Substrate with antiglare layer, image display device, and method for producing substrate with antiglare layer

Abstract

The present invention has a substrate and an antiglare layer that is formed on the substrate directly or via another layer and that has a projection-recess structure on the surface. The antiglare layer is formed from a cured product of an antiglare coating forming composition that contains a polysiloxane having a fluorine-containing organic group.

Description

[Technical field]

[0001] The present invention relates to a substrate with an antiglare layer that has excellent antiglare properties (antiglare function) and provides good visibility without causing glare (sparkling), and to an image display device including the same, and a method for producing the substrate with an antiglare layer. [Background technology]

[0002] Image display devices (liquid crystal displays, organic electroluminescence displays, plasma displays, etc.) equipped in various devices such as televisions, personal computers, and smartphones may experience a reduction in image visibility when external light such as indoor lighting (fluorescent lights, etc.) or sunlight is reflected on the display surface.

[0003] One method for suppressing reflection of external light is to apply an anti-glare treatment to the display surface of an image display device. Proposed methods for anti-glare treatment include etching the surface of a transparent substrate such as glass with a chemical such as hydrofluoric acid (see Patent Document 1) and forming an organic anti-glare layer with an uneven surface (see Patent Document 2). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Patent No. 5839134 [Patent Document 2] International Publication No. 2018 / 070426 Summary of the Invention [Problem to be solved by the invention]

[0005] However, in the process of etching the surface of a glass substrate with chemicals, the danger of the chemicals becomes an issue, and in the process of forming an organic anti-glare layer on the surface, problems arise with the coatability onto the glass substrate and with the coatability and adhesion when forming an additional functional layer on the film.

[0006] Furthermore, with the recent trend towards higher definition image display devices, when an antiglare layer is disposed on the display surface side, there is a problem that a glare phenomenon in which random variations in light intensity appear on the surface is likely to occur.

[0007] In view of the above, the present invention aims to provide a substrate with an antiglare layer that is excellent in antiglare properties (antiglare function) and does not cause glare, providing good visibility, and an image display device equipped with the same.Furthermore, the present invention aims to provide a substrate with an antiglare layer that is excellent in coatability and adhesion when forming a functional layer, an image display device equipped with the same, and a method for manufacturing the substrate with an antiglare layer. [Means for solving the problem]

[0008] The inventors have found that the above object can be achieved by the following configuration, and have completed the present invention. The present invention relates to 1. A substrate with an antiglare layer, comprising: a substrate; and an antiglare layer formed on the substrate directly or via another layer, the antiglare layer having a concave-convex structure on the surface, the antiglare layer being formed from a cured product of a composition for forming an antiglare coating film containing a polysiloxane having a fluorine-containing organic group, the convex surface coverage being 5% to 70%. 2. The substrate with an antiglare layer according to 1, wherein the height of the convex portions of the concave-convex structure is 50 nm to 2,000 nm. 3. The substrate with an antiglare layer according to 1 or 2, wherein the haze of the antiglare layer is 0.3% to 40%. 4. The substrate with an antiglare layer according to any one of 1 to 3, wherein the refractive index of the antiglare layer is in the range of 1.3 to 1.49. 5. The substrate with an antiglare layer according to any one of 1 to 4, wherein the antiglare layer is formed on a high refractive index layer, and the refractive index of the high refractive index layer is higher than the refractive index of the antiglare layer. 6. The substrate with an antiglare layer according to 5, wherein the refractive index of the high refractive index layer is in the range of 1.5 to 2.1. 7. The substrate with an antiglare layer according to any one of 1 to 6, further comprising a functional layer formed on the antiglare layer. 8. An image display device comprising the substrate with an antiglare layer according to any one of 1 to 7. 9. A method for producing a substrate with an antiglare layer, comprising a step of applying a coating liquid for forming an antiglare coating film, which contains a polysiloxane having a fluorine-containing organic group, onto a substrate to form an antiglare layer; is located. Effect of the Invention

[0009] According to the present invention, it is possible to provide a substrate with an antiglare layer that has excellent antiglare properties (antiglare function) and does not cause glare (sparkling) and provides good visibility, and an image display device including the same. It is also possible to provide a substrate with an antiglare layer that is excellent in coatability and adhesion when forming a functional layer, an image display device including the same, and a method for manufacturing the substrate with an antiglare layer. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] The present invention will now be described in more detail.

[0011] <Composition for forming anti-glare coating layer> The antiglare forming composition used in the present invention contains at least a polysiloxane having a fluorine-containing organic group (hereinafter also referred to as component (A)), and further contains a solvent for dissolving this.

[0012] <Component (A)> Component (A) is a polysiloxane having an organic group substituted with a fluorine atom in the side chain. Such an organic group substituted with a fluorine atom is an organic group in which some or all of the hydrogen atoms of an aliphatic group or aromatic group are substituted with fluorine atoms. The organic group substituted with a fluorine atom is preferably an alkyl group in which some or all of the hydrogen atoms are substituted with fluorine atoms, an alkyl group containing an ether bond in which some or all of the hydrogen atoms are substituted with fluorine atoms, or an organic group containing a phenyl group in which some or all of the hydrogen atoms are substituted with fluorine atoms. The number of fluorine atoms in the organic group substituted with a fluorine atom is not particularly limited. The carbon number of the organic group substituted with a fluorine atom is preferably 1 to 20, more preferably 3 to 15, and particularly preferably 3 to 8. Specific examples of these include a trifluoropropyl group, a tridecafluorooctyl group, a heptadecafluorodecyl group, and a pentafluorophenylpropyl group.

[0013] Among these, from the viewpoint of facilitating the production of a highly transparent coating film, an organic group having a perfluoroalkyl group is preferred, and an organic group represented by the following formula (F) is more preferred. CF3(CF2) k CH2CH2-* (F) (In the formula, k is an integer of 0 to 12. * represents a bonding position.) Specific examples of the organic group represented by the above formula (F) include a trifluoropropyl group, a tridecafluorooctyl group, and a heptadecafluorodecyl group.

[0014] In the present invention, a plurality of types of polysiloxanes having side chains as described above may be used in combination.

[0015] There is no particular limitation on the method for obtaining the polysiloxane having the above-mentioned fluorine atom-substituted organic group on the side chain, but it is generally obtained by polycondensation of an alkoxysilane compound having the above-mentioned organic group on the side chain.

[0016] Among these, polysiloxanes obtained by polycondensation of an alkoxysilane component containing an alkoxysilane compound represented by formula (1) are preferred. R 11 Si(OR 12 )3(1)

[0017] Here, R in Equation (1) 11 represents the above-mentioned organic group substituted with a fluorine atom, but the number of fluorine atoms contained in this organic group is not particularly limited.

