Manufacturing method of substrate with anti-reflective film and substrate with anti-reflective film

Abstract

This invention provides a method for manufacturing a substrate with an anti-reflective film and a substrate with an anti-reflective film obtained by the method. The method for manufacturing the substrate with an anti-reflective film can obtain a substrate with an anti-reflective film that can suppress liquid accumulation at the outer peripheral edge of the substrate. A method for manufacturing a substrate with an anti-reflective film includes: step (1), coating a substrate (A) with a coating liquid (P) to form a coating film; and step (2), curing the coating film by firing. The coating liquid (P) is a coating liquid containing polysiloxane (P) as a polymer component, and the viscosity of the coating liquid is 0.3 to 100 mPa·s, and the surface tension is 20 to 40 mN / m. Substrate (A): A substrate for which a first corner formed by the main surface of the substrate for coating film formation and the end face of the substrate has been subjected to an R-shaped chamfer, wherein the radius of the R-shaped chamfer is 0.2 to 3.0 mm, the distance from the outermost periphery of the substrate subjected to the R-shaped chamfer is 0.1 to 2.0 mm, and the contact point between the R-shaped chamfer and the main surface of the substrate for coating film formation does not have an angle formed by a height difference.

Description

Technical Field

[0001] The present invention relates to a method for manufacturing a substrate with an anti-reflective film and a substrate with an anti-reflective film obtained by the manufacturing method. The method for manufacturing the substrate with an anti-reflective film uses a coating liquid for film formation and a substrate having a specific structure. The coating liquid for film formation mainly contains a polysiloxane obtained by polycondensation of a specific alkoxysilane and further has a specific liquid composition. Background Technology

[0002] Previously, it was known that if a low-refractive-index coating with a refractive index lower than that of a substrate is formed on the surface of a substrate, the reflectivity of light reflected from the surface of the coating will decrease. Such low-refractive-index coatings exhibiting reduced light reflectivity are used as anti-reflective films and applied to various substrate surfaces.

[0003] Typically, wet or dry processes are known as methods for depositing low-refractive-index coatings on substrates represented by glass substrates.

[0004] Dry processes include vacuum evaporation and CVD (Chemical Vapor Deposition), among others. However, productivity and cost become issues in these methods.

[0005] As a wet process, well-known methods such as spin coating, dip coating, or spray coating can be listed.

[0006] Among these methods, spray coating has attracted attention due to its low substrate dependence and its advantages in terms of productivity and cost. Spray coating involves adding fine droplets of liquid to a substrate, which then spreads to form a film through wetting. It offers the advantages of low substrate dependence and minimal waste of coating liquid. Therefore, it is expected to reduce the cost of low-reflection glass and improve production efficiency. Patent Document 1 discloses a coating liquid for spray coating that contains specific polysiloxane and solvent components.

[0007] Existing technical documents

[0008] Patent documents

[0009] Patent Document 1: WO2011 / 136370 Summary of the Invention

[0010] The problem that the invention aims to solve

[0011] In recent years, large-screen and high-definition display elements have become the mainstream for the application of low-reflective coatings. From a design perspective, these display elements sometimes use substrates with curved edges.

[0012] After research, the inventors discovered that if a conventional coating solution is applied to a substrate that has undergone curved surface processing, liquid will accumulate at the outer peripheral edge of the substrate.

[0013] Based on the above, the object of the present invention is to provide a method for manufacturing a substrate with an anti-reflective film and a substrate with an anti-reflective film obtained by the manufacturing method, wherein the method for manufacturing a substrate with an anti-reflective film can obtain a substrate with an anti-reflective film that can suppress liquid accumulation at the outer peripheral edge of the substrate.

[0014] Solution for solving the problem

[0015] In order to solve the above-mentioned technical problems, the inventors conducted in-depth research and found that using a coating liquid with a specific liquid composition and a substrate with a specific structure is extremely effective in achieving the above-mentioned objectives, thus completing the present invention.

[0016] The present invention includes the following solutions.

