resin components. In the anti-glare layer, the fine uneven shape and particles formed by the phase separation structure of the resin components It may also have a fine uneven shape corresponding to the shape. In particular, one or more curing resin precursors In a cured product of a curable composition containing a certain component, spinodal decomposition from the liquid phase (wet spinodal decomposition) The uneven shape formed by decomposition, or the particles (for example, thermoplastic resins such as polyamide particles) Lipid particles, cross-linked poly(meth)acrylic acid ester particles, cross-linked polystyrene particles, cross-linked poly Concaves formed by the particle shape, containing cross-linked polymer particles such as polyurethane particles. A convex shape is preferred, and it is easy to form an uneven shape that can achieve both transparency and anti-glare properties, which is why wet s The uneven surface formed by pinodal decomposition is particularly preferred.

[0027] The anti-glare layer, which has an uneven surface formed by wet spinodal decomposition, is made of one or more polymers. It may be a cured product of a curable composition containing one component and one or more curable resin precursor components. For more details, the anti-glare layer consists of one or more polymer components, one or more curing resin precursor components, and a solvent. Using a composition (mixture) containing the above, the solvent is evaporated from the liquid phase of this composition by drying or other means. During the removal process, as the concentration increases, phase separation occurs due to spinodal decomposition, and the interphase distance This can form a relatively regular phase separation structure. More specifically, the wet spinodal decomposition Typically, the above composition (homogeneous solution) is coated onto a support, and the solvent is evaporated from the coated layer. This can be done by doing so. When a peelable support is used as the support, By peeling the glare layer from the support, an anti-glare film composed solely of the anti-glare layer can be obtained. By using a transparent, non-peelable support (transparent substrate layer) as the support, the transparent substrate An anti-glare film with a laminated structure consisting of a layer and an anti-glare layer can be obtained.

[0028] (Polymer components) Typically, thermoplastic resins are used as polymer components. If the brightness is high and the aforementioned surface irregularities can be formed by spinodal decomposition, then it is not particularly limited. However, for example, styrene resins, (meth)acrylic polymers, organic acid vinyl ester polymers Combination, vinyl ether polymer, halogen-containing resin, polyolefin (alicyclic polyolefin) (including vinyl), polycarbonate, polyester, polyamide, thermoplastic polyurethane, Polysulfone resins (polyethersulfone, polysulfone, etc.), polyphenylene Cellulose resins (such as polymers of 2,6-xylenol), cellulose derivatives (cellulose s (Polyesters, cellulose carbamates, cellulose ethers, etc.), silicone resins (Polyesters) (e.g., didimethylsiloxane, polymethylphenylsiloxane), rubber or elastomer ( Diene rubbers such as polybutadiene and polyisoprene, styrene-butadiene copolymer, Acrylonitrile-butadiene copolymer, acrylic rubber, urethane rubber, silicone rubber Examples include the following. These thermoplastic resins can be used individually or in combination of two or more types. It can be used.

[0029] Among these polymer components, styrene resin, (meth)acrylic polymer, vinyl acetate Poly-based polymers, vinyl ether polymers, halogen-containing resins, alicyclic polyolefins, poly Carbonate, polyester, polyamide, cellulose derivatives, silicone resins, rubber Alternatively, elastomers are commonly used. Furthermore, polymer components are usually amorphous. Furthermore, an organic solvent (especially a common solvent capable of dissolving multiple polymer components and curing resin precursor components) ) A polymer component soluble in ) is used. In particular, a polymer with high moldability or film-forming properties, transparency and weather resistance is used. Polymer components, for example, styrene resins, (meth)acrylic polymers, alicyclic polyolefins Materials such as vinyl, polyester resins, and cellulose derivatives (cellulose esters, etc.) are preferred. (Meth)acrylic polymers and cellulose esters are particularly preferred.

[0030] (Meth)acrylic polymers include (meth)acrylic monomers alone or copolymers. Copolymers of (meth)acrylic monomers and copolymerizable monomers can be used. Examples of krill monomers include (meth)acrylic acid; methyl (meth)acrylate; (meth ) Ethyl acrylate, (meth)butyl acrylate, (meth)butyl acrylate, (meth)butyl acrylate (T) Isobutyl acrylate, (meth)hexyl acrylate, (meth)octyl acrylate , (meth)acrylate C such as 2-ethylhexyl (meth)acrylate 1-10 Alkyl ;(meth)acrylate aryl such as phenyl methacrylate; hydroxyethyl ( Hydroxyalkyl compounds such as meth)acrylate and hydroxypropyl (meth)acrylate Glycidyl(meth)acrylate; N,N-dialkylamino Alkyl (meth)acrylates; (meth)acrylonitriles; lipids such as tricyclodecane Examples include (meth)acrylates having cyclic hydrocarbon groups. Copolymerizable monomers include: Styrene and other styrene monomers, vinyl ester monomers, maleic anhydride, maleic acid Examples include acids and fumaric acid. These monomers can be used individually or in combination of two or more. It can be used.

[0031] Examples of (meth)acrylic polymers include polymethyl methacrylate and other polymers. (T) Acrylic acid ester, methyl methacrylate-(meth)acrylic acid copolymer, methacrylate Methyl methacrylate-(meth)acrylic acid ester copolymer, methyl methacrylate-acrylic acid Steryl-(meth)acrylic acid copolymer, (meth)acrylic acid ester-styrene copolymer Examples include (MS resin, etc.). Among these, poly(meth)acrylate, etc. Poly(meth)acrylate C 1-6 Alkyl, especially methyl methacrylate, is the main component (50~ A methyl methacrylate polymer in an amount of 100% by weight, preferably about 70-100% by weight. It is preferable.

[0032] Examples of cellulose esters include aliphatic organic acid esters (cellulose diacetate). Cellulose acetate such as cellulose triacetate; cellulose propionate Cellulose butyrate, cellulose acetate propionate, cellulose acetate C such as Tobutyrate 1-6 Aliphatic carboxylic acid esters, etc., aromatic organic acid esters ( Cellulose phthalate, cellulose benzoate, etc. 7-12 Aromatic carboxylic acid S Examples include cellulose phosphate and inorganic acid esters (for example, cellulose sulfate, etc.). These can be shown, and may also be mixed acid esters such as acetate-nitrate cellulose ester. Cellulose esters can be used individually or in combination of two or more types. Of these, Cellulose diacetate, cellulose triacetate, cellulose acetate propionate Cellulose C, such as cellulose acetate butyrate. 2―4 Acylates are preferred. cellulose acetate C such as cellulose acetate propionate 3-4 Aspirate That is particularly preferable.