[0018] In addition, R in Eq. (1) 12 represents a hydrocarbon group having 1 to 5 carbon atoms, preferably a saturated hydrocarbon group having 1 to 5 carbon atoms, and more preferably a methyl group, an ethyl group, a propyl group, or a butyl group.

[0019] Among such alkoxysilanes represented by formula (1), R 11 is preferably a perfluoroalkyl group; 11 More preferred is an alkoxysilane in which the organic group is represented by the above formula (F).

[0020] Specific examples of alkoxysilanes having an organic group represented by formula (F) include trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane, tridecafluorooctyltrimethoxysilane, tridecafluorooctyltriethoxysilane, heptadecafluorodecyltrimethoxysilane, and heptadecafluorodecyltriethoxysilane.

[0021] In particular, from the viewpoint of facilitating the production of a highly transparent coating, it is preferable that k is an integer of 2 to 12.

[0022] In the present invention, at least one of the alkoxysilanes represented by formula (1) may be used, but multiple types may be used as necessary.

[0023] The polysiloxane having an organic group substituted with a fluorine atom in a side chain may be a polysiloxane obtained by polycondensation of an alkoxysilane component containing an alkoxysilane compound other than the alkoxysilane compound represented by the above formula (1) (hereinafter, also referred to as other alkoxysilane compounds). Specific examples of the other alkoxysilane compounds include at least one selected from the group consisting of alkoxysilane compounds represented by the following formula (2) and alkoxysilane compounds represented by the following formula (3), but are not limited thereto. Si(OR 2 )4(2) R 31 n Si(OR 32 ) 4-n (3) (In the formula, R 31 represents an organic group not substituted with a fluorine atom or a hydrogen atom, R 32 represents a hydrocarbon group having 1 to 5 carbon atoms, and n is an integer of 1 to 3.

[0024] R in Equation (2) 2 represents a hydrocarbon group, and since the fewer the carbon atoms, the higher the reactivity, a saturated hydrocarbon group having 1 to 5 carbon atoms is preferred, and a methyl group, ethyl group, propyl group, or butyl group is more preferred.

[0025] Specific examples of such tetraalkoxysilanes include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetrabutoxysilane, which are readily available as commercial products.

[0026] R in Equation (3) 32 R each independently represents a hydrocarbon group having 1 to 5 carbon atoms. 32 may be the same or different.

[0027] R in Equation (3) 31 R is preferably an organic group having 1 to 20 carbon atoms, and more preferably an organic group having 1 to 15 carbon atoms. 31may be the same or different. Examples of the organic group not substituted with a fluorine atom include an alkyl group having 1 to 18 carbon atoms, such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, or a stearyl group (octadecyl group); an alkenyl group having 2 to 18 carbon atoms, such as a vinyl group; a cycloalkyl group, such as a cyclohexyl group; an alkyl group containing a (meth)acryloxy group, such as a 3-(meth)acryloxypropyl group (γ-(meth)acryloxypropyl group); an alkyl group containing a hydroxyl group, such as a 3-hydroxypropyl group; and a γ-ureido(3-ureido)propyl group. ureido group-containing alkyl groups such as γ-amino(3-amino)propyl group, 2-aminoethylaminomethyl group, 3-(N-styrylmethyl-2-aminoethylamino)propyl group, etc.; epoxy group-containing alkyl groups such as γ-glycidoxy(3-glycidyloxy)propyl group, 2-(3,4-epoxycyclohexyl)ethyl group, etc.; mercapto group-containing alkyl groups such as γ-mercapto(3-mercapto)propyl group, etc.; isocyanate group-containing alkyl groups such as 3-isocyanatopropyl group, etc.; and aryl groups such as phenyl group, etc. Among these, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a heptyl group, an octyl group, a dodecyl group, a hexadecyl group, an octadecyl group, a phenyl group, a vinyl group, a γ-aminopropyl group, a γ-glycidoxypropyl group, and a γ-methacryloxypropyl group are more preferable.

[0028] Specific examples of such alkoxysilanes represented by formula (3) include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, pentyltrimethoxysilane, pentyltriethoxysilane, heptyltrimethoxysilane, heptyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, hexadecyltrimethoxysilane, hexadecyltriethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, Examples of the alkoxysilane include trialkoxysilanes such as 3-isocyanatepropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-ureidopropyltrimethoxysilane, and γ-ureidopropyltriethoxysilane, and dialkoxysilanes such as dimethyldimethoxysilane and dimethyldiethoxysilane, but are not limited thereto.

[0029] The total amount of the alkoxysilane compounds represented by formula (1) used is preferably 3 mol% or more, more preferably 5 mol% or more, based on 100 mol% of the total of the alkoxysilane compounds used to obtain component (A), from the viewpoint of facilitating the production of a coating film, and is preferably 40 mol% or less, more preferably 30 mol% or less, from the viewpoint of suppressing the production of gels or foreign matter.

[0030] The amount of the other alkoxysilane compounds used is preferably 97 mol% or less, more preferably 95 mol% or less, relative to the total of all alkoxysilane compounds used to obtain component (A), 100 mol%, and the lower limit is preferably 60 mol% or more, more preferably 70 mol% or more.

[0031] (Synthesis of Polysiloxane) The method for condensing the polysiloxane used in the present invention is not particularly limited, but may be, for example, a method in which an alkoxysilane is hydrolyzed and condensed in a solvent such as alcohol or glycol. In this case, the hydrolysis and condensation reaction may be either partial hydrolysis or complete hydrolysis. In the case of complete hydrolysis, theoretically, 0.5 times the molar amount of water is added to the total alkoxy groups in the alkoxysilane, but usually, an amount of water in excess of 0.5 times the molar amount is added.

[0032] In the present invention, the amount of water used in the above reaction can be appropriately selected as desired, but is usually 0.1 to 7 times by mole, and preferably 0.1 to 5 times by mole, the total alkoxy groups in the alkoxysilane.

[0033] In addition, for the purpose of promoting the hydrolysis and condensation reaction, acids such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid, formic acid, oxalic acid, and maleic acid; alkalis such as ammonia, methylamine, ethylamine, ethanolamine, and triethylamine; and metal salts such as hydrochloric acid, sulfuric acid, and nitric acid may be used as catalysts. In this case, the amount of catalyst used in the reaction is preferably about 0.001 to 0.1 times by mole, more preferably 0.01 to 0.06 times by mole, of the total alkoxy groups in the alkoxysilane. Furthermore, it is common to promote the hydrolysis and condensation reaction by heating a solution in which the alkoxysilane is dissolved. In this case, the heating temperature and heating time can be appropriately selected as desired, and the reaction is preferably performed in a closed container or under reflux for several tens of minutes to several tens of hours at a reaction system of 50°C to 180°C so that evaporation, volatilization, etc. of the liquid does not occur. For example, a method of heating and stirring at 50°C for 24 hours or heating and stirring under reflux for 2 to 10 hours can be mentioned.

