Anti-glare film, method for producing same, and

Abstract

According to the anti-dazzle film, the ratio R / V of the diffuse reflection specular reflection intensity R to the total diffuse reflection intensity V is 0.01-0.12, and the absolute value of the chromaticity b * of transmitted light is 3 or less. The anti-glare film comprises a transparent base material layer and an anti-glare layer formed on at least one surface of the transparent base material layer, and the anti-glare layer may be a cured product of a curable composition containing one or more polymer components and one or more cured resin precursor components. At least two components selected from the group consisting of a polymer component and a cured resin precursor component can be phase-separated by wet spironodal decomposition. The anti-glare film can give consideration to both non-coloring properties and anti-glare properties.

Description

[0001] This application is a divisional application of the application filed on September 21, 2018, with application number 201880078443.9 and invention title "Anti-glare film, and its manufacturing method and use". Technical Field

[0002] This invention relates to anti-glare films that can be used in various display devices such as liquid crystal displays (LCDs) and organic electroluminescent displays (ELs), as well as their manufacturing methods and applications. Background Technology

[0003] Anti-glare films are widely used to prevent external light from reflecting onto the display surface of image display devices such as LCDs and OLEDs, thereby improving visual clarity. The optical properties required for anti-glare films, besides improving anti-glare performance through high haze, also include high transparency (total light transmittance) and imparting a neutral white hue to the visible side rather than a yellowish or reddish tint, thus improving visual clarity. To achieve this function, conventional methods for anti-glare films involve coating a mixture of microparticles and adhesive or curing resin onto a substrate, forming fine irregularities on the surface to prevent specular reflection and thus exhibit anti-glare properties. However, in anti-glare films utilizing microparticles, since the intensity distribution of transmitted and scattered light is controlled based on particle size, it is not effective in preventing glare on the display surface or blurry text. Furthermore, for anti-glare films containing dispersed particles, the greater the difference in refractive index between the matrix material constituting the anti-glare film and the dispersed particles, the higher the haze value and the higher the light diffusion. However, as the internal haze increases, light from the short wavelength side is scattered towards a wide angle. Therefore, when viewing the display device from the front, a yellowish or dull appearance will be observed, reducing visual discernibility. Moreover, due to the ease of backscattering, transparency is also reduced.

[0004] To this end, a method is also known to form an uneven shape on a surface by utilizing the decomposition of the helix lines of incompatible resin components. Japanese Patent Application Publication No. 2014-85371 (Patent Document 1) discloses an anti-glare film comprising an anti-glare layer having elongated protrusions formed on the surface by phase separation of multiple resin components. These elongated protrusions have a branched structure and a total length of 100 μm or more. Furthermore, on the surface of the anti-glare layer, on average, every 1 mm... 2 There is one or more of the aforementioned elongated protrusions. This anti-glare film has an excellent balance between haze and sharpness, and can improve anti-glare performance even when installed on high-resolution display devices (such as LCDs and organic EL displays with a resolution of 200ppi or higher), can highly suppress glare, and can also suppress text blurring.

[0005] However, for this anti-glare film, sometimes increasing transparency can lead to a decrease in anti-glare performance. Furthermore, in existing methods, to prepare a transparent film with low yellow tint and high anti-glare performance, adjustments are mainly made to haze and gloss, but this does not necessarily correlate with anti-glare performance. That is, to improve anti-glare performance, light scattering needs to be increased, resulting in high haze, but anti-glare performance and transparency (especially the suppression of yellow tint) are in a trade-off relationship, making it difficult to achieve both simultaneously.

[0006] In Japanese Patent No. 5531388 (Patent Document 2), as a method for stably supplying optical sheets with good contrast, a method for manufacturing an optical sheet is disclosed, wherein the optical sheet has a functional layer on at least one side of a transparent substrate, and a diffusion element is provided on the outermost surface and / or inside the functional layer. The method includes: controlling such that the ratio of the diffuse specular reflection intensity measured at a given angle to the sum of the diffuse reflection intensity exceeds 0.19, thereby stably manufacturing an optical sheet with excellent contrast.

[0007] However, the optical sheets obtained by this method may have insufficient anti-glare performance depending on the application.

[0008] Existing technical documents

[0009] Patent documents

[0010] Patent Document 1: Japanese Patent Application Publication No. 2014-85371 (Claim 1, Paragraph

[0021] )

[0011] Patent Document 2: Japanese Patent No. 5531388 (Claim 1) Summary of the Invention

[0012] The problem that the invention aims to solve

[0013] Therefore, the object of the present invention is to provide an anti-glare film that can take into account both hue (non-coloring) and anti-glare properties, as well as its manufacturing method and uses.

[0014] Another object of the present invention is to provide an anti-glare film with less yellow tint and higher transparency, as well as a method for manufacturing the film and its uses.

[0015] Problem Solving Methods

[0016] To achieve the aforementioned goals, the inventors conducted in-depth research and discovered that by preparing a diffuse specular surface with a diffuse reflection intensity R to the sum of diffuse reflection intensity V, R / V being 0.01~0.12, and the chromaticity b of the transmitted light being... ＊ An anti-glare film with an absolute value of less than 3 can balance non-coloring and anti-glare properties, thus completing the present invention.

[0017] That is, the ratio of the diffuse specular reflection intensity R of the anti-glare film of the present invention to the sum of diffuse reflection intensity V, R / V (wherein, the diffuse specular reflection intensity R is the diffuse reflection intensity measured by a variable angle photometer with an opening angle of 1 degree when visible light is irradiated at an angle of 45 degrees relative to the normal to the surface of the anti-glare film, and the sum of diffuse reflection intensity V is the sum of diffuse reflection intensity measured by a variable angle photometer with an opening angle of 1 degree for each degree from -45 degrees to +45 degrees, including 0 degrees, in the diffuse reflection direction when visible light is irradiated at an angle of 45 degrees relative to the normal to the surface of the anti-glare film,) is 0.01 to 0.12, and the chromaticity b of the transmitted light is... ＊ The absolute value is 3 or less. The aforementioned anti-glare film may comprise a transparent substrate layer and an anti-glare layer formed on at least one side of the transparent substrate layer, and the aforementioned anti-glare layer is a cured product of a curable composition containing one or more polymer components and one or more curing resin precursor components. It is possible that at least two components selected from the aforementioned polymer components and the aforementioned curing resin precursor components are capable of phase separation through wet cyclohexane decomposition. The aforementioned polymer components may contain cellulose esters and / or optionally (meth)acrylate polymers having polymerizable groups. The aforementioned curing resin precursor components may contain at least one selected from polyfunctional (meth)acrylates, epoxy (meth)acrylates, polyester (meth)acrylates, urethane (meth)acrylates, and organosilicon (meth)acrylates. The aforementioned curing resin precursor components may contain silica nanoparticles and / or fluorine atoms.

[0018] This invention also includes a method for manufacturing the aforementioned anti-glare film, the method comprising a curing step of curing a curable composition by means of heat or active energy radiation. The manufacturing method may further comprise a phase separation step of coating a curable composition containing one or more polymer components and one or more curing resin precursor components onto a support and drying it, thereby causing at least two components selected from the polymer components and curing resin precursor components to undergo phase separation through wet gyroscopic decomposition. The aforementioned curing step may be a curing step in which the phase-separated curable composition is cured by means of heat or active energy radiation.

[0019] The present invention also includes a display device having the aforementioned anti-glare film. This display device may be an organic EL display or a liquid crystal display.

[0020] This invention also includes the above-mentioned R / V and chromaticity b ＊ The method of adjusting the absolute value to the range of 0.01~0.12 and below 3 respectively to improve the anti-glare and transparency of the anti-glare film.

[0021] It should be noted that in this specification and claims, (meth)acrylate includes both methacrylate and acrylate.