[0017] A method for manufacturing a substrate with an anti-reflective film includes: step (1), coating a substrate (A) with a coating liquid (P) to form a coating film; and step (2), curing the coating film by firing.

[0018] Coating liquid (P): A coating liquid containing polysiloxane (P) as a polymer component, wherein the viscosity of the coating liquid is 0.3 to 100 mPa·s and the surface tension is 20 to 40 mN / m.

[0019] Substrate (A): A substrate for which a first corner formed by the main surface of the substrate for coating film formation and the end face of the substrate has been subjected to an R-shaped chamfer, wherein the radius of the R-shaped chamfer is 0.2 to 3.0 mm, the distance from the outermost periphery of the substrate subjected to the R-shaped chamfer is 0.1 to 2.0 mm, and the contact point between the R-shaped chamfer and the main surface of the substrate for coating film formation does not have an angle formed by a height difference.

[0020] It should be noted that, throughout this specification, halogen atoms may include fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc., and * in any case represents a bonded bond.

[0021] Invention Effects

[0022] According to the present invention, a substrate with an anti-reflective film that suppresses liquid accumulation at the outer peripheral edge of the substrate can be obtained, and a display element with high design flexibility and excellent display quality can be obtained. Attached Figure Description

[0023] Figure 1 This is a partial cross-sectional view of the outer periphery of a substrate (A) according to one embodiment.

[0024] Figure 2 yes Figure 1 A three-dimensional schematic diagram of the substrate 11.

[0025] Figure 3-1 This is an optical microscope photograph of the cross-sectional shape of the end of substrate I in Example 1.

[0026] Figure 3-2 This is a schematic cross-sectional view of the end of substrate I in Example 1.

[0027] Figure 4-1 This is an optical microscope photograph of the cross-sectional shape of the end of substrate II in Comparative Example 1.

[0028] Figure 4-2 This is a schematic cross-sectional view of the end of substrate II in Comparative Example 1.

[0029] Figure 5 This is a schematic cross-sectional view of the end of substrate III in Comparative Example 2.

[0030] Figure 6 This is an optical microscope photograph of the end of the coating in Example 1.

[0031] Figure 7 This is an optical microscope photograph of the coating tip in Comparative Example 1. Detailed Implementation

[0032] <Polysiloxane (P)>

[0033] The substrate with antireflective film of the present invention is obtained by using a coating liquid containing polysiloxane (P) as a polymer component.

[0034] The structure of the aforementioned polysiloxane (P) is not particularly limited. For example, the aforementioned polysiloxane (P) can be obtained by polycondensation of an alkoxysilane compound component containing an alkoxysilane compound.

[0035] Polysiloxanes (P) can be composed of one or more polymers.

[0036] The aforementioned polysiloxane (P) may be, for example, a polysiloxane having urea groups and / or urea bonds.

[0037] With this configuration, the following effect can be achieved: a high-hardness coating can be obtained even when firing at a relatively low temperature.

[0038] The aforementioned polysiloxanes having urea groups and / or urea bonds can be obtained, for example, by polycondensation of an alkoxysilane compound component containing an alkoxysilane compound as shown in formula (1) below.

[0039] R 1 {Si(OR)} 1’)3} p (1)

[0040] In equation (1), p represents an integer of 1 or 2.

[0041] R 1 It is a p-valent organic group having 2 to 13 carbon atoms and having a urea group and / or a urea bond, more preferably a p-valent organic group having 2 to 7 carbon atoms. When p is 1, R 1 Preferably, it is a monovalent organic group formed by replacing any hydrogen atom of a hydrocarbon group having 1 to 12 carbon atoms with a urea group; more preferably, it is a monovalent organic group formed by replacing any hydrogen atom of a hydrocarbon group having 1 to 6 carbon atoms with a urea group. When p is 2, R 1 Preferably, it is a divalent organic group formed by inserting a urea bond between any carbon-carbon bonds of a hydrocarbon group having 2 to 12 carbon atoms; more preferably, it is a divalent organic group formed by inserting a urea bond between any carbon-carbon bonds of a hydrocarbon group having 2 to 6 carbon atoms.