[0034] Another method is, for example, a method of heating a mixture of alkoxysilane, solvent and oxalic acid. Specifically, oxalic acid is added to alcohol in advance to prepare an alcohol solution of oxalic acid, and then the solution is mixed with alkoxysilane and heated. In this case, the amount of oxalic acid is generally 0.2 to 2 moles per mole of the total alkoxy groups of the alkoxysilane, and is preferably 0.5 to 2 moles. In this method, heating can be performed at a liquid temperature of 50°C to 180°C, and is preferably performed for several tens of minutes to several tens of hours in a sealed container or under reflux so as not to cause evaporation or volatilization of the liquid.

[0035] In each of the above methods, when a plurality of alkoxysilanes are used, the plurality of alkoxysilanes may be mixed in advance or may be added sequentially.

[0036] When polycondensing alkoxysilanes using the above method, the concentration of the total amount of silicon atoms in the charged alkoxysilane converted into SiO2 (hereinafter referred to as SiO2 conversion concentration) is generally set to 20 mass% or less, preferably 15 mass% or less. By selecting any concentration within this concentration range, it is possible to suppress the formation of gel and obtain a homogeneous polysiloxane solution.

[0037] The solvent used in polycondensing alkoxysilane is not particularly limited as long as it dissolves the above-mentioned alkoxysilane compound. In general, alcohols or organic solvents having good compatibility with alcohols are used because alcohols are produced by the polycondensation reaction of alkoxysilane.

[0038] Specific examples of the solvent used in the polycondensation include alcohols such as methanol, ethanol, propanol, and n-butanol, and glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, and diethylene glycol monoethyl ether. In the present invention, a mixture of two or more of the above organic solvents may be used.

[0039] <Composition for forming anti-glare film> The method for preparing the coating liquid (hereinafter, simply referred to as coating liquid or coating liquid for forming antiglare coating film) which is the composition for forming antiglare coating film of the present invention is not particularly limited. As an example, the following solvent group (A), solvent group (B), and other solvent groups as necessary may be added to the polysiloxane solution obtained above. In addition, as necessary, a method of preparing the polysiloxane solution after concentrating it or replacing it with another solvent may be used.

[0040] <Solvent group (A)> The solvent group (A) contained in the coating liquid for forming an antiglare film of the present invention is at least one selected from glycol ethers and their derivatives or ketones having a boiling point of less than 160° C. Specific examples include glycol ethers and their derivatives such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, propylene glycol dimethyl ether, and propylene glycol diethyl ether, and ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone. Among these, from the viewpoint of coating stability, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, and methyl isobutyl ketone are preferred.

[0041] The content of the solvent group (A) in the coating solution for forming an antiglare coating film is 0.1 to 300 parts by mass, preferably 0.3 to 100 parts by mass, and particularly preferably 0.8 to 50 parts by mass, per part by mass of the total amount of silicon atoms contained in component (A) calculated as SiO2.

[0042] <Solvent group (B)> The solvent group (B) contained in the coating liquid for forming an antiglare film of the present invention is at least one selected from alcohols having a boiling point of 120° C. or less. Specific examples include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, and 2-methyl-2-propanol. Among these, from the viewpoint of storage stability of the composition, methanol, ethanol, 2-propanol, 2-butanol, and 2-methyl-1-propanol are preferred.

[0043] The content of the solvent group (B) in the coating liquid for forming an antiglare coating film is 0.5 to 500 parts by mass, preferably 1 to 200 parts by mass, and particularly preferably 2 to 150 parts by mass, per part by mass of the total amount of silicon atoms contained in component (A) calculated as SiO2.

[0044] <Other solvents> From the viewpoint of the stability of the coating solution, etc., the coating solution for forming an antiglare film of the present invention may contain solvents other than the solvent groups (A) and (B) (hereinafter also referred to as other solvents) as necessary.

[0045] Examples of other solvents include alcohols such as hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, and diacetone alcohol; glycols such as ethylene glycol, diethylene glycol, dipropylene glycol, 2-methyl-2,4-pentanediol, propanediol, butanediol, pentanediol, hexanediol, and heptanediol; ethylene glycol monobutyl ether, ethylene glycol dibutyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, and propylene glycol diisopropyl ether. Examples of the glycol ethers include diethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether; esters such as methyl acetate, ethyl acetate, and ethyl lactate; N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, γ-butyrolactone, dimethylsulfoxide, tetramethylurea, hexamethylphosphotriamide, m-cresol, and tetrahydrofuran.Among these, from the viewpoints of availability and storage stability of the composition, ethylene glycol, diethylene glycol, 2-methyl-2,4-pentanediol, propanediol, butanediol, ethylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, N-methyl-2-pyrrolidone, N,N-dimethylformamide, and tetrahydrofuran are preferably used.

[0046] The concentration of the total amount of silicon atoms contained in component (A) in the coating liquid for forming an antiglare film, calculated as SiO2 (SiO2 equivalent concentration), is preferably 0.2 to 10 mass %, more preferably 0.5 to 8 mass %.

[0047] <Other ingredients> In the present invention, other components than the component (A) and the solvent group (A) and (B), such as inorganic fine particles, metalloxane oligomers, metalloxane polymers, leveling agents, surfactants, etc. may be contained.

[0048] As the inorganic fine particles, silica fine particles, alumina fine particles, titania fine particles, magnesium fluoride fine particles, etc. are preferable, and a colloidal solution of these inorganic fine particles is particularly preferable. This colloidal solution may be one in which inorganic fine particle powder is dispersed in a dispersion medium, or may be a commercially available colloidal solution.

[0049] In the present invention, by incorporating inorganic fine particles, it becomes possible to impart a surface shape and other functions to the cured coating film to be formed. The inorganic fine particles preferably have an average particle size of 0.001 to 0.2 μm, more preferably 0.001 to 0.1 μm. If the average particle size of the inorganic fine particles exceeds 0.2 μm, the transparency of the cured coating film formed using the prepared coating liquid may decrease.

[0050] Examples of the dispersion medium for the inorganic fine particles include water and organic solvents. From the viewpoint of the stability of the coating solution for forming a coating film, the colloidal solution is preferably adjusted to have a pH or pKa of 1 to 10. More preferably, it is 2 to 7.