[0033] Polymer components [especially (meth)acrylic polymers] have functional groups (or The polymer may have functional groups that can react with the curing resin precursor component. - The functional group may be present in the main chain or in the side chain. The functional group is copolymerized. They may be introduced into the main chain by processes such as synthesis or co-condensation, but are usually introduced into the side chains. Functional groups include condensing groups and reactive groups (e.g., hydroxyl groups, acid anhydride groups, carboxylic acid groups). (Syl group, amino group or imino group, epoxy group, glycidyl group, isocyanate group, etc.) Polymerizable groups (e.g., vinyl, propenyl, isopropenyl, butenyl, allyl, etc. C2) -6 Alkenyl groups, such as ethynyl, propynyl, and butynyl C1 2-6 Alkynyl group, vinyl C such as Redene 2-6 Alkenylidene groups, or groups having polymerizable groups thereof [(meth)a Examples include [cryloyl groups, etc.]. Of these functional groups, polymerizable groups are preferred. stomach.

[0034] One method for introducing polymerizable groups into the side chain is to introduce functional groups such as reactive groups or condensable groups. A method of reacting a thermoplastic resin with a polymerizable compound having a reactive group with the functional group. Laws and other similar examples can be given.

[0035] In a thermoplastic resin having a functional group, the functional group may be a carboxyl group or its acid-free form. Examples include aqueous groups, hydroxyl groups, amino groups, and epoxy groups.

[0036] A thermoplastic resin having a functional group is a thermoplastic resin having a carboxyl group or its acid anhydride group. In the case of a fat, polymerizable compounds having a reactive group with the functional group include, for example, epoxy Examples include polymerizable compounds having groups such as hydroxyl, amino, and isocyanate groups. This can be demonstrated. Among these, polymerizable compounds having an epoxy group, for example, epoxycyclohexyl Epoxycycloacrylate such as xenyl (meth)acrylate 5-8 Alkenil (Meta) Acrylic Commonly used compounds include glycidyl (meth)acrylate, allyl glycidyl ether, etc. .

[0037] Typical examples include thermoplastic resins having carboxyl groups or their acid anhydride groups and epoxy Xyl group-containing compounds, especially (meth)acrylic polymers ((meth)acrylic acid-(meth)acrylic (such as lylic acid ester copolymers) and epoxy group-containing (meth)acrylates (epoxycyclo Combinations with alkenyl (meth)acrylates and glycidyl (meth)acrylates, etc. This can be illustrated by polymerizing a portion of the carboxyl groups of a (meth)acrylic polymer. Polymers into which a sex-unsaturated group has been introduced, for example, (meth)acrylic acid - (meth)acrylic acid E A portion of the carboxyl groups of the ter copolymer contains 3,4-epoxycyclohexenylmethylacrylate. The epoxy group of the relate was reacted to introduce a polymerizable group (photopolymerizable unsaturated group) into the side chain. Meta-acrylic polymers (such as Cyclomer P, manufactured by Daicel Corporation) can be used.

[0038] The amount of functional groups (especially polymerizable groups) introduced into the curing reaction of thermoplastic resins is related to thermoplasticity. For 1 kg of resin, 0.001 to 10 moles, preferably 0.01 to 5 moles, more preferably The amount is approximately 0.02 to 3 moles.

[0039] These polymer components can be used in combination as appropriate. That is, the polymer components are It may be composed of multiple polymers. The multiple polymers are obtained by wet spinodal decomposition. Furthermore, the polymers may be phase-separable. Also, the multiple polymers may be immiscible with each other. When combining multiple polymers, the combination of the first polymer and the second polymer... There are no particular limitations, but multiple polymers that are incompatible with each other near the processing temperature, for example, They can be used in appropriate combinations as two incompatible polymers. For example, the first polymer (Meth)acrylic polymers (for example, polymethyl methacrylate, having polymerizable groups) (T) In the case of acrylic polymers, etc., the second polymer is cellulose esters (C) Cellulose acetate C such as cellulose acetate propionate 3-4 Acrylate etc. ), or polyester (such as urethane-modified polyester).

[0040] Furthermore, from the viewpoint of scratch resistance after curing, at least one polymer among multiple polymers For example, one of two polymers that are incompatible with each other (the first polymer and the second polymer) When combined with polymers, at least one of the polymers must react with the curing resin precursor component. It is preferable that the polymer has functional groups (especially polymerizable groups) in its side chains that can be adapted.

[0041] The weight ratio of the first polymer to the second polymer is, for example, former / latter = 1 / 99~9 9 / 1, preferably selected from a range of about 5 / 95 to 95 / 5, and the first polymer is ( (T) In the case of an acrylic polymer, where the second polymer is a cellulose ester, both polymers The weight ratio of the rimer is former / latter = 50 / 50 to 99 / 1, preferably 55 / 45 to 90 / 10, more preferably around 60 / 40~80 / 20 (especially 65 / 35~75 / 25). That is the case.

[0042] Furthermore, the polymer used to form the phase separation structure is the two incompatible polymers mentioned above. In addition, the thermoplastic resin or other polymers may be included.

[0043] The glass transition temperature of the polymer component is, for example, -100°C to 250°C, preferably -50°C. ~230°C, more preferably in the range of 0~200°C (for example, 50~180°C) You can choose from these options. Furthermore, from the viewpoint of surface hardness, the glass transition temperature should be 50°C or higher (for example, 70°C~). The temperature is preferably around 200°C, and more preferably 100°C or higher (for example, around 100-170°C). This is advantageous. The weight-average molecular weight of the polymer component is preferably, for example, 1,000,000 or less. The range can be selected from approximately 1,000 to 500,000.

[0044] (cured resin precursor component) As a component of the curing resin precursor, it is produced by heat or active energy rays (such as ultraviolet rays or electron beams). These compounds have functional groups that react, and can be cured or crosslinked by heat or active energy rays. Various curable compounds capable of forming resins (especially curable or crosslinked resins) can be used. Examples of curing resin precursor components include thermosetting compounds or resins [epoxy groups, polymerizable groups]. , low molecular weight compounds having isocyanate groups, alkoxysilyl groups, silanol groups, etc. For example, epoxy resins, unsaturated polyester resins, urethane resins, silicone resins Photocurable compounds (photocurable compounds) that can be cured by active light (such as ultraviolet rays), such as fats, etc. Examples include UV-curable compounds such as nomers and oligomers, and photocurable compounds EB (electron beam) curable compounds may also be used. Furthermore, photocurable monomers and oligomers may also be used. - Photocurable compounds such as photocurable resins, which may have low molecular weight, are simply referred to as "photocurable resins." There are cases where this is the case.