[0022] The effects of the invention

[0023] In this invention, the anti-glare film has an R / V of 0.01~0.12, and the chromaticity b of the transmitted light is... ＊ With an absolute value of 3 or less, both non-coloring and anti-glare properties can be achieved. Furthermore, by causing wet spinel decomposition of specific curable compositions, anti-glare properties can be ensured while reducing yellowness, thus improving transparency while suppressing yellowing. Detailed Implementation

[0024] [Optical properties of anti-glare film]

[0025] The anti-glare film of this invention utilizes the ratio of diffuse specular reflection intensity R to the sum of diffuse reflection intensity V, R / V, and the chromaticity b of transmitted light. ＊ The absolute value is adjusted to a specific range, thus achieving a balance between anti-glare and transparency.

[0026] The anti-glare film of the present invention has an R / V of 0.01 to 0.12, for example, it can be 0.01 to 0.1, preferably 0.01 to 0.08, more preferably 0.01 to 0.05 (particularly preferably 0.01 to 0.03). When the R / V is too large, the anti-glare performance is reduced; when it is too small, the transparency is reduced.

[0027] It should be noted that, in this specification and claims, R / V can be measured using the method described in Japanese Patent No. 5531388, and more specifically, it can be measured using the method described in the embodiments described later.

[0028] The anti-glare film of this invention only requires the yellowness to be suppressed and the chromaticity (transmitted hue) of the transmitted light to be reduced. ＊ The absolute value of the yellow tint should be 3 or less (e.g., 0 to 3), preferably 2.5 or less (e.g., 0.01 to 2.5), more preferably 2 or less (e.g., 0.05 to 2), and even more preferably 1 or less (e.g., 0.1 to 1). When the yellow tint is too high, the yellow and blue tints increase, making it look dull and reducing transparency.

[0029] It should be noted that, in this specification and claims, hue b is used... ＊ It can be measured according to JIS Z8781 using a spectrophotometer (Hitachi High-Tech Science Co., Ltd. "U-3010").

[0030] The anti-glare film of the present invention can have a high degree of haze. Specifically, the haze of the anti-glare film of the present invention is 30% or more (e.g., 30-100%), for example 50-98%, preferably 70-97%, more preferably 80-96% (particularly preferably 85-95%). When the haze is too low, there is a risk of reduced anti-glare performance.

[0031] The anti-glare film of the present invention has a total light transmittance of, for example, 70% or more (e.g., 70-100%), preferably 80-99.9%, more preferably 85-99% (particularly preferably 90-98%). If the total light transmittance is too low, there is a risk of reduced transparency.

[0032] It should be noted that in this specification and claims, haze and total light transmittance can be measured according to JIS K7105 using a haze meter (NDH-5000W manufactured by Nippon Denshoku Kogyo Co., Ltd.).

[0033] The 60-degree gloss level of the anti-glare film of the present invention (when the anti-glare film is a laminate of an anti-glare layer and a transparent substrate layer, it refers to the 60-degree gloss level of the surface of the anti-glare layer) can be less than 90%, for example, 0-25%, preferably 0.1-20% (e.g., 0.2-10%), more preferably 0.3-5% (particularly preferably about 0.5-1%). If the 60-degree gloss level is too high, there is a risk of reduced anti-glare performance.

[0034] In this specification and claims, a gloss level of 60 degrees can be measured according to JIS K8741 using a gloss meter (Horiba Manufacturing Co., Ltd. "IG-320").

[0035] [Anti-glare layer]

[0036] The anti-glare film of the present invention may include an anti-glare layer for displaying the above-mentioned optical properties. The material and structure are not limited, but it is usually formed of a transparent material with fine concave and convex shapes formed on the surface. The concave and convex shapes can suppress the reflection of the outside scene caused by surface reflection, thereby improving the anti-glare performance.

[0037] The anti-glare film of the present invention may be formed by anti-glare layer alone, or may include a transparent substrate layer and an anti-glare layer formed on at least one side of the transparent substrate layer.

[0038] The anti-glare layer can be formed from a transparent material, or from any material among organic and inorganic materials. However, considering factors such as productivity and processability, an anti-glare layer formed from a composition containing resin components is preferred. The surface of the anti-glare layer typically has an uneven shape. This uneven shape is not particularly limited and can be formed through physical processing, transfer using a mold, etc. However, considering factors such as productivity, in an anti-glare layer formed from a composition containing resin components, it can be a fine uneven shape formed by the phase separation structure of the resin components, or a fine uneven shape corresponding to the shape of the particles. Among the cured products of curable compositions containing one or more curable resin precursor components, it is preferable to have an uneven shape formed by decomposition of the spool line from the liquid phase (wet spool line decomposition), or an uneven shape formed by containing particles (e.g., thermoplastic resin particles such as polyamide particles, cross-linked poly(meth)acrylate particles, cross-linked polystyrene particles, cross-linked polyurethane particles, and other cross-linked polymer particles) and the shape of the particles. From the viewpoint of easily forming an uneven shape that can take into account both transparency and anti-glare properties, an uneven shape formed by wet spool line decomposition is particularly preferred.

[0039] An anti-glare layer with an uneven shape formed by wet swirl decomposition can be a cured product of a curable composition containing one or more polymer components and one or more curing resin precursor components. Specifically, for the anti-glare layer, a composition (mixture) containing one or more polymer components, one or more curing resin precursor components, and a solvent is used. During the process of evaporating or removing the solvent from the liquid phase of the composition by drying or the like, phase separation based on swirl decomposition occurs along with the concentration of the mixture, thereby forming a phase separation structure with a substantially regular interphase spacing. More specifically, the aforementioned wet swirl decomposition is generally carried out by coating the aforementioned composition (uniform mixture) onto a support and evaporating the solvent from the coating layer. When a peelable support is used as the support, an anti-glare film consisting solely of the anti-glare layer can be obtained by peeling the anti-glare layer from the support. When a transparent, non-peelable support (transparent substrate layer) is used as the support, an anti-glare film with a laminated structure consisting of a transparent substrate layer and an anti-glare layer can be obtained.

[0040] (Polymer composition)

[0041] Thermoplastic resins are commonly used as polymer components. There are no particular limitations on the thermoplastic resin as long as it has high transparency and can be decomposed through the helix to form the aforementioned surface irregularities. Examples include: styrene-based resins, (meth)acrylic polymers, organic acid vinyl ester polymers, vinyl ether polymers, halogenated resins, polyolefins (including alicyclic polyolefins), polycarbonates, polyesters, polyamides, thermoplastic polyurethanes, polysulfone resins (polyethersulfone, polysulfone, etc.), polyphenylene ether resins (polymers of 2,6-xylenol, etc.), cellulose derivatives (cellulose esters, cellulose carbamates, cellulose ethers, etc.), silicone resins (polydimethylsiloxane, polymethylphenylsiloxane, etc.), rubbers or elastomers (polybutadiene, polyisoprene, and other diene rubbers, styrene-butadiene copolymers, acrylonitrile-butadiene copolymers, acrylic rubbers, carbamate rubbers, silicone rubbers, etc.). These thermoplastic resins can be used alone or in combination of two or more.

[0042] Commonly used polymer components include styrene resins, (meth)acrylic polymers, vinyl acetate polymers, vinyl ether polymers, halogenated resins, alicyclic polyolefins, polycarbonates, polyesters, polyamides, cellulose derivatives, silicone resins, rubbers, and elastomers. Additionally, non-crystalline polymer components that are soluble in organic solvents (especially common solvents that dissolve multiple polymer components and curing resin precursor components) are typically used. Polymer components with high moldability or film-forming properties, transparency, and weather resistance are particularly preferred, such as styrene resins, (meth)acrylic polymers, alicyclic polyolefins, polyester resins, and cellulose derivatives (cellulose esters, etc.), with (meth)acrylic polymers and cellulose esters being especially preferred.