[0042] R 1’ It is an alkyl group having 1 to 5 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms, and more preferably methyl or ethyl. Multiple R 1’ They can be the same or different.

[0043] R 1 R 1’ It can have a straight chain structure or a branched chain structure.

[0044] In the alkoxysilane compound shown in formula (1), when p is 1, it is the alkoxysilane compound shown in formula (1-1).

[0045] R 1 Si(OR) 1’ 3 (1-1)

[0046] Furthermore, when p is 2, it is an alkoxysilane compound as shown in formula (1-2).

[0047] (R) 1’ O)3Si-R 1 -Si(OR) 1’ 3 (1-2)

[0048] The following are specific examples of alkoxysilane compounds represented by formula (1-1), but are not limited to these. For example, γ-ureopropyltriethoxysilane, γ-ureopropyltrimethoxysilane, γ-ureopropyltripropoxysilane, (R)-N-1-phenylethyl-N'-triethoxysilylpropylurea, (R)-N-1-phenylethyl-N'-trimethoxysilylpropylurea, etc.

[0049] γ-Uretopropyltriethoxysilane or γ-Uretopropyltrimethoxysilane are readily available as commercially available products and are therefore particularly preferred.

[0050] The following are specific examples of alkoxysilane compounds represented by formulas (1-2), but are not limited to these. Examples include 1,3-bis[3-(triethoxysilyl)propyl]urea, 1,3-bis[2-(triethoxysilyl)ethyl]urea, 1,3-bis[3-(trimethoxysilyl)propyl]urea, and 1,3-bis[3-(tripropoxysilyl)propyl]urea. Among these, 1,3-bis[3-(triethoxysilyl)propyl]urea is readily available as a commercially available product and is therefore particularly preferred.

[0051] From the viewpoint of properly obtaining the effects of the present invention, the amount of the alkoxysilane compound represented by formula (1) used is preferably 0.5 mol% or more, more preferably 1.0 mol% or more, and even more preferably 2.0 mol% or more, of all alkoxysilanes used to obtain polysiloxane (P). Furthermore, from the viewpoint of properly obtaining the effects of the present invention, it is preferably 60 mol% or less, more preferably 50 mol% or less, and even more preferably 40 mol% or less.

[0052] From the viewpoint of obtaining a low refractive index coating, the above-mentioned polysiloxane (P) can be a polysiloxane with fluorinated organic groups.

[0053] Such fluorine-containing organic groups are organic groups in which some or all of the hydrogen atoms of an aliphatic or aromatic group are replaced by fluorine atoms. Specific examples include trifluoropropyl, tridecafluorooctyl, heptadecafluorodecyl, and pentafluorophenyl.

[0054] Perfluoroalkyl groups are preferred as they readily produce highly transparent coatings. More preferably, they are perfluoroalkyl groups with 3 to 15 carbon atoms.

[0055] Specific examples include perfluoropropyl, perfluorooctyl, and perfluorodecyl.

[0056] In this invention, a variety of polysiloxanes having fluorinated organic groups on their side chains can be used together.

[0057] There are no particular limitations on the method for obtaining the polysiloxane having fluorinated organic groups in the side chain as described above. Typically, it is obtained by polycondensation of an alkoxysilane having the aforementioned organic groups in the side chain.

[0058] Preferably, the polysiloxane is obtained by polycondensation of an alkoxysilane component containing an alkoxysilane compound as shown in formula (2a).

[0059] R 2 Si(OR)2’ 3 (2a)

[0060] The alkoxysilane compound shown in formula (2a) is an alkoxysilane having the above-mentioned fluorinated organic groups on its side chain.

[0061] Here, R in equation (2a) 2 The above-mentioned fluorine-containing organic group is not particularly limited in the number of fluorine atoms in the organic group.