[0045] Photocurable compounds include, for example, monomers, oligomers (or resins, especially low molecular weight resins). It is included.

[0046] Examples of monomers include monofunctional monomers such as (meth)acrylic acid esters. ) Acrylic monomers, vinyl monomers such as vinylpyrrolidone, isobornyl(meth) (Me)acrylates and adamantyl(meth)acrylates have bridging cyclic hydrocarbon groups. [e.g., acrylates], polyfunctional monomers having at least two polymerizable unsaturated bonds [ Ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate Butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate Alkylene glycol di(meth)acrylate such as hydrate, hexanediol di(meth)acrylate (T) Acrylate; Diethylene glycol di(meth)acrylate, dipropylene glycol Di(meth)acrylate, polyoxytetramethylene glycol di(meth)acrylate Polyoxyalkylene glycol di(meth)acrylate, tricycloacrylate, etc. Candimethanol di(meth)acrylate, adamantane di(meth)acrylate, etc. Di(meth)acrylates having bridging cyclic hydrocarbon groups; glycerin tri(meth)acrylate Trimethylolpropane tri(meth)acrylate, trimethylolethane tri( Meth)acrylate, pentaerythritol tri(meth)acrylate, ditrimethylol Lupropanetetra (meth)acrylate, Pentaerythritoltetra (meth)acrylate Dipentaerythritol penta(meth)acrylate, dipentaerythritol polyfunctional monomers having approximately 3 to 6 polymerizable unsaturated bonds, such as xa(meth)acrylates. Examples include [etc.].

[0047] As an oligomer or resin, a bisphenol A alkylene oxide adduct ( Acrylate, epoxy (meth)acrylate [Bisphenol A type epoxy (meth )Acrylate, novolac-type epoxy (meth)acrylate, etc., polyester (meth (T) Acrylate [e.g., aliphatic polyester type (meth)acrylate, aromatic polyester [Stellacean-type (meth)acrylate, etc.], (poly)urethane (meth)acrylate [poly Stellate-type urethane (meth)acrylate, polyether-type urethane (meth)acrylate Examples include silicone (meth)acrylate.

[0048] These photocurable compounds can be used individually or in combination of two or more. , photocurable compounds that can be cured in a short time, for example, UV-curable compounds (monomers, oligos) EB-curable compounds are preferred, such as resins that may have low molecular weights or other properties. In particular, practical A resin precursor that is advantageous for this purpose is an ultraviolet-curable resin. Furthermore, resistance such as scratch resistance can be improved. Therefore, the photocurable resin contains 2 or more molecules (preferably 2 to 6, more preferably 2 to 6) It is preferable that the compound has approximately 4 polymerizable unsaturated bonds.

[0049] The weight-average molecular weight of the curing resin precursor component is not particularly limited, but gel permeation In chromatography (GPC), compatibility with polymers is considered in terms of polystyrene equivalent. And it is 5000 or less, preferably 2000 or less, and even more preferably around 1000 or less. .

[0050] Depending on the type, the curing resin precursor component is used to improve transparency and anti-glare properties. It may contain fluorine and / or fluorine atoms.

[0051] Examples of fillers include silica particles, titania particles, zirconia particles, and alumina particles. Inorganic particles such as children, cross-linked (meth)acrylic polymer particles, cross-linked styrene resin particles, etc. These fillers may contain organic particles. They may be used individually or in combination of two or more. It can be used.

[0052] Among these fillers, those with excellent optical properties exhibit transparency and glare reduction through spinodal decomposition. Because it is easy to form an uneven surface that can achieve both properties, nanometer-sized silica particles (silica Silica nanoparticles are preferred because they can suppress the yellowing of the anti-glare film. Real silica nanoparticles are preferred. Furthermore, the average particle size of the silica nanoparticles is, for example, 1 to 800. The wavelength is approximately nm, preferably 3 to 500 nm, and more preferably 5 to 300 nm.

[0053] The proportion of fillers (especially silica nanoparticles) is 10-9% of the total curing resin precursor components. It may be as low as 0% by weight, for example, 10-80% by weight, preferably 15-70% by weight. More preferably, it is about 20-50% by weight.

[0054] Precursor components containing fluorine atoms (fluorine-containing curable compounds or fluorine-containing compounds having polymerizable groups) Examples of elemental compounds include fluorides of the monomers and oligomers, such as alkyl fluorides. (meth)acrylate [for example, perfluorooctylethyl (meth)acrylate and [e.g., refluoroethyl (meth)acrylate, fluoride (poly)oxyalkylene glycosides] Di(meth)acrylate [e.g., fluoroethylene glycol di(meth)acrylate] Fluoropolyethylene glycol di(meth)acrylate, fluoropropylene [e.g., methyl(meth)acrylate], fluorine-containing epoxy resin, fluorine-containing urethane Examples include fluoropolymer resins. Among these, fluoropolymer resins having (meth)acryloyl groups are also available. Ether compounds are preferred. Fluorine-containing curable compounds include commercially available fluorine-based polymerizable leveling compounds. It may also be a steroid.

[0055] Depending on its type, the curing resin precursor component may further contain a curing agent. For example Thermosetting resins may contain curing agents such as amines and polycarboxylic acids, and light Curable resins may contain a photopolymerization initiator. Conventional components may be used as photopolymerization initiators. For example, acetophenones or propiophenones, benzyl compounds, benzoins, benzo Examples include phenones, thioxanthones, and acylphosphine oxides. Photopolymerization The proportion of curing agents such as initiators is 0.1 to 20% by weight relative to the total curing resin precursor components. The amount is approximately 0.5 to 10% by weight, and more preferably 1 to 8% by weight.

[0056] The curing resin precursor component may further contain a curing accelerator. For example, a photocurable resin This includes photocuring accelerators, such as tertiary amines (dialkylaminobenzoic acid esters, etc.). It may also contain phosphine-based photopolymerization accelerators, etc.

[0057] Among these curing resin precursor components, polyfunctional (meth)acrylates (e.g., dipene) (Me) erythritol hexa(meth)acrylate and other polymerizable groups of about 2 to 8 (T)Acrylate, etc.), epoxy (meth)acrylate, polyester (meth)acrylate Preferred materials include phosphates, urethane (meth)acrylate, and silicone (meth)acrylate. Furthermore, the curing resin precursor component preferably contains silica nanoparticles and / or fluorine atoms. Furthermore, photocurable compounds containing silica nanoparticles [especially polyfunctional compounds containing silica nanoparticles ( (T)Acrylate, urethane (meth)acrylate containing silica nanoparticles, silica nanoparticles In particular, it contains silicone (meth)acrylate containing [a specific compound] and a fluorine-containing curable compound. preferable.