[0043] As (meth)acrylic acid polymers, homopolymers or copolymers of (meth)acrylic acid monomers, copolymers of (meth)acrylic acid monomers and copolymers, etc., can be used. Examples of (meth)acrylic acid monomers include: (meth)acrylic acid; methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, tert-butyl (meth)acrylate, isobutyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, etc. (meth)acrylic acid C 1-10Alkyl esters; aryl methacrylates such as phenyl methacrylate; hydroxyethyl methacrylate, hydroxypropyl methacrylate, and hydroxyalkyl methacrylates; glycidyl methacrylate; N,N-dialkylaminoalkyl methacrylate; methacrylonitrile; tricyclodecane and other methacrylates with alicyclic hydrocarbon groups. Examples of comonomers include styrene monomers such as styrene, vinyl ester monomers, maleic anhydride, maleic acid, fumaric acid, etc. These monomers can be used alone or in combination of two or more.

[0044] Examples of (meth)acrylic polymers include, for example, poly(meth)acrylates such as polymethyl methacrylate, methyl methacrylate-(meth)acrylic acid copolymers, methyl methacrylate-(meth)acrylate copolymers, methyl methacrylate-acrylate-(meth)acrylic acid copolymers, and (meth)acrylate-styrene copolymers (MS resin, etc.). Among these, poly(meth)acrylic acid C, such as poly(methyl methacrylate), is preferred. 1-6 Alkyl esters, especially methyl methacrylate polymers with methyl methacrylate as the main component (e.g., 50-100% by weight, preferably around 70-100% by weight).

[0045] Examples of cellulose esters include: aliphatic organic esters (cellulose acetate such as cellulose diacetate, cellulose triacetate, etc.; cellulose propionate, cellulose butyrate, cellulose acetate propionate, cellulose acetate butyrate, etc.). 1-6 Aliphatic carboxylic esters, etc.), aromatic organic esters (cellulose phthalate, cellulose benzoate, etc. C 7-12 Aromatic carboxylic acid esters, inorganic acid esters (e.g., cellulose phosphate, cellulose sulfate, etc.), and mixed acid esters such as cellulose acetate / cellulose nitrate esters are also acceptable. These cellulose esters can be used alone or in combination of two or more. Among these, cellulose diacetate, cellulose triacetate, cellulose acetate propionate, and cellulose acetate butyrate are preferred. 2-4 Acetic cellulose, especially cellulose acetate propionate and other cellulose acetate C, are preferred. 3-4 Acid cellulose.

[0046] The polymer component [especially (meth)acrylic acid polymers] can be a polymer having functional groups that participate in the curing reaction (or functional groups that can react with the precursor component of the curing resin). The polymer may have functional groups in the main chain or in the side chains. These functional groups can be introduced into the main chain through copolymerization, co-condensation, etc., but are usually introduced into the side chains. Examples of such functional groups include condensation groups, reactive groups (e.g., hydroxyl, anhydride, carboxyl, amino or imino, epoxy, glycidyl, isocyanate, etc.), and polymerizable groups (e.g., vinyl, propenyl, isopropenyl, butenyl, allyl, etc.).2-6 alkenyl, ethynyl, propynyl, butynyl, etc. C 2-6 C-type alkynyl groups, vinyl groups, etc. 2-6 Alkenes, or groups having these polymerizable groups [(meth)acryloyl group, etc.], etc. Among these functional groups, polymerizable groups are preferred.

[0047] As a method for introducing polymerizable groups into the side chain, examples include reacting a thermoplastic resin having functional groups such as reactive groups and condensation groups with a polymerizable compound having groups that are reactive with the aforementioned functional groups.

[0048] In thermoplastic resins having functional groups, examples of functional groups include carboxyl groups or their anhydride groups, hydroxyl groups, amino groups, epoxy groups, etc.

[0049] When the thermoplastic resin having functional groups is a thermoplastic resin having a carboxyl group or its anhydride group, examples of polymeric compounds having groups reactive with the aforementioned functional groups include, for example, polymeric compounds having epoxy, hydroxyl, amino, isocyanate, etc. Among these, polymeric compounds having epoxy groups are commonly used, such as (meth)acrylate epoxycyclohexene ester, etc. 5-8 Alkenyl esters, (meth)acrylate glycidyl esters, allyl glycidyl ethers, etc.

[0050] Representative examples include thermoplastic resins having carboxyl groups or their anhydride groups, epoxy-containing compounds, particularly (meth)acrylic polymers ((meth)acrylic acid-(meth)acrylate copolymers, etc.), and epoxy-containing (meth)acrylates ((meth)acrylate epoxycycloalkenyl ester, (meth)acrylate glycidyl ester, etc.). Specifically, polymers in which polymerizable unsaturated groups are introduced into a portion of the carboxyl group of a (meth)acrylic polymer can be used. For example, a (meth)acrylic polymer (CYCLOMER P, manufactured by Daicel Co., Ltd.) is formed by reacting a portion of the carboxyl group of a (meth)acrylic acid-(meth)acrylate copolymer with the epoxy group of 3,4-epoxycyclohexenyl methyl acrylate to introduce polymerizable groups (photopolymerizable unsaturated groups) into its side chain.

[0051] Relative to 1 kg of thermoplastic resin, the amount of functional groups (especially polymerizable groups) involved in the curing reaction relative to the thermoplastic resin is, for example, 0.001 to 10 mol, preferably 0.01 to 5 mol, and more preferably about 0.02 to 3 mol.

[0052] These polymer components can be used in appropriate combinations. That is, the polymer components can consist of multiple polymers. Multiple polymers can undergo phase separation through wet cyclohexane decomposition. In addition, multiple polymers can be incompatible with each other. In the case of combining multiple polymers, the combination of the first polymer and the second polymer is not particularly limited, and can be used in appropriate combinations of multiple polymers that are incompatible near the processing temperature, such as two incompatible polymers. For example, if the first polymer is a (meth)acrylic acid polymer (e.g., polymethyl methacrylate, (meth)acrylic acid polymers with polymerizable groups, etc.), the second polymer can be a cellulose ester (cellulose acetate propionate, etc., C4 acetate). 3-4 (e.g., acid cellulose) and polyester (e.g., urethane-modified polyester).

[0053] Furthermore, from the viewpoint of scratch resistance after curing, it is preferable that at least one polymer from a plurality of polymers, such as at least one polymer from a plurality of incompatible polymers (in the case of combining the first polymer and the second polymer), is a polymer having functional groups (especially polymerizable groups) on its side chains that are capable of reacting with the precursor components of the cured resin.

[0054] The weight ratio of the first polymer to the second polymer can be selected from, for example, the former / the latter = 1 / 99 to 99 / 1, preferably from about 5 / 95 to 95 / 5. When the first polymer is a (meth)acrylic acid polymer and the second polymer is a cellulose ester, the weight ratio of the two polymers is, for example, the former / the latter = 50 / 50 to 99 / 1, preferably 55 / 45 to 90 / 10, more preferably 60 / 40 to 80 / 20 (particularly preferably 65 / 35 to 75 / 25).

[0055] It should be noted that, in addition to the two incompatible polymers mentioned above, the polymers used to form the phase-separated structure may also include the thermoplastic resins and other polymers.

[0056] The glass transition temperature of the polymer component can be selected from, for example, a range of -100°C to 250°C, preferably -50°C to 230°C, and more preferably around 0°C to 200°C (e.g., around 50°C to 180°C). It should be noted that, from the viewpoint of surface hardness, a glass transition temperature of 50°C or higher (e.g., around 70°C to 200°C), preferably 100°C or higher (e.g., around 100°C to 170°C), is advantageous. The weight-average molecular weight of the polymer component can be selected from, for example, a range of 1,000,000 or less, preferably around 1,000 to 500,000.