[0051] Examples of organic solvents used as the dispersion medium of the colloidal solution include alcohols such as methanol, ethanol, propanol, butanol, ethylene glycol, propylene glycol, butanediol, pentanediol, 2-methyl-2,4-pentanediol, diethylene glycol, dipropylene glycol, and ethylene glycol monopropyl ether; ketones such as methyl ethyl ketone and methyl isobutyl ketone; aromatic hydrocarbons such as toluene and xylene; amides such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone; esters such as ethyl acetate, butyl acetate, and γ-butyrolactone; and ethers such as tetrahydrofuran and 1,4-dioxane. Among these, alcohols and ketones are preferred. These organic solvents can be used as the dispersion medium alone or in combination of two or more.

[0052] The metalloxane oligomer or metalloxane polymer may be a precursor of a single or complex oxide of silicon, titanium, zirconium, aluminum, tantalum, antimony, bismuth, tin, indium, zinc, etc. The metalloxane oligomer or metalloxane polymer may be a commercially available product or may be obtained by a conventional method such as hydrolysis from a monomer such as a metal alkoxide, nitrate, hydrochloride, or carboxylate.

[0053] <Anti-glare layer and formation of anti-glare layer> The antiglare layer of the present invention can be obtained by applying the above-mentioned coating liquid for forming an antiglare film to a substrate and thermally curing the coating liquid. That is, the antiglare layer is made of a cured product of the polysiloxane having a fluorine-containing organic group contained in the coating liquid for forming an antiglare film.

[0054] Here, the antiglare layer has a concave-convex structure on its surface. The concave-convex structure is a fine concave-convex structure with a height of convex parts of 50 nm to 2,000 nm. The thickness of the entire antiglare layer is 50 nm to 3,000 nm, and the surface side of this antiglare layer has a fine concave-convex structure. That is, since the fine concave-convex structure is formed on a uniform and flat coating, it can also be expressed as convex parts being intermittently formed on a flat coating. In this case, the parts where no convex parts are formed are concave parts. The convex part surface coverage rate, which is the occupancy rate of the convex parts of the fine concave-convex structure, is 5% to 70%, preferably 10% to 60%.

[0055] Specifically, the above-mentioned convex surface coverage can be measured by the following method. That is, a white light interference optical microscope (ContourGT, manufactured by BRUKER) is used to measure the surface shape, and further shape analysis is performed. The surface shape measurement is performed using a high-density CCD camera in a VSI measurement method, with a zoom lens magnification of 0.55 times, an objective lens magnification of 50 times, a measurement area of ​​230 μm × 170 μm, a white light source, and light quantity and threshold under appropriate conditions that minimize noise in the measurement. Furthermore, as a shape analysis, after filtering with TermsRemoval (Cylinder and Tilt), the image is processed into a grayscale of 256 gradations. The above-mentioned convex surface coverage is measured at any point on the film surface, the processed image is divided into 1900, the brightness of the area is obtained, the area with high brightness is the convex part, and the area with low brightness and uniformity is the flat part, and the value calculated as convex part / flat part × 100 is the convex surface coverage of the film surface. The measurement was performed in an environment of 23°C and 30% RH.

[0056] From the viewpoint of obtaining an image display device with high visibility while suppressing glare, the antiglare layer preferably has a haze of 0.3% to 40%, more preferably 0.5% to 30%. In this specification and claims, the haze can be measured using a haze meter (Haze Meter HZ-V3, manufactured by Suga Test Instruments Co., Ltd.) in accordance with JIS K7163.

[0057] The flat coating portion and the fine uneven structure can be formed by one application, but the fine uneven structure can also be formed after the flat coating portion is formed. The coating liquid for forming the antiglare coating film forming the flat coating portion and the coating liquid for forming the fine uneven structure can be the same coating liquid, but the two coating liquids can be different. For example, the solid content composition of both is the same, but the solid content concentration of the coating liquid for forming the fine uneven structure can be higher than that of the flat coating portion, or the solid content composition of both can be different. Furthermore, the solid content composition of both is the same, but the solvent composition of both can be different, but is not limited thereto.

[0058] The fine unevenness structure may be formed on the surface by, for example, applying a coating liquid for forming an antiglare coating film and then blowing air on the surface before the coating liquid hardens, or by forming a flat coating portion and then spraying a coating liquid with a slightly higher concentration to form partial convex portions. Alternatively, the fine unevenness may be formed by adjusting the flow rate of the coating liquid for forming an antiglare coating film and the gas flow rate described below during spray application, but is not limited to these methods.

[0059] The refractive index of the antiglare layer is selected, for example, from the range of 1.3 to 1.49 from the viewpoint of suppressing reflected light.

[0060] The coating liquid for forming an antiglare coating to form an antiglare layer can be applied by any known or well-known method, such as dip coating, flow coating, spin coating, flexographic printing, inkjet coating, bar coating, gravure roll coating, roll coating, blade coating, air doctor coating, air knife coating, wire doctor coating, reverse coating, transfer roll coating, microgravure coating, kiss coating, cast coating, slot orifice coating, calendar coating, and die coating. However, the coating liquid for forming an antiglare coating of the present invention is characterized in that it is particularly suitable for the spray coating method.

[0061] Examples of the substrate include known or well-known substrates such as plastics, glass, ceramics, etc. Examples of plastics include plates and films of polycarbonate, poly(meth)acrylate, polyethersulfone, polyarylate, polyurethane, polysulfone, polyether, polyetherketone, trimethylpentene, polyolefin, polyethylene terephthalate, (meth)acrylonitrile, triacetyl cellulose, diacetyl cellulose, acetate butyrate cellulose, etc.

[0062] The uniform film thickness obtained by the spray coating method can be adjusted by the amount of chemical solution, the nozzle / stage distance (the distance between the nozzle and the stage), the coating speed, the gas flow rate or gas pressure, and the like.

[0063] The amount of the chemical solution is a parameter that determines the film thickness, and increasing the amount of the chemical solution makes the film thicker, and decreasing the amount of the chemical solution makes the film thinner. In spray coating, the amount of the chemical solution is, for example, 0.5 to 20 mL (milliliters) / min, and preferably 0.8 to 12 mL / min.

[0064] The gas flow rate is a parameter for forming fine droplets, and examples of the gas used include N2 and dry air, but are not limited to these. In spray coating, the gas flow rate is, for example, 3 to 70 L (liters) / min, and preferably 6 to 60 L / min. In the case of gas pressure, it is 30 to 700 kPa, and preferably 50 to 650 kPa.