[0058] A preferred combination of curing resin precursor components is, for example, a photocurable resin containing silica nanoparticles. Compound and silicone (meth)acrylate combination, urethane (meth)acrylate and 3-6 functional (meth)acrylates, silicone (meth)acrylates, and fluorine-containing curing agents. Combinations with chemical compounds, photocurable compounds containing silica nanoparticles and fluorine-containing curable compounds This is a combination, and a particularly preferred combination is a photocurable compound containing silica nanoparticles. This is a combination of a fluorine-containing curable compound.

[0059] In this invention, silica nano The particles are added to the cured resin precursor component in such a proportion as described above relative to the entire cured resin precursor component. Preferably, it contains a silica nanoparticle-containing curing resin precursor component. Also, fluorine-containing curing The proportion of the compound is, for example, 0.001 to 1% by weight (for example) relative to the total curing resin precursor components. 0.01-0.5% by weight, preferably 0.02-0.3% by weight (e.g., 0.03-0.0). 2% by weight, more preferably about 0.05 to 0.1% by weight.

[0060] (Combination of polymer components and curing resin precursor components) In the present invention, at least two of the polymer component and the cured resin precursor component are The components are used in combinations that undergo phase separation at or near the processing temperature. For example, (a) combinations in which multiple polymer components are incompatible with each other and undergo phase separation. (b) A combination in which the polymer component and the curing resin precursor component are immiscible and undergo phase separation, c) Combinations in which multiple curing resin precursor components are mutually immiscible and undergo phase separation, etc. These combinations typically include (a) combinations of multiple polymer components or (b) a combination of polymer components and curing resin precursor components, in particular (a) multiple A combination of rimer components is preferable. If the two components to be phase-separated have high compatibility, the solvent is During the drying process for evaporation, the two do not effectively separate into phases, resulting in a decrease in the anti-glare layer's function.

[0061] Furthermore, polymer components and curing resin precursor components are usually incompatible with each other. When the component and the curing resin precursor component are immiscible and undergo phase separation, multiple polymer components are used. A polymer component may be used. When using multiple polymer components, at least one polymer - The component only needs to be incompatible with the cured resin precursor component, and the other polymer components are cured It may be compatible with the resin precursor component. Alternatively, two polymer components that are incompatible with each other may be compatible with the cured resin. Combination with precursor components (especially monomers or oligomers having multiple curable functional groups) It's okay to do that.

[0062] When a polymer component is composed of multiple polymer components that are incompatible with each other and undergoes phase separation, the cured resin The lipid precursor component is processed with at least one polymer component from among several incompatible polymers. It is used in combinations that are mutually compatible at a certain temperature. That is, multiple polymers that are mutually incompatible - When the components consist of, for example, a first polymer and a second polymer, the cured resin precursor The component only needs to be compatible with either the first polymer or the second polymer, and both polymers It may be compatible with one of the components, but it is preferable that it be compatible with only one of the polymer components. When compatible with the polymer component of the first polymer and the curing resin precursor component are used as the main components. A mixture of the above and a mixture mainly composed of a second polymer and a curing resin precursor component, It also undergoes phase separation into two phases.

[0063] If the selected polymer components have high compatibility, during the drying process to evaporate the solvent... Multiple polymers fail to effectively separate into different phases, resulting in a reduced function as an anti-glare layer. The phase separation of the components is determined by preparing a homogeneous solution using good solvents for both components, and then gradually removing the solvent. During the evaporation process, it can be easily determined by visually checking whether or not the remaining solids become cloudy. It can be determined.

[0064] Furthermore, the cured or bonded resin is typically produced by the curing of polymer components and curing resin precursor components. The bridge resin has a different refractive index from each other. Also, it has multiple polymer components (the first polymer and the second polymer) The refractive indices of the polymers also differ from each other. The difference in refractive index between the polymer component and the cured or crosslinked resin, The difference in refractive index between multiple polymer components (the first polymer and the second polymer) is, for example, 0. The value may be around 0.01 to 0.2, preferably around 0.05 to 0.15.

[0065] The ratio (by weight) of polymer components to curing resin precursor components is not particularly limited; for example, The former / latter can be selected from a range of approximately 1 / 99 to 95 / 5, for example, 2 / 98 to 90 / 10. Preferably, it is around 3 / 97 to 80 / 20, and more preferably around 5 / 95 to 70 / 30. Furthermore, if the curing resin precursor component contains a photocurable compound containing silica nanoparticles, the polymer The ratio (by weight) of the component to the curing resin precursor component is preferably, for example, 2 / 98 to 30 / 70. It may be around 3 / 97 to 20 / 80, and more preferably around 5 / 95 to 15 / 85. Furthermore, if the curing resin precursor component does not contain a photocurable compound containing silica nanoparticles, for example... For example, 10 / 90 to 60 / 40, preferably 20 / 80 to 50 / 50, and even more preferably 3 A ratio of around 0 / 70 to 40 / 60 is also acceptable.

[0066] (Other ingredients) The anti-glare layer formed from a composition containing resin components may contain various additives, such as leveling agents. Stabilizers (antioxidants, UV absorbers, etc.), surfactants, water-soluble polymers, fillers, crosslinking agents Coupling agents, colorants, flame retardants, lubricants, waxes, preservatives, viscosity modifiers, thickeners, and other additives. It may contain foaming agents, etc. The proportion of additives may be, for example, 0 relative to the entire anti-glare layer. It is approximately 0.01-10% by weight (especially 0.1-5% by weight).

[0067] (Thickness of the anti-glare layer) The thickness of the anti-glare layer (average thickness) is, for example, about 0.3 to 20 μm, preferably 1 to 15 μm. It can be as small as (for example, 1-10 μm), and is usually around 3-12 μm (especially 4-10 μm). It is a degree. Furthermore, when the anti-glare layer alone constitutes the anti-glare film, the thickness of the anti-glare layer (average thickness) This is, for example, 1 to 100 μm, preferably about 3 to 50 μm.

[0068] (Transparent base layer) The transparent substrate layer can be made of any transparent material, and can be selected according to the application, such as glass. Inorganic materials may also be used, but organic materials are commonly used due to their strength and moldability. Examples of materials include cellulose derivatives, polyesters, polyamides, polyimides, and polyamides. Examples include recarbonates and (meth)acrylic polymers. Among these, cellulose Polyester and other similar materials are commonly used.