[0062] Furthermore, R in equation (2a) 2’ The R group represents a hydrocarbon group having 1 to 5 carbon atoms, preferably a saturated hydrocarbon group having 1 to 5 carbon atoms, and more preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, or sec-butyl. Here, n- indicates n, i- indicates iso, s- indicates sec, and t- indicates tert. Multiple R groups... 2’ They can be the same or different.

[0063] In the alkoxysilane compound represented by formula (2a), R is more preferably preferred. 2 Perfluoroalkyl alkoxysilane compounds or R 2 An alkoxysilane compound having an organic group represented by the following formula (2F).

[0064] CF3 (CF2) k CH2CH2-*(2F)

[0065] In equation (2F), k represents an integer from 0 to 12. From the viewpoint of properly obtaining the effects of the present invention, k is preferably an integer from 0 to 8.

[0066] Preferred specific examples of alkoxysilane compounds represented by formula (2a) include: 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, (1H,1H,2H,2H-tridecylfluorooctyl)trimethoxysilane, (1H,1H,2H,2H-tridecylfluorooctyl)triethoxysilane, (1H,1H,2H,2H-heptadecylfluorodecyl)trimethoxysilane, (1H,1H,2H,2H-heptadecylfluorodecyl)triethoxysilane, etc.

[0067] In this invention, at least one of the alkoxysilane compounds shown in formula (2a) may be used, or multiple compounds may be used as needed.

[0068] The total molar amount of the alkoxysilane compound shown in formula (2a) is preferably 5 mol% or more, more preferably 10 mol% or more, relative to the total molar amount of silicon atoms in the alkoxysilane compound used in the synthesis of polysiloxane (P). Furthermore, from the viewpoint of obtaining a uniform coating solution, it is preferably 40 mol% or less, more preferably 30 mol% or less.

[0069] Polysiloxane (P) can be a polysiloxane having fluorinated organic groups in the main chain direction of the polysiloxane. As a monomeric component for synthesizing such a polysiloxane (P), an alkoxysilane compound having two trialkoxysilyl groups bonded to a divalent organic group having fluorine atoms can be used, for example. Specific examples of such alkoxysilane compounds include the alkoxysilane compound shown in formula (2b) below.

[0070] (OR) 2b’ 3Si-R 2b -Si(OR) 2b’ 3 (2b)

[0071] Here, R in equation (2b) 2b The above-mentioned fluorine-containing organic group is not particularly limited in the number of fluorine atoms in the organic group. R in formula (2b) 2b Preferably, it is a divalent perfluoroalkyl chain or *-CH2-CH2-(CF2). p -CH2-CH2-* (p is an integer from 1 to 12) represents a divalent organic group.

[0072] Furthermore, R in equation (2b) 2b’ Each R independently represents a hydrocarbon group having 1 to 5 carbon atoms, preferably a saturated hydrocarbon group having 1 to 5 carbon atoms, and more preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, or sec-butyl. 2b’ They can be the same or different.

[0073] As specific examples of formula (2b), examples include: 1,6-bis(2-trimethoxysilylethyl)dodecylfluorohexane or 1,6-bis(2-triethoxysilylethyl)dodecylfluorohexane, etc.

[0074] In addition, other alkoxysilane compounds may be used as monomer components for obtaining polysiloxane (P), besides the alkoxysilane compounds shown in formula (1) above and formula (2a) or (2b) above as needed.

[0075] Furthermore, polysiloxane (P) can also be a polymer obtained by polycondensation of an alkoxysilane compound component that contains only other alkoxysilane compounds.

[0076] The other alkoxysilane compounds mentioned above may use one or more compounds.

[0077] Preferred examples of other alkoxysilane compounds include, but are not limited to, the alkoxysilane compound shown in formula (3), the alkoxysilane compound shown in formula (4), and the alkoxysilane compound shown in formula (5).

[0078] R 3 n Si(OR) 3’ ) 4－n (3)

[0079] (In equation (3), R) 3 R indicates a monovalent organic group that does not have a urea group, urea bond, or fluorine atom. 3’ (This represents a hydrocarbon group with 1 to 5 carbon atoms, where n represents an integer from 1 to 3.)