[0057] (Components of the cured resin precursor)

[0058] As precursor components for curable resins, compounds having functional groups that react with heat, active energy rays (ultraviolet light, electron beams, etc.) can be used, as well as various curable compounds capable of curing or crosslinking to form resins (especially curable or crosslinked resins) by heat, active energy rays, etc. Examples of such precursor components for curable resins include: thermosetting compounds or resins [low molecular weight compounds having epoxy groups, polymerizable groups, isocyanate groups, alkoxysilyl groups, silanol groups, etc. (e.g., epoxy resins, unsaturated polyester resins, urethane resins, silicone resins, etc.)]; and photocurable compounds that can be cured by active light (ultraviolet light, electron beams (EB), etc.) (photocurable monomers, oligomers, etc., ultraviolet-curable compounds, electron beam-curable compounds, etc.). It should be noted that photocurable compounds such as photocurable monomers, oligomers, and optionally low molecular weight photocurable resins are sometimes simply referred to as "photocurable resins".

[0059] Photocurable compounds contain, for example, monomers, oligomers (or resins, especially low molecular weight resins).

[0060] Examples of monomers include: monofunctional monomers [(meth)acrylate monomers such as (meth)acrylates, vinyl monomers such as vinylpyrrolidone, isobornyl (meth)acrylate, adamantane (meth)acrylate, and other (meth)acrylates with bridged ring hydrocarbon groups], and polyfunctional monomers having at least two polymerizable unsaturated bonds [alkylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, hexanediol di(meth)acrylate, and other alkylene glycol di(meth)acrylates; diethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, polyoxyethylene glycol di(meth)acrylate, etc.] Tetramethylene glycol di(meth)acrylate and other (poly)oxyalkylene glycol di(meth)acrylates; tricyclodecanediethanol di(meth)acrylate, adamantane di(meth)acrylate and other di(meth)acrylates with bridged ring hydrocarbon groups; glycerol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, di(trimethylolpropane)tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate and other polyfunctional monomers with polymerizable unsaturated bonds of about 3 to 6, etc.

[0061] Examples of oligomers or resins include bisphenol A-oxidized olefin adducts (meth)acrylates, epoxy (meth)acrylates [bisphenol A type epoxy (meth)acrylates, phenolic varnish type epoxy (meth)acrylates, etc.], polyester (meth)acrylates [e.g., aliphatic polyester type (meth)acrylates, aromatic polyester type (meth)acrylates, etc.], (poly)urethane (meth)acrylates [polyester type urethane (meth)acrylates, polyether type urethane (meth)acrylates, etc.], and organosilicon (meth)acrylates.

[0062] These photocurable compounds can be used alone or in combination of two or more. Among these, photocurable compounds that can cure in a short time are preferred, such as ultraviolet-curable compounds (monomers, oligomers, optionally low molecular weight resins, etc.) and EB-curable compounds. In particular, ultraviolet-curable compounds (resin precursor components) are advantageous for practical use. Furthermore, in order to improve scratch resistance and other resistance properties, photocurable compounds are preferably compounds having 2 or more polymerizable unsaturated bonds in their molecules (preferably 2 to 6, more preferably about 2 to 4).

[0063] The weight-average molecular weight of the cured resin precursor component is not particularly limited. Considering the compatibility with the polymer, in gel permeation chromatography (GPC), it is converted to polystyrene and is, for example, 5000 or less, preferably 2000 or less, and more preferably about 1000 or less.

[0064] To improve the transparency and anti-glare properties of the anti-glare film, the precursor components of the cured resin may contain fillers and / or fluorine atoms, depending on their type.

[0065] As fillers, they can contain inorganic particles such as silica particles, titanium dioxide particles, zirconium oxide particles, and alumina particles, as well as organic particles such as cross-linked (meth)acrylic acid polymer particles and cross-linked styrene resin particles. These fillers can be used alone or in combination of two or more.

[0066] Among these fillers, nano-sized silica particles (silica nanoparticles) are preferred due to their excellent optical properties and ease of forming uneven shapes that balance transparency and anti-glare properties through helix decomposition. Solid silica nanoparticles are preferred to suppress the yellowing of the anti-glare film. Furthermore, the average particle size of the silica nanoparticles is, for example, 1-800 nm, preferably 3-500 nm, and more preferably around 5-300 nm.

[0067] The proportion of filler (especially silica nanoparticles) relative to the overall curing resin precursor components can be about 10 to 90% by weight, for example, 10 to 80% by weight, preferably 15 to 70% by weight, and even more preferably about 20 to 50% by weight.

[0068] As precursor components containing fluorine atoms (fluorinated curable compounds or fluorinated compounds with polymerizable groups), examples include fluorinated monomers and oligomers such as fluoroalkyl methacrylates [e.g., perfluorooctyl ethyl methacrylate, trifluoroethyl methacrylate, etc.], fluorinated (poly)oxyalkylene glycol di(meth)acrylates [e.g., fluoroethylene glycol di(meth)acrylate, fluoropolyethylene glycol di(meth)acrylate, fluoropropylene glycol di(meth)acrylate, etc.], fluorinated epoxy resins, fluorinated urethane resins, etc. Among these, fluorinated polyether compounds having (meth)acryloyl groups are preferred. Fluorinated curable compounds can also be commercially available fluorinated polymerizable leveling agents.

[0069] The precursor component of the curing resin may further contain a curing agent, depending on its type. For example, thermosetting resins may contain curing agents such as amines and polycarboxylic acids, while photocurable resins may contain photopolymerization initiators. Commonly used photopolymerization initiators include acetophenones, benzoyl groups, benzoin groups, benzophenones, thioxanones, and phosphine oxides. The proportion of the photopolymerization initiator or other curing agent relative to the total precursor component of the curing resin is, for example, 0.1 to 20% by weight, preferably 0.5 to 10% by weight, and more preferably about 1 to 8% by weight.

[0070] The precursor components of the curing resin may further contain curing accelerators. For example, photocurable resins may contain photocuring accelerators, such as tertiary amines (dialkylaminobenzoates, etc.) and phosphine photopolymerization accelerators.

[0071] Among these curing resin precursor components, polyfunctional (meth)acrylates (such as dipentaerythritol hexa(meth)acrylate and other (meth)acrylates having about 2 to 8 polymerizable groups), epoxy (meth)acrylates, polyester (meth)acrylates, urethane (meth)acrylates, and organosilicon (meth)acrylates are preferred. Furthermore, the curing resin precursor components preferably contain silica nanoparticles and / or fluorine atoms, and particularly preferably contain photocurable compounds containing silica nanoparticles [especially polyfunctional (meth)acrylates containing silica nanoparticles, urethane (meth)acrylates containing silica nanoparticles, and organosilicon (meth)acrylates containing silica nanoparticles] and fluorinated curing compounds.

[0072] Preferred combinations of the precursor components for the curing resin include, for example, a combination of a photocurable compound containing silica nanoparticles and an organosilicon (meth)acrylate, a combination of urethane (meth)acrylate, 3-6 functional (meth)acrylate, an organosilicon (meth)acrylate and a fluorinated curable compound, a combination of a photocurable compound containing silica nanoparticles and a fluorinated curable compound, and a particularly preferred combination is a combination of a photocurable compound containing silica nanoparticles and a fluorinated curable compound.

[0073] In this invention, considering the ease of forming an uneven shape that balances transparency and anti-glare properties, it is preferable that the curing resin precursor component contains silica nanoparticles in order to achieve the aforementioned ratio of silica nanoparticles to the curing resin precursor component as a whole. Furthermore, the proportion of the fluorinated curable compound relative to the curing resin precursor component as a whole is, for example, 0.001 to 1% by weight (e.g., 0.01 to 0.5% by weight), preferably 0.02 to 0.3% by weight (e.g., 0.03 to 0.2% by weight), and more preferably approximately 0.05 to 0.1% by weight.

[0074] (Combination of polymer components and curing resin precursor components)

[0075] In this invention, at least two of the aforementioned polymer components and the aforementioned curing resin precursor components are used in a combination that causes phase separation between them near the processing temperature. Examples of combinations that cause phase separation include: (a) a combination incompatible with each other and undergoing phase separation; (b) a combination incompatible with the curing resin precursor component and undergoing phase separation; and (c) a combination incompatible with each other and undergoing phase separation. Among these combinations, (a) a combination of multiple polymer components, (b) a combination of the polymer component and the curing resin precursor component are generally preferred, and (a) a combination of multiple polymer components is particularly preferred. When the compatibility of the two components undergoing phase separation is high, they will not effectively separate during the drying process used to evaporate the solvent, thus reducing the function of the anti-glare layer.