[0069] Examples of cellulose esters include cellulose triacetate (TAC) and other cellulose compounds. Acetate, cellulose acetate propionate, cellulose acetate butyrate Which cellulose acetate C 3-4 Examples include acylate. , polyethylene terephthalate (PET), polyethylene naphthalate (PEN), etc. Examples include polyalkylene arylates.

[0070] Of these, PET and PEN are superior in their balance of mechanical properties and transparency. Which PolyC 2-4 Alkylene arylate is preferred.

[0071] The transparent substrate layer may also contain the conventional additives exemplified in the section on the anti-glare layer. The same principle applies to the anti-glare layer.

[0072] The transparent substrate layer may be a uniaxial or biaxially oriented film, but it has a low birefringence and optical Due to its excellent isotropic properties, it may also be an unstretched film.

[0073] The transparent substrate layer undergoes surface treatment (e.g., corona discharge treatment, flame treatment, plasma treatment, ozone treatment). It may be treated with UV irradiation or other processes, and may have an easy-adhesion layer.

[0074] The thickness (average thickness) of the transparent substrate layer is, for example, 5 to 2000 μm, preferably 15 to 100 The thickness is 0 μm, and more preferably around 20 to 500 μm.

[0075] (Adhesive layer) The anti-glare film of the present invention is used in various devices including smartphones and PCs (such as tablet PCs). It can also be used as a protective film for various types of touch panel display devices. In these applications, An adhesive layer may be formed on at least a portion of the other surface of the transparent substrate layer.

[0076] The adhesive layer is formed of a conventional transparent adhesive. Examples of adhesives include rubber-based adhesives. Adhesives, acrylic adhesives, olefin adhesives (modified olefin adhesives, etc.), silicone Examples include ion-based adhesives. Among these adhesives, points such as optical properties and reworkability Therefore, silicone-based adhesives are preferred.

[0077] The thickness of the adhesive layer is, for example, 1 to 150 μm, preferably 10 to 100 μm, more preferably The size is approximately 20-70 μm (especially 25-50 μm).

[0078] The adhesive layer may be formed on the entire other surface, or on a part of the other surface (for example, the periphery). Either method is acceptable. Furthermore, when formed on the periphery, the handling for adhesion is improved. For this purpose, a frame-like member (for example, a plastic sheet on the periphery) is attached to the edge of the anti-glare film. A laminated structure may be formed, and an adhesive layer may be formed on the frame-shaped member.

[0079] [Manufacturing method for anti-glare film] The method for manufacturing the anti-glare film of the present invention is not particularly limited and can be appropriately selected depending on the type of material. It is possible to form it by physical processing or transfer using a mold, but from the standpoint of productivity, A preferred method is to manufacture the composition through a curing process in which the curable composition is cured with heat or active energy rays. In particular, anti-glare layer including an anti-glare layer having an uneven shape formed by wet spinodal decomposition. In a glare film, one or more polymer components and one type are placed on a support (especially a transparent substrate layer). By applying and drying the curable composition containing the above curable resin precursor components, polymer At least two components selected from the components and curing resin precursor components are used in a wet spinodal Phase separation step to separate phases by decomposition, and the phase-separated curable composition is treated with heat or activated energy rays. It may also be a method that involves a curing process to harden the material.

[0080] In the phase separation step, the curable composition may contain a solvent. The solvent is the polymer. The type and solubility of the components and curing resin precursor components can be selected, and the minimum solid content (e.g.) For example, a uniform mixture of multiple polymer components and curing resin precursor components, reaction initiators, and other additives. Any solvent that can dissolve the polymer component and the cured resin precursor is acceptable. In particular, the solvent must be suitable for the polymer component and the cured resin precursor. The phase separation structure may be controlled by adjusting the solubility. Such solvents include: For example, ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexyl ketone) Xanones, ethers (dioxane, tetrahydrofuran, etc.), aliphatic hydrocarbons alicyclic hydrocarbons (such as hexane), cyclohexane, aromatic hydrocarbons (such as cyclohexane), (e.g., xylene, hydroxyl), halogenated carbon compounds (e.g., dichloromethane, dichloroethane), Esters (methyl acetate, ethyl acetate, butyl acetate, etc.), water, alcohols (ethanol) (Isopropanol, butanol, cyclohexanol, etc.), cellosolves [methyl Cellosolve, ethyl cellosolve, propylene glycol monomethyl ether (1-methoxy C-2-propanol, etc., cellosolve acetates, sulfoxides (dimethyl sulfates) Examples include ruhozides, amides (dimethylformamide, dimethylacetamide, etc.), etc. Examples can be given. Furthermore, the solvent may be a mixed solvent.

[0081] Of these solvents, it is preferable that they contain ketones such as methyl ethyl ketone. Alcohols (such as butanol) and / or cellosolves (1-methoxy-2-p A mixed solvent with alcohols (such as ropanol) is particularly preferred. Alternatively, the proportion of cellosolves (total amount if both are mixed) is as follows: per 100 parts by weight of ketones For example, 10 to 150 parts by weight, preferably 15 to 100 parts by weight, and more preferably 20 It is approximately 80 parts by weight (especially 25-50 parts by weight). It is a mixture of alcohols and cellosolves. When combining, the proportion of cellosolves is, for example, 1 part by weight of alcohol. ~100 parts by weight, preferably 10 to 80 parts by weight, more preferably 30 to 70 parts by weight (special (Approximately 40-60 parts by weight). In this invention, by appropriately combining solvents, By adjusting the phase separation caused by pinodial decomposition, a surface texture can be formed that achieves both transparency and anti-glare properties. Cut.

[0082] Solutes in the mixture (polymer components, curing resin precursor components, reaction initiators, and other additives) The concentration should be selected within a range that does not impair phase separation, casting properties, coating properties, etc. For example, 1 to 80% by weight, preferably 10 to 70% by weight, more preferably 20 to 60% It is approximately % by weight (especially 30-55% by weight).

[0083] Conventional coating methods include, for example, roll coaters, air knife coaters, and breezes. Rod coater, rod coater, reverse coater, bar coater, comma coater, de Tip squeeze coater, die coater, gravure coater, microgravure coater Examples include the silkscreen coating method, the dipping method, the spraying method, and the spinner method. Of these methods, the bar coater method and the gravure coater method are commonly used. If necessary, the coating solution may be applied multiple times.