[0065] In terms of forming fine irregularities, the gas flow rate is preferably 150 to 140,000 times, and more preferably 500 to 75,000 times, the flow rate of the coating liquid for forming an anti-glare coating film in the air, so that the coating liquid for forming an anti-glare coating film is applied to the surface of the substrate while micronizing the droplets of the coating liquid.

[0066] The nozzle / stage distance is a parameter related to the film thickness, the applicability, and the amount of coverage of the protrusions on the surface. For example, the film thickness increases as the distance decreases, but decreases as the distance increases. A preferred nozzle / stage distance is, for example, 30 to 200 mm, and more preferably 50 to 150 mm.

[0067] The coating speed is a parameter related to the film thickness and the amount of coating of the protrusions on the surface. For example, the faster the speed, the thinner the film thickness becomes, and the slower the speed, the thicker the film thickness becomes. In spray coating, the coating speed is, for example, 50 to 2000 mm / sec, and preferably 100 to 1500 mm / sec.

[0068] The thickness of the coating formed on the substrate can be adjusted by the above-mentioned parameters during coating, but can also be easily adjusted by the SiO2 equivalent concentration of the coating solution.

[0069] The coating film formed on the substrate is obtained by heating. In consideration of the heat resistance of the substrate, the baking temperature is preferably in the range of 80°C to 300°C, and more preferably in the range of 100°C to 250°C.

[0070] A high refractive index layer having a higher refractive index than the antiglare layer may be provided below the antiglare layer of the present invention. In this case, by appropriately adjusting the refractive indexes of the antiglare layer and the high refractive index layer, the reflected light reflected on the surface of the antiglare layer and the reflected light reflected on the surface of the high refractive index layer can be made to interfere in opposite phases, thereby further adding the effect of reducing the reflected light.

[0071] Here, the high refractive index layer is not particularly limited as long as it is a layer having a higher refractive index than the antiglare layer. However, in consideration of adhesion to the antiglare layer, it is preferable to use a cured product of a coating liquid containing a metal alkoxide and an alkoxysilane. For example, the coating disclosed in International Publication WO2012-057165 can be used.

[0072] The high refractive index layer disclosed in the above publication can be, for example, a film formed by applying and curing a coating liquid containing one or more of a metal alkoxide represented by the following formula (A), an alkoxysilane represented by the following formula (B), or a condensate thereof.

[0073] M1(OR 1 )n (A) (In the formula, M1 represents a metal such as silicon (Si), titanium (Ti), tantalum (Ta), zirconium (Zr), boron (B), aluminum (Al), magnesium (Mg), tin (Sn), and zinc (Zn); R 1 represents an alkyl group having 1 to 5 carbon atoms, and n represents the valence of M1. (R 102 ) n Si(OR 103 ) 4-n (B) (In the formula, R 102 R represents an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, or a heteroatom-containing group including a group having a heteroatom between the carbon-carbon of the alkyl group, the alkenyl group, the cycloalkyl group, and the aryl group. However, some or all of the hydrogen atoms of the alkyl group, the alkenyl group, the cycloalkyl group, the aryl group, and the heteroatom-containing group may be substituted with a substituent, and the alkyl group and the alkenyl group may have a cycloalkyl group or an aryl group in part. 103represents an alkyl group having 1 to 5 carbon atoms, and n represents an integer of 1 or 2.

[0074] Examples of the group having a hetero atom include groups having at least one atom selected from the group consisting of an oxygen atom, a nitrogen atom, and a sulfur atom, such as -O-, -NR- (R represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), -CO-, -S-, -CO-, and combinations thereof.

[0075] Examples of the substituent include halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, a cyano group, a nitro group, a hydroxyl group, an amino group, a ureido group, an isocyanate group and a mercapto group.

[0076] Representative examples of metal alkoxides represented by formula (A) when M1 is titanium include alkoxytitanium such as tetramethoxytitanium, tetraethoxytitanium, tetraisopropoxytitanium, tetra-n-propoxytitanium, tetra-n-butoxytitanium, tetraisobutoxytitanium, tetra-t-butoxytitanium, and tetrapentoxytitanium. When M1 is silicon, examples of the alkoxysilane include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetrabutoxysilane.

[0077] R in formula (B) 102Specific examples of the alkyl group include alkyl groups having 1 to 18 carbon atoms, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and stearyl groups; alkenyl groups, such as vinyl groups; cycloalkyl groups, such as cyclohexyl groups; alkyl groups containing (meth)acryloxy groups, such as 3-(meth)acryloxypropyl groups; halogen-containing alkyl groups, such as 3-chloropropyl, trifluoropropyl, tridecafluorooctyl, and heptadecafluorodecyl groups; hydroxyl-containing alkyl groups, such as 3-hydroxypropyl groups; and γ-ureido(3-uracil) groups. Examples of such alkyl groups include ureido group-containing alkyl groups such as γ-amino(3-amino)propyl group, 2-aminoethylaminomethyl group, and 3-(N-styrylmethyl-2-aminoethylamino)propyl group; amino group-containing alkyl groups such as γ-glycidoxy(3-glycidyloxy)propyl group and 2-(3,4-epoxycyclohexyl)ethyl group; mercapto group-containing alkyl groups such as γ-mercapto(3-mercapto)propyl group; isocyanate group-containing alkyl groups such as 3-isocyanatepropyl group; and aryl groups such as phenyl group.

[0078] Specific examples of the formula (B) include alkoxysilanes such as trialkoxysilane and dialkoxysilane. Specific examples of trialkoxysilanes include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, pentyltrimethoxysilane, pentyltriethoxysilane, heptyltrimethoxysilane, heptyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, dodecyltrimethoxysilane, and dodecyltriethoxysilane. ethoxysilane, hexadecyltrimethoxysilane, hexadecyltriethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2-aminoethylaminomethyltrimethoxysilane, γ-aminopropyltrimethoxysilane, 3-(2-aminoethylaminopropyl)trimethoxysilane, 3-(2-aminoethylaminopropyl)triethoxysilane, γ-Aminopropyltriethoxysilane, γ-Glycidoxypropyltrimethoxysilane, γ-Glycidoxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, Styrylethyltriethoxysilane, 3-(N-styrylmethyl-2-aminoethylamino)propyltrimethoxysilane, p-Styryltrimethoxysilane, γ-Mercaptopropyltrimethoxysilane, γ-Mercaptopropyltriethoxysilane, γ-Methacryloxypropyltrimethoxy Silane, γ-methacryloxypropyltriethoxysilane, γ-ureidopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane, tridecafluorooctyltrimethoxysilane, tridecafluorooctyltriethoxysilane, heptadecafluorodecyltrimethoxysilane, heptadecafluorodecyltriethoxysilane, and 3-isocyanatopropyltriethoxysilane can be mentioned. Specific examples of dialkoxysilane include dimethyldimethoxysilane and dimethyldiethoxysilane.