[0076] It should be noted that the polymer component and the curing resin precursor component are generally incompatible. When the polymer component and the curing resin precursor component are incompatible and phase separation occurs, multiple polymer components can be used. When using multiple polymer components, at least one polymer component only needs to be incompatible with the curing resin precursor component, while the other polymer components can be compatible with the aforementioned curing resin precursor component. Alternatively, a combination of two incompatible polymer components and the curing resin precursor component (especially monomers or oligomers having multiple curable functional groups) can also be used.

[0077] When phase separation occurs due to the polymer composition consisting of multiple incompatible polymer components, the curing resin precursor component can be used in a combination that is compatible with at least one of the incompatible polymer components near the processing temperature. That is, for example, in the case where the polymer composition consists of multiple incompatible polymer components consisting of a first polymer and a second polymer, the curing resin precursor component can be compatible with either the first polymer or the second polymer, or it can be compatible with both polymer components, but is more preferably compatible with only one polymer component. When compatible with both polymer components, phase separation will occur, resulting in at least two phases: a mixture primarily composed of the first polymer and the curing resin precursor component, and a mixture primarily composed of the second polymer and the curing resin precursor component.

[0078] When the selected polymer components have high compatibility, they will not effectively separate from each other during the drying process used to evaporate the solvent, thus reducing the function of the anti-glare layer. The phase separation of multiple polymer components can be easily determined by the following operation: prepare a homogeneous solution using a solvent that is a good solvent for both components, and visually confirm whether the remaining solid components are cloudy during the slow evaporation of the solvent.

[0079] Furthermore, the refractive indices of the cured or crosslinked resin formed by curing the polymer components and the curing resin precursor components are usually different. Additionally, the refractive indices of the various polymer components (first polymer and second polymer) are also different. The difference in refractive index between the polymer component and the cured or crosslinked resin, and the difference in refractive index between the various polymer components (first polymer and second polymer), can be, for example, 0.001 to 0.2, preferably around 0.05 to 0.15.

[0080] The ratio (by weight) of the polymer component to the curing resin precursor component is not particularly limited and can be selected from, for example, a range of approximately 1 / 99 to 95 / 5, such as 2 / 98 to 90 / 10, preferably 3 / 97 to 80 / 20, and more preferably approximately 5 / 95 to 70 / 30. Furthermore, when the curing resin precursor component contains a photocurable compound containing silica nanoparticles, the above ratio can be, for example, 2 / 98 to 30 / 70, preferably 3 / 97 to 20 / 80, and more preferably approximately 5 / 95 to 15 / 85. Moreover, when the curing resin precursor component does not contain a photocurable compound containing silica nanoparticles, the above ratio can be, for example, 10 / 90 to 60 / 40, preferably 20 / 80 to 50 / 50, and more preferably approximately 30 / 70 to 40 / 60.

[0081] (Other ingredients)

[0082] The anti-glare layer formed from a composition containing resin components can 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, tackifiers, defoamers, etc. The total proportion of these additives relative to the overall anti-glare layer is, for example, about 0.01 to 10% by weight (particularly preferably 0.1 to 5% by weight).

[0083] (Thickness of the anti-glare layer)

[0084] The thickness (average thickness) of the anti-glare layer can be, for example, about 0.3 to 20 μm, preferably about 1 to 15 μm (e.g., 1 to 10 μm), and typically about 3 to 12 μm (especially about 4 to 10 μm). It should be noted that when the anti-glare layer constitutes the anti-glare film alone, the thickness (average thickness) of the anti-glare layer is, for example, about 1 to 100 μm, preferably about 3 to 50 μm.

[0085] (Transparent substrate layer)

[0086] The transparent substrate layer can be formed of a transparent material, which can be selected according to the application. It can also be an inorganic material such as glass, but organic materials are commonly used from the perspectives of strength and formability. Examples of organic materials include cellulose derivatives, polyesters, polyamides, polyimides, polycarbonates, and (meth)acrylic polymers. Among these, cellulose esters and polyesters are commonly used.

[0087] Examples of cellulose esters include cellulose triacetate (TAC), cellulose acetate, cellulose acetate propionate, and cellulose acetate butyrate. 3-4 Examples of polyesters include cellulose acids, etc. Examples of polyesters include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and other polyarylates.

[0088] Among these, considering the excellent balance of mechanical properties and transparency, PET and PEN are preferred polycarbonate materials. 2-4 Aryl alkylene esters.

[0089] The transparent substrate layer may also contain the conventional additives exemplified in the section on anti-glare layers. The proportions of the additives are also the same as those in the anti-glare layer.

[0090] The transparent substrate layer can be a unidirectional or bidirectional stretched film, but considering its low birefringence and excellent optical isotropy, it can also be an unstretched film.

[0091] The transparent substrate layer may have undergone surface treatment (such as corona discharge treatment, flame treatment, plasma treatment, ozone treatment, ultraviolet irradiation treatment, etc.) and may also have an easy-to-adhere layer.

[0092] The thickness (average thickness) of the transparent substrate layer is, for example, 5 to 2000 μm, preferably 15 to 1000 μm, and more preferably about 20 to 500 μm.

[0093] (Adhesive layer)

[0094] The anti-glare film of the present invention can be used as a protective film for various touch panel display devices, including smartphones, PCs (tablet PCs, etc.). In these applications, an adhesive layer may also be formed on at least a portion of the other side of the aforementioned transparent substrate layer.

[0095] The adhesive layer is formed by a conventional transparent adhesive. Examples of adhesives include rubber-based adhesives, acrylic adhesives, olefin-based adhesives (modified olefin-based adhesives, etc.), and silicone adhesives. Among these adhesives, silicone adhesives are preferred considering optical properties and reworkability.

[0096] The thickness (average thickness) of the adhesive layer is, for example, 1 to 150 μm, preferably 10 to 100 μm, more preferably 20 to 70 μm (particularly preferably 25 to 50 μm).

[0097] The adhesive layer can be formed entirely on the other side of the aforementioned transparent substrate layer, or it can be formed on a portion of the other side (e.g., the periphery). Furthermore, when formed on the periphery, to improve the processability for bonding, a frame-like member (e.g., a plastic sheet laminated on the periphery) can be formed on the periphery of the anti-glare film, and the adhesive layer can be formed on the frame-like member.

[0098] [Manufacturing method of anti-glare film]

[0099] The manufacturing method of the anti-glare film of the present invention is not particularly limited, and can be appropriately selected according to the type of material. It can be formed by physical processing, transfer using a mold, etc. However, from the perspective of productivity, it is preferable to manufacture it by a curing process in which the curable composition is cured by heat or active energy rays. In particular, for anti-glare films comprising an anti-glare layer having an uneven shape formed by wet swirl decomposition, it can be a method in which the following steps are performed: coating a curable composition containing one or more polymer components and one or more curing resin precursor components onto a support (especially a transparent substrate layer) and drying it, thereby causing at least two components selected from the polymer components and curing resin precursor components to undergo phase separation by wet swirl decomposition; and a curing process in which the curable composition after phase separation is cured by heat or active energy rays.