[0084] After casting or coating the mixture, the mixture is heated to a temperature lower than the boiling point of the solvent (for example, below the boiling point of the solvent). The solvent is evaporated at a temperature of 1 to 120°C, preferably 5 to 50°C, and especially at a temperature about 10 to 50°C lower. By causing this, phase separation by spinodal decomposition can be induced. Decomposition usually occurs in a dry environment, for example, depending on the boiling point of the solvent, at 30-200°C (e.g., 30-100°C). °C), preferably 40 to 120°C, more preferably 50 to 90°C (especially 60 to 85°C) This can be done by drying at a certain temperature.

[0085] This spinodal decomposition, accompanied by the evaporation of the solvent, averages the domains of the phase-separated structure. It is possible to assign regularity or periodicity to distance.

[0086] In the curing process, the dried curable composition is subjected to active light (ultraviolet rays, electron beams, etc.) or heat. By further hardening the structure, the phase separation structure formed by spinodal decomposition is directly It can be fixed immediately. The curing of the curable composition is done by heating, depending on the type of curable resin precursor component. Light irradiation and other methods may be combined.

[0087] The heating temperature can be selected from an appropriate range, for example, from about 50 to 150°C. Light irradiation is performed using light. The curing method can be selected according to the type of curing component, and typically ultraviolet light, electron beams, etc., can be used. The light source is typically an ultraviolet irradiation device.

[0088] For example, in the case of ultraviolet light, there are Deep UV lamps, low-pressure mercury lamps, High-pressure mercury lamps, ultra-high-pressure mercury lamps, halogen lamps, laser light sources (helium-cadmium Light sources such as luminous lasers and excimer lasers can be used. The glycemic index (Ghee) varies depending on the thickness of the coating, for example, 10 to 10,000 mJ / cm². 2 Preferably 20-5000 mJ / cm² 2 More preferably 30-3000 mJ / cm² 2 It is to that extent. If necessary, light irradiation may be performed in an inert gas atmosphere.

[0089] [Display device] The anti-glare film of the present invention achieves both transparency and anti-glare properties, and is therefore suitable for various display devices, for example... Examples include liquid crystal displays (LCDs), organic EL displays, and touch panel displays. It can be used as an optical component, and is particularly useful as an optical element in LCD and organic EL displays. be.

[0090] In more detail, an LCD uses external light to illuminate a display unit containing liquid crystal cells. It may be an infrared LCD and may be equipped with a backlight unit for illuminating the display unit. It may also be a transmissive LCD. In a reflective LCD, incident light from the outside is reflected in the display unit. The light is captured through the display unit, and the transmitted light that passes through the display unit is reflected by a reflective material. The light can be illuminated. In a reflective LCD, the anti-glare filter of the present invention is placed in the light path forward from the reflective member. A film can be installed. For example, the anti-glare film of the present invention can be installed on the front of the display unit (viewing side front). ) can be installed or stacked, and in particular has a collimated backlight unit and a Pris It may be placed on the front of an LCD that does not have a backing sheet.

[0091] In a transmissive LCD, the backlight unit includes a light source (a tubular light source such as a cold cathode fluorescent lamp, etc.) Light from a point light source such as a photodiode is incident from one side and emitted from the front surface. A light guide plate (for example, a light guide plate with a wedge-shaped cross-section) may be provided for emitting light. If necessary, a prism sheet may be placed on the front side of the light guide plate. A reflective element is provided on the back of the board to reflect light from the light source back to the emission side. In such transmissive LCDs, the anti-glare film of the present invention is typically placed in the light path forward from the light source. It can be installed, for example, between the light guide plate and the display unit, on the front of the display unit, etc. The anti-glare film of the invention can be arranged or laminated.

[0092] In an organic EL display, each pixel of the organic EL is composed of a light-emitting element. This light-emitting element typically consists of a cathode / electron injection layer / electron transport layer / luminescence layer / hole transport layer, such as a metal. Using a hole injection layer, a positive electrode such as ITO, and a substrate such as a glass plate or transparent plastic plate. It is formed. In organic EL displays as well, the anti-glare film of the present invention is arranged in the optical path. It may be installed.

[0093] Furthermore, the anti-glare film of the present invention is used for LCDs (which are also LCDs with touch panels). (including) and OLED displays (OLED displays which are also touch panel displays) Aftermarket protection or protective film to prevent scratches (including i) It can also be used as a m. [Examples]

[0094] The present invention will be described in more detail below based on examples, but the present invention is not limited to these examples. Therefore, it is not limited to the following. The raw materials used in the examples and comparative examples are as follows, The anti-glare films were evaluated using the following method.

[0095] [Raw materials] Acrylic polymer with polymerizable groups: "Cychromer P" manufactured by Daicel Ornex Co., Ltd. " Cellulose acetate propionate: Eastman Corporation "CAP-482-20", Acetylated degree = 2.5%, propionyl degree = 46%, number-average molecular weight in polystyrene equivalent = 7 5000 Silicone acrylate: "EB1360" manufactured by Daicel Ornex Co., Ltd. Silicone-based hard coat material: "AS-201S" manufactured by Tokushiki Co., Ltd. Urethane acrylate A: "U-15HA" manufactured by Shin-Nakamura Chemical Industry Co., Ltd. Urethane acrylate B: "AU-230" manufactured by Tokushiki Co., Ltd. Dipentaerythritol hexaacrylate: Manufactured by Daicel Ornex Co., Ltd. "DPH A" Nanosilica-containing acrylic UV-curable compound: Momentive Performance Material "XR39-C6210" manufactured by Reals Japan LLC. Silica-containing acrylic UV-curable compound: "Z-757-4RL" manufactured by Aica Kogyo Co., Ltd. " Acrylic UV-curable compound: "Z-757-4CL" manufactured by Aica Kogyo Co., Ltd. PMMA Beads A: "SSX-115" manufactured by Sekisui Chemical Co., Ltd. PMMA Beads B: "SSX-105" manufactured by Sekisui Chemical Co., Ltd. Cross-linked styrene beads: "SX-130H" manufactured by Soken Chemical Co., Ltd. Polymerizable fluorine-based compound A: "KY-1203" manufactured by Shin-Etsu Chemical Co., Ltd. Polymerizable fluorine compound B: "Futergent 602A" manufactured by Neos Co., Ltd. Photoinitiator A: "Irgacure 184" manufactured by BASF Japan Ltd. Photoinitiator B: "Irgacure 907" manufactured by BASF Japan Ltd. Polyethylene terephthalate (PET) film: "Diafoil" manufactured by Mitsubishi Plastics, Inc. Cellulose triacetate (TAC) film: Fujifilm Corporation's "Fujitac T G60UL.