[0079] Specific examples of the above condensates include silicone resins manufactured by Dow Corning Toray, silicone resins manufactured by Momentive Performance Materials Japan, LLC, silicone resins manufactured by Shin-Etsu Chemical Co., Ltd., hydroxyl group-containing polydimethylsiloxanes manufactured by Dow Corning Asia, silicone oligomers manufactured by Dow Corning Toray, and titanium oligomers such as titanium tetra-n-butoxide, tetramer (manufactured by Kanto Chemical Co., Ltd.).

[0080] The refractive index of the high refractive index layer is higher than that of the antiglare layer, and is preferably such that the reflected light reflected at the surface of the antiglare layer and the reflected light reflected at the surface of the high refractive index layer, which is the interface between the antiglare layer and the high refractive index layer, have opposite phases; for example, the refractive index is selected from the range of 1.5 to 2.1, more preferably 1.5 to 1.8.

[0081] The refractive index of the high refractive index layer may be adjusted by adjusting the curing temperature. In this case, a higher curing temperature is preferable in terms of increasing the refractive index of the high refractive index layer. From the viewpoint of heat resistance of the substrate, etc., the baking temperature is preferably in the range of 100°C to 300°C, and more preferably in the range of 150°C to 250°C.

[0082] The refractive index of the high refractive index layer may be adjusted by further irradiating the coating with ultraviolet (UV) rays after curing. The ultraviolet irradiation for obtaining a desired refractive index of the high refractive index layer may be performed, for example, using a high pressure mercury lamp. When a high pressure mercury lamp is used, the total light irradiation is 1000 mJ / cm2 in terms of 365 nm. 2 The preferred dose is 2000 mJ / cm or more. 2 ~10000mJ / cm 2The irradiation amount is more preferable. The UV light source is not particularly specified, and another UV light source can be used. When using another light source, it is sufficient that the same cumulative light amount as that when the high pressure mercury lamp is used is irradiated.

[0083] Next, a functional layer obtained from a specific coating agent may be formed on the surface of the antiglare layer. In the present invention, since the antiglare layer is formed from the above-mentioned coating liquid, the coating liquid for forming the functional layer on the antiglare layer and the adhesion to the functional layer are excellent.

[0084] In the present invention, the functional layer provided on the antiglare layer is not particularly limited. Specific examples include functional layers obtained from antifouling agents, paints, adhesives, antireflection agents, water repellents, hydrophilic agents, oil repellents, lipophilic agents, hard coat agents, antislip agents, etc.

[0085] The thickness of each of the antiglare layer and the functional layer is preferably from 5 to 1000 nm, more preferably from 10 to 400 nm.

[0086] The coating solution for forming a coating film of the present invention has excellent coating properties and can form a coating film with high transmittance. It also has excellent adhesion efficiency when spray-coated. Therefore, it can be suitably used in the fields of displays such as televisions, computers, car navigation systems, and mobile phones. EXAMPLES

[0087] The present invention will be described in more detail below with reference to examples, but is not limited to these. The abbreviations used below are as follows:

[0088] TEOS: Tetraethoxysilane F13: Tridecafluorooctyltrimethoxysilane UPS: γ-ureidopropyltriethoxysilane TTE:Tetraethoxytitanium AN: Aluminum nitrate nonahydrate MeOH: Methanol EtOH: Ethanol IPA: Isopropanol PGME: Propylene glycol monomethyl ether BCS: Butyl cellosolve PB: Propylene glycol monobutyl ether PG: Propylene glycol HG: 2-methyl-2,4-pentanediol NMP: N-methyl-2-pyrrolidone

[0089] <Synthesis Example 1> TEOS (31.6 g), F13 (6.2 g), and MeOH (30.3 g) were added to a 200 mL four-neck flask equipped with a reflux condenser and stirred, and MeOH (15.1 g), water (15.0 g), and oxalic acid (0.8 g) were added thereto and stirred for 30 minutes in an ice bath at 10 ° C. Then, the mixture was stirred at 65 ° C. for 2 hours, and then UPS (0.5 g) and MeOH (0.5 g) were added and reacted at 65 ° C. for another 2 hours. Then, the mixture was allowed to cool to room temperature to obtain solution K1.

[0090] <Synthesis Example 2> In a 200 mL flask, AN (2.9 g), water (2.6 g), and EtOH (50.6 g) were added and stirred to obtain an AN solution. TEOS (21.2 g) was added to the AN solution and stirred at room temperature for 30 minutes. Then, TTE (10.0 g) and EtOH (12.7 g) were added and stirred at room temperature for another 30 minutes to obtain solution K2.

[0091] <Synthesis Example 3> In a 200 mL flask, AN (2.8 g), water (2.6 g), and EtOH (51.2 g) were added and stirred to obtain an AN solution. TEOS (17.7 g) was added to the AN solution and stirred at room temperature for 30 minutes. Then, TTE (12.9 g) and EtOH (12.8 g) were added and stirred at room temperature for another 30 minutes to obtain solution K3.

[0092] <Synthesis Example 4> In a 200 mL flask, AN (2.7 g), water (2.5 g), and EtOH (51.8 g) were added and stirred to obtain an AN solution. TEOS (14.3 g) was added to the AN solution and stirred at room temperature for 30 minutes. Then, TTE (15.7 g) and EtOH (13.0 g) were added and stirred at room temperature for another 30 minutes to obtain solution K4.

[0093] <Synthesis Example 5> TEOS (33.0 g) and MeOH (32.5 g) were added to a 200 mL four-neck flask equipped with a reflux condenser and stirred, and MeOH (13.8 g), water (15.0 g) and oxalic acid (0.9 g) were added thereto and stirred for 30 minutes in an ice bath at 10°C. After that, the mixture was stirred at 60°C for 2 hours, and then UPS (2.4 g) and MeOH (2.4 g) were added and reacted at 60°C for another 30 minutes. After that, the mixture was allowed to cool to room temperature to obtain solution K5.

[0094] <Preparation Example 1> PGME (20 g) and EtOH (20 g) were added to the K1 and K5 solutions (60 g) to obtain solutions KL1-1 and KM2-1, respectively.

[0095] <Preparation Example 2> To the K1 solution (12 g), PG (5 g), NMP (20 g) and MeOH (63 g) were added to obtain a solution KL1-2.