[0100] In the phase separation process, the curable composition may contain a solvent. The solvent can be selected based on the type and solubility of the polymer components and the curing resin precursor components, as long as it is a solvent capable of uniformly dissolving the solid components (e.g., various polymer components and curing resin precursor components, reaction initiators, other additives). In particular, the phase separation structure can be controlled by adjusting the solubility of the solvent in the polymer components and the curing resin precursor. Examples of such solvents include ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.) and ethers (diethyl ethyl ketone, methyl ethyl ketone, cyclohexanone, etc.). The solvents include alkanes, tetrahydrofurans, aliphatic hydrocarbons (hexane, etc.), alicyclic hydrocarbons (cyclohexane, etc.), aromatic hydrocarbons (toluene, xylene, etc.), halogenated hydrocarbons (dichloromethane, dichloroethane, etc.), esters (methyl acetate, ethyl acetate, butyl acetate, etc.), water, alcohols (ethanol, isopropanol, butanol, cyclohexanol, etc.), cellosols [methyl cellosol, ethyl cellosol, propylene glycol monomethyl ether (1-methoxy-2-propanol), etc.], acetic acid cellosols, sulfoxides (dimethyl sulfoxide, etc.), and amides (dimethylformamide, dimethylacetamide, etc.). Additionally, solvents can also be mixed solvents.

[0101] Among these solvents, solvents containing ketones such as methyl ethyl ketone are preferred, and mixed solvents of ketones and alcohols (such as butanol) and / or solvents (such as 1-methoxy-2-propanol) are particularly preferred. In the mixed solvent, the proportion of alcohols and / or solvents (total amount when both are mixed) relative to 100 parts by weight of ketones is, for example, about 10 to 150 parts by weight, preferably 15 to 100 parts by weight, more preferably 20 to 80 parts by weight (particularly preferably 25 to 50 parts by weight). When alcohols and solvents are combined, the proportion of solvents relative to 100 parts by weight of alcohols is, for example, about 1 to 100 parts by weight, preferably 10 to 80 parts by weight, more preferably 30 to 70 parts by weight (particularly preferably 40 to 60 parts by weight). In this invention, by appropriately combining solvents, phase separation based on spiking line decomposition can be adjusted, and an uneven shape that balances transparency and anti-glare properties can be formed.

[0102] The concentration of the solute (polymer component, curing resin precursor component, reaction initiator, other additives) in the mixture can be selected within a range that does not impair phase separation and the properties of casting and coating, for example, 1 to 80% by weight, preferably 10 to 70% by weight, more preferably 20 to 60% by weight (particularly preferably about 30 to 55% by weight).

[0103] Commonly used coating methods include roller coating, air knife coating, doctor blade coating, bar coating, reverse coating, wire rod coating, corner wheel coating, dip-squeeze coating, die coating, gravure coating, micro-gravure coating, screen coating, dip coating, spray coating, and spin coating. Among these methods, wire rod coating and gravure coating are commonly used. It should be noted that, depending on the requirements, the coating solution can be applied multiple times.

[0104] After the above mixture is cast or coated, phase separation based on spinoline decomposition can be induced by evaporating the solvent at a temperature lower than the boiling point of the solvent (e.g., 1-120°C, preferably 5-50°C, and particularly preferably about 10-50°C lower). The solvent evaporation can typically be carried out by drying, for example, at a temperature corresponding to the boiling point of the solvent, for example, around 30-200°C (e.g., 30-100°C), preferably 40-120°C, further preferably 50-90°C (particularly preferably 60-85°C).

[0105] The decomposition of spinolines that occurs with the evaporation of such solvents can impart order or periodicity to the average distances between domains in a phase-separated structure.

[0106] In the curing process, the dried curable composition is ultimately cured by utilizing active light (ultraviolet light, electron beams, etc.) and heat, which can immediately fix the phase separation structure formed by the decomposition of the spinolines. The curing of the curable composition can be achieved by combining heating, light irradiation, etc., depending on the type of precursor component of the curing resin.

[0107] The heating temperature can be selected from an appropriate range, such as around 50~150℃. The light source can be selected according to the type of light-curing component, and ultraviolet light or electron beams are commonly used. The most commonly used light source is an ultraviolet irradiation device.

[0108] As a light source, for example in the case of ultraviolet light, Deep UV lamps, low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, halogen lamps, and laser light sources (helium-cadmium lasers, excimer lasers, etc.) can be used. The amount of light irradiated (irradiation energy) varies depending on the thickness of the coating, for example, from 10 to 10000 mJ / cm². 2 The preferred value is 20~5000mJ / cm. 2 Further preferably, it is 30~3000mJ / cm 2 Left and right. Depending on the need, illumination can also be carried out in an inert gas atmosphere.

[0109] [Display device]

[0110] The anti-glare film of the present invention can balance transparency and anti-glare properties, and therefore can be used as an optical component in various display devices, such as liquid crystal displays (LCDs), organic EL displays, and display devices with touch panels. In particular, it is useful as an optical element for LCDs and organic EL displays.

[0111] In detail, the LCD can be a reflective LCD that uses external light to illuminate a display unit equipped with liquid crystal cells, or a transmissive LCD that has a backlight unit for illuminating the display unit. In a reflective LCD, incident light from the outside can be introduced through the display unit, and the transmitted light passing through the display unit can be reflected by a reflective member to illuminate the display unit. In a reflective LCD, the anti-glare film of the present invention can be disposed in the optical path located in front of the aforementioned reflective member. For example, the anti-glare film of the present invention can be disposed or laminated on the front surface (viewable front surface) of the display unit, etc., and in particular, it can be disposed on the front surface of an LCD that has a collimating backlight unit and does not have a prism sheet.

[0112] In transmissive LCDs, the backlight unit may include a light guide plate (e.g., a wedge-shaped light guide plate) for allowing light from a light source (such as a tubular light source like a cold cathode tube, or a point light source like a light-emitting diode) to enter from one side and exit from an exit surface on the front surface. Additionally, a prism sheet may be provided on the front surface of the light guide plate as needed. It should be noted that a reflective member is typically provided on the back of the light guide plate for reflecting light from the light source towards the exit surface. In such transmissive LCDs, the anti-glare film of the present invention can typically be provided within the light path located in front of the light source. For example, the anti-glare film of the present invention can be provided between the light guide plate and the display unit, or on the front surface of the display unit.

[0113] In organic EL displays, each pixel of an organic EL contains a light-emitting element, which is typically formed from a substrate such as a metal cathode, an electron injection layer, an electron transport layer, a light-emitting layer, a hole transport layer, a hole injection layer, an indium tin oxide (ITO) anode, a glass plate, or a transparent plastic plate. In organic EL displays, the anti-glare film of this invention can be disposed within the optical path.

[0114] In addition, the anti-glare film of the present invention can be used as an aftermarket protective film for preventing damage to LCDs (including LCDs that are also display devices with touch panels) and organic EL displays (including organic EL displays that are also display devices with touch panels).

[0115] Example

[0116] The present invention will now be described in more detail based on embodiments, but the invention is not limited to these embodiments. The raw materials used in the embodiments and comparative examples are as described below, and the obtained anti-glare films were evaluated by the following methods.

[0117] [raw material]

[0118] Acrylic polymers with polymerizable groups: "CYCLOMER P" manufactured by DAICEL ALLNEX Co., Ltd.

[0119] Cellulose acetate propionate: EASTMAN "CAP-482-20", degree of acetylation = 2.5%, degree of propionylation = 46%, number average molecular weight converted from polystyrene 75,000.

[0120] Organosilicon acrylate: DAICEL ALLNEX Co., Ltd., "EB1360"

[0121] Silicone-based hard coating material: "AS-201S" manufactured by Tokushiki Co., Ltd.

[0122] Carbamate acrylate A: Manufactured by Shin-Nakamura Chemical Industry Co., Ltd., "U-15HA"

[0123] Urethane acrylate B: "AU-230" manufactured by Tokushiki Co., Ltd.

[0124] Dipentaerythritol hexaacrylate: "DPHA" manufactured by DAICEL ALLNEX Co., Ltd.

[0125] Acrylic UV-curable compound containing nano-silica: MOMENTIVE PERFORMANCE MATERIALS JAPAN, Ltd., "XR39-C6210"

[0126] Acrylic UV-curable compound containing silica: "Z-757-4RL" manufactured by Agk Industries, Ltd.

[0127] Acrylic UV-curable compounds: Agk Industries, Ltd., "Z-757-4CL"; PMMA beads A: Sekisui Chemicals, Ltd., "SSX-115".