[0096] [Thickness of the coating layer] An optical film thickness gauge was used to measure at 10 arbitrary locations, and the average value was calculated.

[0097] [Hayes] Using a haze meter (NDH-5000W manufactured by Nippon Denshoku Co., Ltd.), JIS K7 In accordance with 136, the measurement was performed with the surface having an uneven structure facing the photodetector.

[0098] [Transparent hue (b * )] In accordance with JIS Z8781, the spectrophotometer (Hitachi High-Tech Science Co., Ltd. "U- Measurements were taken using "3010".

[0099] [60° Gloss] Gross meter (IG-320, manufactured by Horiba, Ltd.) in accordance with JIS K7105. The measurement was taken at an angle of 60° using ).

[0100] [Anti-glare] The anti-glare film that was created was attached to a commercially available black acrylic sheet with optical adhesive, and then illuminated with a three-wavelength fluorescent lamp. The reflected image was visually inspected and evaluated according to the following criteria.

[0101] ◎: Fluorescent lights are completely invisible ○: The outline of the fluorescent light is blurred. △: The shape of the fluorescent light is visible, but the glare is suppressed.

[0102] [Color] The fabricated anti-glare film was directed towards a three-wavelength fluorescent lamp, and the color of the transmitted light was observed visually. The following criteria were used for evaluation.

[0103] ○: When the film is observed through a fluorescent light, it appears colorless and transparent. △: Appears slightly yellowish or bluish. ×: Clearly appears yellow or blue.

[0104] [Example 1] 15.0 parts by weight of an acrylic polymer having polymerizable groups, cellulose acetate propionate 3 parts by weight of t, 150 parts by weight of nanosilica-containing acrylic UV-curable compound, silicone 1 part by weight of acrylate, 10 parts by weight of methyl ethyl ketone, and 24 parts by weight of 1-butanol The solution was prepared by dissolving it in a mixed solvent with the other components.

[0105] This solution was cast onto a PET film using a wire bar (#20), and then 80 The material was left in an oven at °C for 1 minute to evaporate the solvent and form a coating layer approximately 9 μm thick.

[0106] Then, ultraviolet light is irradiated onto the coating layer for about 5 seconds using a high-pressure mercury lamp (cumulative light intensity about 10 0 mJ / cm 2 The coating layer was treated with ultraviolet light (irradiation, and so on) to obtain an anti-glare film.

[0107] [Example 2] 12.5 parts by weight of an acrylic polymer having polymerizable groups, cellulose acetate propionate 4 parts by weight of t, 150 parts by weight of nanosilica-containing acrylic UV-curable compound, silicone 1 part by weight of acrylate, 81 parts by weight of methyl ethyl ketone, and 24 parts by weight of 1-butanol The solution was prepared by dissolving it in a mixed solvent with 13 parts by weight of 1-methoxy-2-propanol.

[0108] This solution was cast onto a PET film using a wire bar (#20), and then left in an oven at 80 °C for 1 minute to evaporate the solvent and form a coating layer with a thickness of approximately 9 μm.

[0109] Then, the coating layer was irradiated with ultraviolet light by a high-pressure mercury lamp for about 5 seconds to subject the coating layer to ultraviolet curing treatment, obtaining an antiglare film.

[0110] [Example 3] 45.6 parts by weight of an acrylic polymer having a polymerizable group, 2.3 parts by weight of cellulose acetate propionate, 70.7 parts by weight of urethane acrylate A, 8.2 parts by weight of dipentaerythritol hexaacrylate, 0.6 parts by weight of silicone acrylate, 0.1 part by weight of a fluorine-based compound B having a polymerizable group, 1 part by weight of photoinitiator A, and 1 part by weight of photoinitiator B were dissolved in 128 parts by weight of methyl ethyl ketone, 25 parts by weight of 1-butanol, and 31 parts by weight of cyclohexanone to prepare a solution. ート2.3重量部、ウレタンアクリレートA70.7重量部、ジペンタエリスリトールヘ キサアクリレート8.2重量部、シリコーンアクリレート0.6重量部、重合性基を有す るフッ素系化合物B0.1重量部、光開始剤A1重量部、光開始剤B1重量部を、メチル エチルケトン128重量部と1-ブタノール25重量部とシクロヘキサノン31重量部と [[ID=~25]]の混合溶媒に溶解し、溶液を調製した。

[0111] This solution was cast onto a TAC film using a wire bar (#16), and then left in an oven at 80 °C for 1 minute to evaporate the solvent and form a coating layer with a thickness of approximately 7 μm.

[0112] Then, the coating layer was irradiated with ultraviolet light by a high-pressure mercury lamp for about 5 seconds to subject the coating layer to ultraviolet curing treatment, obtaining an antiglare film.

[0113] [Example 4] 12.5 parts by weight of an acrylic polymer having a polymerizable group, 5.5 parts by weight of cellulose acetate propionate, 149 parts by weight of a nano-silica-containing acrylic ultraviolet curable compound, 0.1 part by weight of a fluorine-based compound B having a polymerizable group were dissolved in 129 parts by weight of methyl ethyl ketone and 1-b ート5.5重量部、ナノシリカ含有アクリル系紫外線硬化性化合物149重量部、重合性 基を有するフッ素系化合物B0.1重量部を、メチルエチルケトン129重量部と1-ブ Dissolved in a mixed solvent of 24 parts by weight of tanol and 13 parts by weight of 1-methoxy-2-propanol , a solution was prepared.

[0114] This solution was cast onto a PET film using a wire bar (#14), and then left in an oven at 80 °C for 1 minute to evaporate the solvent and form a coating layer with a thickness of about 5 μm.

[0115] Then, the coating layer was irradiated with ultraviolet light by a high-pressure mercury lamp for about 5 seconds to subject the coating layer to ultraviolet curing treatment to obtain an antiglare film.

[0116] [Example 5] 36.9 parts by weight of an acrylic polymer having a polymerizable group, cellulose acetate propionate 3.0 parts by weight, 55.0 parts by weight of urethane acrylate A, 0 .7 parts by weight of silicone acrylate, 22.9 parts by weight of dipentaerythritol hexaacrylate, having a polymerizable group 0.1 part by weight of a fluorine-based compound A having a polymerizable group, 1 part by weight of photoinitiator A, 1 part by weight of photoinitiator B were dissolved in a mixed solvent of 144 parts by weight of methyl ethyl ketone and 21 parts by weight of 1-butanol to prepare a solution.