[0096] <Preparation Example 3> EtOH (2.5 g), IPA (42 g), BCS (9.4 g), PB (9.4 g) and HG (18.7 g) were added to the K2 to K4 solutions (18 g) to obtain solutions KL2 to KL4, respectively.

[0097] <Preparation Example 4> To the K1 solution (40 g), PGME (20 g) and EtOH (40 g) were added to obtain a solution KM1.

[0098] <Preparation Example 5> To the K5 solution (15 g), MeOH (1.8 g), EtOH (18.5 g), PGME (18.5 g), PB (27.7 g) and HG (18.5 g) were added to obtain a solution KM2-2.

[0099] [Spray application conditions] The spray coating was carried out using the following equipment and conditions. Equipment name: API-240-3D spray coater manufactured by Apiros Co., Ltd.

[0100] <Coating Condition I-1> Nozzle type: LPVN45, nozzle height: 100mm, Y-axis pitch: 2mm, air pressure: 550kPa, chemical flow rate 1.0mL / min, nozzle speed: 900mm / sec

[0101] <Coating Condition I-2> The Y-axis pitch was changed to 3 mm from coating condition I-1, while the other conditions were kept the same.

[0102] <Coating Condition I-3> The Y-axis pitch was changed to 5 mm from coating condition I-1, while the other conditions were kept the same.

[0103] <Coating Condition I-4> The Y-axis pitch was changed to 1.4 mm from coating condition I-1, while the other conditions were kept the same.

[0104] <Coating Conditions II-1> Nozzle type: LPVN12, nozzle height: 100mm, Y-axis pitch: 7mm, air pressure: 560kPa, chemical flow rate: 4.9mL / min, nozzle speed: 500mm / sec

[0105] <Coating Conditions II-2> The nozzle speed was changed to 550 mm / sec from coating condition II-1, while the other conditions were kept the same.

[0106] <Coating Condition III> Nozzle type: LPVN45, nozzle height: 100mm, Y-axis pitch: 7mm, air pressure: 470kPa, chemical flow rate: 4.9mL / min, nozzle speed: 170mm / sec

[0107] <Coating conditions IV> Nozzle type: LPVN45, nozzle height: 100mm, Y-axis pitch: 7mm, air pressure: 365kPa, chemical flow rate: 4.9mL / min, nozzle speed: 500mm / sec

[0108] <Coating Condition V> Nozzle type: LPVN45, nozzle height: 50mm, Y-axis pitch: 3mm, air pressure: 550kPa, chemical flow rate 1.0mL / min, nozzle speed: 700mm / sec

[0109] [Firing conditions] <Firing condition A> The coating was dried on a hot plate at 70°C for 5 minutes and then baked in a hot air circulating oven at 160°C for 30 minutes.

[0110] <Firing condition B> Dry in a hot air circulating oven at 130°C for 3 minutes and irradiate with UV at 3000mJ / cm 2 (365 nm equivalent, high pressure mercury lamp) and baked in a hot air circulating oven at 160°C for 30 minutes.

[0111] <Firing condition C> The coating was dried on a hot plate at 40°C for 5 minutes and then baked in a hot air circulating oven at 160°C for 30 minutes.

[0112] <Various evaluation conditions> [HAZE] A soda lime glass substrate was used, and a film was formed by spray coating under the same coating conditions as in the examples and comparative examples. The haze of the obtained substrate with the coating was measured using a haze meter HZ-V3 manufactured by Suga Test Instruments Co., Ltd.

[0113] [Surface observation] Soda lime glass was used as the substrate, and the substrate with the film thus produced was observed with a 3D white light interference microscope Contour GT manufactured by Bruker Japan Ltd.

[0114] [Convex surface coverage] From the images obtained by surface observation, the area ratio of the convex portion and the flat portion in any measurement point was calculated from the brightness component of the image analysis, and the convex portion surface coverage was calculated. The convex portion surface coverage was calculated in the same manner as the convex portion surface coverage calculation method described above.

[0115] [Reflectance] <Specular reflection, reflective color> The substrate was soda lime glass, and the substrate with the coating was measured for reflectance in the wavelength range of 380 nm to 800 nm at an incident angle of light of 5° using a UV-3600 ultraviolet, visible, and near infrared spectrophotometer manufactured by Shimadzu Corporation. From the obtained spectral reflectance curve, the average luminous reflectance (regular reflection) and reflected color a were calculated according to JIS R 3106. * , b * asked for.

[0116] <SCI、SCE> Soda lime glass was used as the substrate, and the reflectance of the prepared coated substrate was measured in the wavelength range of 360 nm to 740 nm at a light incidence angle of 8° using a spectrophotometer CM-3700A manufactured by Konica Minolta, Inc., and the average luminous reflectance of SCI and SCE was calculated according to JIS Z 8722. Note that SCI (Specular Component Include) is a measurement that takes into account specular reflected light, and SCE (Specular Component Exclude) is a measurement that does not take into account specular reflected light.

[0117] [Sparkling] A yellow-green color was displayed in front on an LCD display with a pixel density of 350 ppi at maximum brightness, and the coated substrate was placed directly on the screen. Sparkling was evaluated as x if it occurred, △ if it was slightly visible, and ◯ if no sparkling occurred.

[0118] [Refractive index] A silicon substrate (100) was used as the substrate, and solutions KL2 to KL4 were spin-coated to form films so that the film thickness after baking would be 100 nm. The films were then baked under the above-mentioned baking condition B, and the refractive index at a wavelength of 633 nm was measured using an ellipsometer (DVA-FLVW, manufactured by Mizojiri Optical Co., Ltd.) using the resulting coated substrate.

[0119] <Example 1> A lower layer was formed on a soda-lime glass substrate by spraying the solution KL1-2 obtained in Preparation Example 2 above under coating condition III and then baking under baking condition A. The resulting substrate was sprayed with the solution KL1-1 obtained in Preparation Example 1 above under coating condition I-1 and then baked under baking condition C to obtain a substrate with a coating. The obtained coated substrate was subjected to various evaluations, and the evaluation results are shown in Table 1-2.

[0120] <Examples 2 to 3, Comparative Examples 1 to 4> A coated substrate was obtained in the same manner as in Example 1, except that the solutions and conditions used were changed as shown in Table 1-1 below. In Comparative Examples 2 and 4, a coated substrate was obtained by forming a lower layer. The obtained coated substrate was subjected to various evaluations, and the evaluation results are shown in Table 1-2.