[0128] PMMA Beads B: SSX-105 manufactured by Sekisui Chemicals Co., Ltd.

[0129] Cross-linked styrene beads: "SX-130H" manufactured by Soken Chemical Co., Ltd.

[0130] Fluorine compound A with polymerizable groups: Shin-Etsu Chemical Co., Ltd. "KY-1203"

[0131] Fluorine compounds B containing polymerizable groups: "FTERGENT 602A" manufactured by NEOS Co., Ltd.

[0132] Photoinitiator A: "IRGACURE 184" manufactured by BASF JAPAN Co., Ltd.

[0133] Photoinitiator B: "IRGACURE 907" manufactured by BASF JAPAN Co., Ltd.

[0134] Polyethylene terephthalate (PET) film: Manufactured by Mitsubishi Resin Co., Ltd., under the brand name "DIAFOIL".

[0135] Cellulose triacetate (TAC) membrane: "FUJITACT TG60UL" manufactured by FUJIFILM Co., Ltd.

[0136] [Coating thickness]

[0137] An optical film thickness gauge was used to measure the thickness at any 10 locations, and the average value was calculated.

[0138] [Through hue (b)] ＊ )]

[0139] The measurements were performed according to JIS Z8781 using a spectrophotometer (Hitachi High-Tech Science Co., Ltd. "U-3010").

[0140] [Diffuse Reflection Intensity]

[0141] An evaluation sample was prepared by attaching the back side of the anti-glare film (the side without unevenness or texture, the side opposite to the observer's side) to a flat, black acrylic sheet without unevenness or warping using a transparent adhesive. Next, the evaluation sample was placed in a measuring apparatus, and a light beam was incident on the anti-glare film side of the sample at an angle of 45 degrees to the normal to the surface. The 45-degree angle, which is the specular reflection direction of the incident light, was defined as the diffuse specular reflection direction, and the reflection intensity in the diffuse specular reflection direction was defined as R. For the light beam incident on the anti-glare film surface of the evaluation sample and diffusely reflected, the diffuse reflection intensity was measured by scanning the receiver for every 1 degree within a range of -45 degrees to +45 degrees relative to the diffuse specular reflection direction, and the sum was defined as V. The apparatus used for measuring the diffuse reflection intensity was a "GP-200" manufactured by Murakami Color Research Institute Co., Ltd.

[0142] [Haze]

[0143] Measurements were performed using a haze meter (NDH-5000W, manufactured by Nippon Denshoku Co., Ltd.) in accordance with JIS K7136, with the surface having an uneven structure on the receiver side.

[0144] [60-degree gloss]

[0145] According to JIS K7105, the gloss was measured at an angle of 60 degrees using a gloss meter (IG-320 manufactured by Hikuba Manufacturing Co., Ltd.).

[0146] [Anti-glare]

[0147] The anti-glare film was applied to a commercially available black acrylic sheet using optical paste. The reflection images under three-wavelength fluorescent lamps were visually observed to confirm the results, and the results were evaluated according to the following criteria.

[0148] ◎: Fluorescent lamps are completely invisible

[0149] ○: The outline of the fluorescent lamp is blurred.

[0150] △: The shape of the fluorescent lamp can be observed, but the glare is suppressed.

[0151] [tone]

[0152] The anti-glare film was oriented towards a three-wavelength fluorescent lamp, and the hue of its transmitted light was observed with the naked eye. It was then evaluated according to the following criteria.

[0153] ○: When observing the membrane through a fluorescent lamp, it appears colorless and transparent.

[0154] △: A slight yellowish or bluish tint was observed.

[0155] ×: Yellow or blue is clearly observed.

[0156] [Example 1]

[0157] A solution was prepared by dissolving 15.0 parts by weight of an acrylic polymer with polymerizable groups, 3 parts by weight of cellulose acetate propionate, 150 parts by weight of an acrylic UV-curable compound containing nano-silica, and 1 part by weight of an organosilicon acrylate in a mixed solvent of 101 parts by weight of methyl ethyl ketone and 24 parts by weight of 1-butanol.

[0158] After casting the solution onto the PET film using a wire rod (#20), it was placed in an oven at 80°C for 1 minute to allow the solvent to evaporate, forming a coating with a thickness of approximately 9 μm.

[0159] Then, the coating is irradiated with ultraviolet light for about 5 seconds using a high-pressure mercury lamp (accumulating a light intensity of about 100 mJ / cm). 2The coating was subjected to ultraviolet curing treatment under ultraviolet light (the same below) to obtain an anti-glare film.

[0160] [Example 2]

[0161] A solution was prepared by dissolving 12.5 parts by weight of an acrylic polymer with polymerizable groups, 4 parts by weight of cellulose acetate propionate, 150 parts by weight of an acrylic UV-curable compound containing nano-silica, and 1 part by weight of an organosilicon acrylate in a mixed solvent of 81 parts by weight of methyl ethyl ketone, 24 parts by weight of 1-butanol, and 13 parts by weight of 1-methoxy-2-propanol.

[0162] After casting the solution onto the PET film using a wire rod (#20), it was placed in an oven at 80°C for 1 minute to allow the solvent to evaporate, forming a coating with a thickness of approximately 9 μm.

[0163] Then, the coating was irradiated with ultraviolet light for about 5 seconds using a high-pressure mercury lamp to perform ultraviolet curing treatment, thus obtaining the anti-glare film.

[0164] [Example 3]

[0165] A solution was prepared by dissolving 45.6 parts by weight of an acrylic polymer with polymerizable groups, 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 parts by weight of a fluorinated compound B with polymerizable groups, 1 part by weight of photoinitiator A, and 1 part by weight of photoinitiator B in a mixed solvent of 128 parts by weight of methyl ethyl ketone, 25 parts by weight of 1-butanol, and 31 parts by weight of cyclohexanone.

[0166] After casting the solution onto the TAC film using a wire rod (#16), it was placed in an oven at 80°C for 1 minute to allow the solvent to evaporate, forming a coating with a thickness of approximately 7 μm.

[0167] Then, the coating was irradiated with ultraviolet light for about 5 seconds using a high-pressure mercury lamp to perform ultraviolet curing treatment, thus obtaining the anti-glare film.

[0168] [Example 4]

[0169] A solution was prepared by dissolving 12.5 parts by weight of an acrylic polymer with polymerizable groups, 5.5 parts by weight of cellulose acetate propionate, 149 parts by weight of an acrylic UV-curable compound containing nano-silica, and 0.1 parts by weight of a fluorine compound B with polymerizable groups in a mixed solvent of 129 parts by weight of methyl ethyl ketone, 24 parts by weight of 1-butanol, and 13 parts by weight of 1-methoxy-2-propanol.

[0170] After casting the solution onto the PET film using a wire rod (#14), place it in an oven at 80°C for 1 minute to allow the solvent to evaporate, forming a coating with a thickness of approximately 5 μm.

[0171] Then, the coating was irradiated with ultraviolet light for about 5 seconds using a high-pressure mercury lamp to perform ultraviolet curing treatment, thus obtaining the anti-glare film.

[0172] [Example 5]

[0173] A solution was prepared by dissolving 36.9 parts by weight of an acrylic polymer with polymerizable groups, 3.0 parts by weight of cellulose acetate propionate, 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, 0.1 parts by weight of a fluorine compound A with polymerizable groups, 1 part by weight of photoinitiator A, and 1 part by weight of photoinitiator B in a mixed solvent of 144 parts by weight of methyl ethyl ketone and 21 parts by weight of 1-butanol.

[0174] After casting the solution onto the TAC film using a wire rod (#18), it was placed in an oven at 80°C for 1 minute to allow the solvent to evaporate, forming a coating with a thickness of approximately 8 μm.

[0175] Then, the coating was irradiated with ultraviolet light for about 5 seconds using a high-pressure mercury lamp to perform ultraviolet curing treatment, thus obtaining the anti-glare film.