[0117] This solution was cast onto a TAC film using a wire bar (#18), and then left in an oven at 80 °C for 1 minute to evaporate the solvent and form a coating layer with a thickness of about 8 μm.

[0118] Then, the coating layer was irradiated with ultraviolet light by a high-pressure mercury lamp for about 5 seconds to subject the coating layer to ultraviolet curing treatment to obtain an antiglare film.

[0119] [Example 6] 50 parts by weight of an acrylic polymer having a polymerizable group, cellulose acetate propionate ​​4 parts by weight, 76 parts by weight of urethane acrylate A, 1 part by weight of silicone acrylate, light-curing 1 part by weight of initiator A and 1 part by weight of photoinitiator B, and 176 parts by weight of methyl ethyl ketone and 1-butano The solution was prepared by dissolving it in a mixed solvent with 28 parts by weight of 0.

[0120] This solution was cast onto the TAC film using a wire bar (#18), and then 80 The material was left in an oven at °C for 1 minute to evaporate the solvent and form a coating layer approximately 8 μm thick.

[0121] Then, ultraviolet light is shone onto the coating layer using a high-pressure mercury lamp for about 5 seconds to remove ultraviolet rays from the coating layer. The film was cured to obtain an anti-glare film.

[0122] [Example 7] 3 parts by weight of cellulose acetate propionate, 97 parts by weight of urethane acrylate A, 90 parts by weight of PMMA beads B, 1 part by weight of photoinitiator A, and 1 part by weight of photoinitiator B are mixed with methyl ethyl Dissolve 277 parts by weight of lucetone and 23 parts by weight of 1-butanol in a mixed solvent to prepare a solution. Ta.

[0123] This solution was cast onto a PET film using a wire bar (#6), and then heated to 80°C. The sample was left in an oven for 1 minute to evaporate the solvent and form a coating layer approximately 1 μm thick.

[0124] Then, ultraviolet light is shone onto the coating layer using a high-pressure mercury lamp for about 5 seconds to remove ultraviolet rays from the coating layer. The film was cured to obtain an anti-glare film.

[0125] [Reference example 1] Urethane acrylate B 39 parts by weight, silicone-based hard coat material 15.7 parts by weight, P 0.3 parts by weight of MMA beads A and 6.1 parts by weight of cross-linked styrene beads are mixed with methyl ethyl ketone 3. It was dissolved in 8 parts by weight to prepare a solution.

[0126] This solution was cast onto a PET film using a wire bar (#14), and then left in an oven at 100 °C for 1 minute to evaporate the solvent and form a coating layer with a thickness of about 6 μm. .

[0127] Then, the coating layer was irradiated with ultraviolet rays by a high-pressure mercury lamp for about 5 seconds to subject the coating layer to ultraviolet curing treatment, and an antiglare film was obtained.

[0128] [Reference Example 2] A solution was prepared by mixing 50 parts by mass of a silica-containing acrylic ultraviolet curable compound and 150 parts by mass of an acrylic ultraviolet curable compound. This solution was cast onto a PET film using a wire bar (#14) and then left in an oven at 80 °C for 1 minute to evaporate the solvent and form a coating layer with a thickness of about 7 μm.

[0129] Then, the coating layer was irradiated with ultraviolet rays by an ultraviolet lamp for about 5 seconds to subject it to ultraviolet curing treatment, and an antiglare film was obtained.

[0130] The evaluation results of the antiglare films obtained in the examples and reference examples are shown in Table 1.

[0131]

Table 1

[0132] As is clear from the results in Table 1, the antiglare film of the example had high antiglare properties and excellent color tone (colorless transparency).

Industrial Applicability

[0133] The antiglare film of the present invention can be used in various display devices, for example, LCDs, cathode ray tube display devices, organic or ​​This includes inorganic EL displays, field emission displays (FEDs), and surface electric field displays. Display (SED), rear projection television display, plasma display (i) It can be used as an anti-glare film for display devices such as touch panel displays. ru.

[0134] Furthermore, the anti-glare film of the present invention can be used with screens of various sizes and is small or portable. Screen display devices (e.g., car navigation displays, game consoles, smartphones) (Displays and touch-panel devices such as smartphones and tablet PCs), Medium-sized screen display devices (e.g., notebook or laptop PCs or desktop PCs) PCs, televisions, etc., large-screen display devices (for example, digital signage) It can be used for things like graphics. Of these, you can choose the appropriate one depending on the difference in resolution, but transparency Because it can achieve both brightness and anti-glare properties, for example, it is suitable for display equipment on medium-sized and large screens. It can be used in a suitable location.

[0135] Furthermore, films with an anti-glare layer containing a curing resin precursor also have excellent scratch resistance, making them suitable for LCDs. Aftermarket protective films (protective films) for OLED displays. It can also be used as such.

Claims

1. It comprises a transparent substrate layer and an anti-glare layer formed on at least one surface of the transparent substrate layer, with a 60-degree gloss of 10% or less and a chromaticity b of transmitted light. ＊ A display device equipped with an anti-glare film in which the absolute value of is 2 or less and the haze is 70% or more, A display device in which the anti-glare layer is a cured product of a curable composition comprising one or more polymer components and one or more curable resin precursor components, wherein the curable resin precursor component is a precursor component containing fluorine atoms, and the layer is cured in a state in which an uneven surface is formed by a phase separation structure resulting from wet spinodal decomposition of at least two components selected from the polymer component and the curable resin precursor component.

2. The display device according to claim 1, wherein the polymer component comprises cellulose esters and / or a (meth)acrylic polymer which may have polymerizable groups.

3. The display device according to claim 1 or 2, wherein the curing resin precursor component comprises at least one selected from polyfunctional (meth)acrylate, epoxy (meth)acrylate, polyester (meth)acrylate, urethane (meth)acrylate, and silicone (meth)acrylate.

4. The display device according to any one of claims 1 to 3, wherein the curing resin precursor component comprises silica nanoparticles.

5. The display device according to any one of claims 1 to 4, which is an organic EL display or a liquid crystal display device.

6. A method for manufacturing a display device according to any one of claims 1 to 5, wherein the method for manufacturing an anti-glare film includes a curing step of curing a curable composition with heat or active energy rays.

7. The method for manufacturing an anti-glare film further comprises a phase separation step of applying a curable composition containing one or more polymer components and one or more curable resin precursor components onto a support and drying it, thereby separating at least two components selected from the polymer components and curable resin precursor components by wet spinodal decomposition, and the curing step is a curing step of curing the phase-separated curable composition with heat or active energy rays, as described in claim 6.

Images