[0121] [Table 1-1]

[0122] [Table 1-2]

[0123] As shown in Table 1-2, in Examples 1 to 3, the regular reflection and SCI values ​​are kept low, and sparkling does not occur. Furthermore, in comparison with Comparative Example 2, SCE, which is a light scattering component of the reflectance, occurs, so that the antiglare function is expressed, and the above suggests that an antiglare functional film with an antireflection function has been constructed.

[0124] In Comparative Example 1, the SCI value was very large and sparkling also occurred.

[0125] In Comparative Example 3, a solution without a fluoroalkyl component was used, and a shape with a low surface coverage rate of the convex portions was not obtained, resulting in a high SCI value. In Comparative Example 4, the antiglare property was not obtained, but the reflected color was small. However, both the SCI and regular reflection were high.

[0126] <Examples 4 to 6 and Comparative Examples 5 to 7> The same procedure as in Example 1 was carried out except that the solutions and conditions used were changed as shown in Table 2-1 below, to obtain substrates with a coating. The obtained coated substrate was subjected to various evaluations, and the evaluation results are shown in Table 2-2.

[0127] [Table 2-1]

[0128] [Table 2-2]

[0129] As shown in Table 2-2, in Examples 4 to 6, the SCI value could be kept low and no sparkling occurred. Furthermore, compared with Comparative Examples 5 to 7, the absolute value of the reflected color was reduced and SCE occurred, so that the antiglare function was exerted. From the above, it is suggested that an antiglare coating with an antireflection function was formed. [Industrial Applicability]

[0130] By using the coating solution for forming a glare coating film of the present invention and the coating film composition using the same, it is possible to provide a laminate that can be formed on a glass substrate and has excellent anti-reflection and anti-glare properties (anti-glare function), which can contribute to improving the display quality of image display devices (liquid crystal displays, organic EL displays, plasma displays, etc.) equipped in various devices such as televisions, personal computers, and smartphones.

Claims

1. The present invention relates to an antiglare coating film, and an antiglare layer having an uneven surface structure formed on the substrate directly or via another layer, the antiglare layer being formed from a cured product of a composition for forming an antiglare coating film, the composition containing a polysiloxane having a fluorine-containing organic group, The polysiloxane is obtained by polycondensation of an alkoxysilane component containing an alkoxysilane compound represented by the following formula (1): A substrate with an antiglare layer, characterized in that in a surface uneven structure in which convex portions are intermittently formed on a flat coating of the antiglare layer, a convex portion surface coverage rate, which is the occupancy rate of the convex portions, is 5% to 70%. R 11 Si(OR 12 ) 3 (1) (R 11 represents an organic group substituted with a fluorine atom, and R 12 represents a hydrocarbon group having 1 to 5 carbon atoms.)

2. The substrate with an antiglare layer according to claim 1, wherein the polysiloxane is obtained by polycondensation of an alkoxysilane component further containing at least one selected from the group consisting of an alkoxysilane compound represented by the following formula (2) and an alkoxysilane compound represented by the following formula (3): Si(OR ２ ) ４ (2) R ３１ ｎ Si(OR ３２ ) ４－ｎ (3) (In the formula, R ２ represents a hydrocarbon group. ３１ represents an organic group not substituted with a fluorine atom or a hydrogen atom; R ３２ represents a hydrocarbon group having 1 to 5 carbon atoms, and n is an integer of 1 to 3.

3. The substrate with an antiglare layer according to claim 1 or 2, wherein the organic group not substituted with a fluorine atom is selected from an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a cycloalkyl group, an alkyl group containing a (meth)acryloyloxy group, an alkyl group containing a hydroxyl group, an alkyl group containing a ureido group, an alkyl group containing an amino group, an alkyl group containing an epoxy group, an alkyl group containing a mercapto group, an alkyl group containing an isocyanate group, or an aryl group.

4. The substrate with an antiglare layer according to claim 2 or 3, wherein the alkoxysilane compound represented by the formula (2) is tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, or tetrabutoxysilane.

5. The alkoxysilane compound represented by the formula (3) is methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, pentyltrimethoxysilane, pentyltriethoxysilane, heptyltrimethoxysilane, heptyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, hexadecyltrimethoxysilane, hexadecyltriethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, vinyl The antiglare layer-attached substrate according to any one of claims 2 to 4, which is triethoxysilane, 3-isocyanatepropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, 3-acryloyloxypropyltrimethoxysilane, 3-acryloyloxypropyltriethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyltriethoxysilane, γ-ureidopropyltrimethoxysilane, or γ-ureidopropyltriethoxysilane.

6. The substrate with an antiglare layer according to any one of claims 1 to 5, wherein the polysiloxane having a fluorine-containing organic group further comprises a polysiloxane containing an organic group represented by the following formula (F): CF ３ (CF ２ ) ｋ CH ２ CH ２ -* (F) (In the formula, k is an integer of 0 to 12. * represents a bonding position.)

7. The antiglare layer-attached substrate according to any one of claims 1 to 6, wherein the composition for forming an antiglare coating film contains at least one selected from ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, and methyl isobutyl ketone.

8. The substrate with an antiglare layer according to any one of claims 1 to 7, wherein the composition for forming an antiglare coating film contains at least one selected from the group consisting of methanol, ethanol, 2-propanol, 2-butanol, and 2-methyl-1-propanol.

9. The substrate with an antiglare layer according to any one of claims 1 to 8, wherein the height of the convex portions of the uneven structure is 50 nm to 2,000 nm.

10. The substrate with an antiglare layer according to any one of claims 1 to 9, wherein the antiglare layer has a haze of 0.3% to 40%.

11. The substrate with an antiglare layer according to any one of claims 1 to 10, wherein the refractive index of the antiglare layer is in the range of 1.3 to 1.

49.

12. The substrate with an antiglare layer according to any one of claims 1 to 11, characterized in that the antiglare layer is formed on a high refractive index layer, and the refractive index of the high refractive index layer is higher than the refractive index of the antiglare layer.

13. The substrate with an antiglare layer according to claim 12, wherein the refractive index of the high refractive index layer is in the range of 1.5 to 2.

1.

14. The substrate with an antiglare layer according to any one of claims 1 to 13, further comprising a functional layer formed on the antiglare layer.

15. An image display device comprising the substrate with an antiglare layer according to any one of claims 1 to 13.

16. A method for producing a substrate with an anti-glare layer, comprising the steps of using a composition for forming an anti-glare coating film described in any one of claims 1 to 14 as a coating liquid for forming an anti-glare coating film, applying the coating liquid for forming an anti-glare coating film onto a substrate to form an anti-glare layer, and obtaining a substrate with an anti-glare layer.

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