[0176] [Example 6]

[0177] A solution was prepared by dissolving 50 parts by weight of an acrylic polymer with polymerizable groups, 4 parts by weight of cellulose acetate propionate, 76 parts by weight of urethane acrylate A, 1 part by weight of silicone acrylate, 1 part by weight of photoinitiator A, and 1 part by weight of photoinitiator B in a mixed solvent of 176 parts by weight of methyl ethyl ketone and 28 parts by weight of 1-butanol.

[0178] After casting the solution onto the TAC film using a wire rod (#18), it was placed in an oven at 80°C for 1 minute to allow the solvent to evaporate, forming a coating with a thickness of approximately 8 μm.

[0179] Then, the coating was irradiated with ultraviolet light for about 5 seconds using a high-pressure mercury lamp to perform ultraviolet curing treatment, thus obtaining the anti-glare film.

[0180] [Example 7]

[0181] A solution was prepared by dissolving 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 in a mixed solvent of 277 parts by weight of methyl ethyl ketone and 23 parts by weight of 1-butanol.

[0182] After casting the solution onto the PET film using a wire rod (#6), place it in an oven at 80°C for 1 minute to allow the solvent to evaporate, forming a coating with a thickness of approximately 1 μm.

[0183] Then, the coating was irradiated with ultraviolet light for about 5 seconds using a high-pressure mercury lamp to perform ultraviolet curing treatment, thus obtaining the anti-glare film.

[0184] [Example 8]

[0185] A solution was prepared by mixing 50 parts by mass of a silica-containing acrylic UV-curable compound and 150 parts by mass of an acrylic UV-curable compound. The solution was cast onto a PET film using a wire rod (#14), and then placed in an oven at 80°C for 1 minute to allow the solvent to evaporate, forming a coating approximately 7 μm thick.

[0186] Then, the coating is irradiated with ultraviolet light for about 5 seconds to perform ultraviolet curing treatment, thus obtaining the anti-glare film.

[0187] [Reference Example 1]

[0188] A solution was prepared by dissolving 39 parts by weight of urethane acrylate B, 15.7 parts by weight of silicone hard coating material, 0.3 parts by weight of PMMA beads A, and 6.1 parts by weight of crosslinked styrene beads in 38 parts by weight of methyl ethyl ketone.

[0189] After casting the solution onto the PET film using a wire rod (#14), it was placed in an oven at 100°C for 1 minute to allow the solvent to evaporate, forming a coating with a thickness of approximately 6 μm.

[0190] Then, the coating was irradiated with ultraviolet light for about 5 seconds using a high-pressure mercury lamp to perform ultraviolet curing treatment, thus obtaining the anti-glare film.

[0191] The evaluation results of the anti-glare films obtained in the examples and reference examples are shown in Table 1.

[0192]

[0193] The results in Table 1 clearly show that the anti-glare film of the embodiment has high anti-glare performance and excellent color tone (colorless transparency).

[0194] Industrial applicability

[0195] The anti-glare film of the present invention can be used in various display devices, such as LCDs, cathode ray tube displays, organic or inorganic EL displays, field emission displays (FEDs), surface electric field displays (SEDs), rear projection television displays, plasma displays, display devices with touch panels, and other display devices.

[0196] Furthermore, the anti-glare film of the present invention can be adapted to screens of various sizes, and can be used in display devices with small or portable screens (e.g., displays for car navigation systems, game consoles, smartphones, tablet PCs, and display devices with touch panels), medium-sized screens (e.g., laptop or portable PCs, desktop PCs, televisions), and large screens (e.g., digital signage). The appropriate choice can be made based on the resolution, but considering both transparency and anti-glare properties, it is suitable for display devices with medium or large screens.

[0197] In addition, anti-glare films containing curing resin precursor components also have excellent scratch resistance, so they can also be used as aftermarket protective films for LCDs and organic EL displays.

Claims

1. An anti-glare film, wherein the ratio of diffuse specular reflection intensity R to the sum of diffuse reflection intensity V, R / V, is 0.01~0.12, and the chromaticity b of the transmitted light is... ＊ The absolute value is less than 3. In the formula R / V, The diffuse specular reflection intensity R is the diffuse reflection intensity measured using a variable angle photometer with an aperture angle of 1 degree when visible light is shone onto the surface of the anti-glare film at an angle of 45 degrees relative to the normal, along the diffuse reflection direction. The sum of diffuse reflection intensity V is the diffuse reflection direction relative to the surface of the object being measured, which is facing the anti-glare film, when illuminated with visible light at an angle of 45 degrees relative to the normal. It is the sum of diffuse reflection intensity measured with an aperture angle of 1 degree using a variable angle photometer for every 1 degree from -45 degrees to +45 degrees, including 0 degrees. in, The anti-glare film includes a transparent substrate layer and an anti-glare layer formed on at least one side of the transparent substrate layer. The anti-glare layer is a cured product of a curable composition containing one or more curable resin precursor components. The cured resin precursor contains silica nanoparticles. Furthermore, the proportion of silica nanoparticles is 10 to 90% by weight relative to the total curing resin precursor component.

2. The anti-glare film according to claim 1, wherein, The curable composition further contains one or more polymer components.

3. The anti-glare film according to claim 2, wherein, At least two components selected from the polymer component and the cured resin precursor component are capable of phase separation via wet cycloid decomposition.

4. The anti-glare film according to claim 2 or 3, wherein, The polymer component contains cellulose esters and / or optionally (meth)acrylic polymers with polymerizable groups.

5. The anti-glare film according to any one of claims 1 to 3, wherein, The precursor component of the cured resin contains at least one selected from polyfunctional (meth)acrylates, epoxy (meth)acrylates, polyester (meth)acrylates, urethane (meth)acrylates, and organosilicon (meth)acrylates.

6. The anti-glare film according to any one of claims 1 to 3, wherein, The precursor components of the cured resin further contain fluorine atoms.

7. A method for manufacturing an anti-glare film, comprising the method of manufacturing the anti-glare film according to any one of claims 1 to 6, the method comprising: A curing process in which a curable composition is cured by heat or active energy rays.

8. The method for manufacturing the anti-glare film according to claim 7, further comprising: A phase separation process involves coating a support with a curable composition containing one or more polymer components and one or more curable resin precursor components, followed by drying, to allow at least two components selected from the polymer components and curable resin precursor components to undergo phase separation via wet cycloid decomposition. The curing process is a curing process that uses heat or active energy rays to cure a curable composition that has undergone phase separation.

9. A display device comprising an anti-glare film according to any one of claims 1 to 6.

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

11. A method for improving the anti-glare performance and transparency of an anti-glare film, the method comprising: R / V and the chromaticity b of transmitted light ＊ The absolute values ​​are adjusted to the ranges of -0.01 to 0.12 and below 3, respectively, to improve the anti-glare performance and transparency of the anti-glare film. The R / V ratio is the ratio of the diffuse specular reflection intensity R to the sum of the diffuse reflection intensity V. In the formula R / V, The diffuse specular reflection intensity R is the diffuse reflection intensity measured using a variable angle photometer with an aperture angle of 1 degree when visible light is shone onto the surface of the anti-glare film at an angle of 45 degrees relative to the normal, along the diffuse reflection direction. The sum of diffuse reflection intensity V is the diffuse reflection direction relative to the surface of the object being measured, which is facing the anti-glare film, when illuminated with visible light at an angle of 45 degrees relative to the normal. It is the sum of diffuse reflection intensity measured with an aperture angle of 1 degree using a variable angle photometer for every 1 degree from -45 degrees to +45 degrees, including 0 degrees. The anti-glare film comprises a transparent substrate layer and an anti-glare layer formed on at least one side of the transparent substrate layer. The anti-glare layer is a cured product of a curable composition containing one or more curable resin precursor components. The cured resin precursor contains silica nanoparticles. Furthermore, the proportion of silica nanoparticles is 10 to 90% by weight relative to the total curing resin precursor component.

Images