[0080] Si(OR) 4 )4(4)

[0081] (R in equation (4)) 4 (Indicates a hydrocarbon group.)

[0082] (R) 5’ O)3Si-R 5 -Si(OR) 5’ 3 (5)

[0083] (In equation (5), R) 5 R represents a divalent organic group with 1 to 20 carbon atoms that does not have a urea group, a urea bond, or a fluorine atom. 5’ (This refers to hydrocarbon groups with 1 to 5 carbon atoms.)

[0084] R in the above formula (3) 3 The number of carbon atoms is preferably 1 to 20, more preferably 1 to 15. When n is 2 or 3, R 3 They can be the same, or they can be different.

[0085] In equation (3) R 3’ In the case where n is 1 or 2, R 3’ They can be the same, or they can be different.

[0086] The following are specific examples of alkoxysilanes represented by formula (3), but are not limited thereto.

[0087] Methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, pentyltrimethoxysilane, pentyltriethoxysilane, heptyltrimethoxysilane, heptyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, hexadecyltrimethoxysilane, hexadecyltriethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane; Vinyltrimethoxysilane, vinyltriethoxysilane; 3-isocyanopropyltrimethoxysilane, 3-isocyanopropyltriethoxysilane; 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane; γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane; γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane; 3-acryloyloxypropyltrimethoxysilane, 3-acryloyloxypropyltriethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyltriethoxysilane, etc., trialkoxysilanes.

[0088] From the viewpoint of properly obtaining the effects of the present invention, the amount of the alkoxysilane compound shown in formula (3) used is preferably 0.5 mol% or more, more preferably 1.0 mol% or more, and even more preferably 2.0 mol% or more, of all alkoxysilane compounds used to obtain polysiloxane (P). Furthermore, from the viewpoint of properly obtaining the effects of the present invention, it is preferably 60 mol% or less, more preferably 50 mol% or less, and even more preferably 40 mol% or less.

[0089] R in equation (4) 4 The term "hydrocarbon group" is preferred from the viewpoint of improving reactivity; saturated hydrocarbon groups with 1 to 5 carbon atoms are preferred, and methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, and sec-butyl are more preferred. 4 They can be the same, or they can be different.

[0090] Specific examples of tetraalkoxysilane compounds of formula (4) include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, etc., which are readily available as commercially available products. In this invention, at least one of the alkoxysilane compounds shown in formula (4) may be used, or multiple compounds may be used as needed.

[0091] The amount of alkoxysilane compound used in formula (4) is preferably 40 mol% or more, more preferably 50 mol% or more, of the total amount of all alkoxysilane compounds used in the synthesis of polysiloxane (P). Furthermore, it is preferably 99 mol% or less, more preferably 96 mol% or less.

[0092] Furthermore, in the alkoxysilane compounds of formula (5), R 5’ It is a hydrocarbon group with 1 to 5 carbon atoms, preferably a saturated hydrocarbon group with 1 to 4 carbon atoms, and more preferably a saturated hydrocarbon group with 1 to 3 carbon atoms. R 5’ They can be the same, or they can be different.

[0093] R 5 It is a divalent organic group with 1 to 20 carbon atoms that does not have a urea group, urea bond, or fluorine atom. This divalent organic group may also contain cyclic structures or branched structures such as double bonds, triple bonds, or phenyl groups. In addition, this divalent organic group may also contain heteroatoms such as nitrogen atoms, oxygen atoms, and fluorine atoms.

[0094] In this invention, the alkoxysilane compound represented by formula (5) can also be used in various ways as needed.

[0095] Preferred examples of alkoxysilane compounds represented by formula (5) include dimethyldimethoxysilane, dimethyldiethoxysilane, etc.

[0096] The amount of alkoxysilane compound shown in formula (5) used is preferably 1 mol% or more, more preferably 2 mol% or more, of the total amount of alkoxysilane compound used in the synthesis of polysiloxane (P). Furthermore, it is preferably 30 mol% or less, more preferably 20 mol% or less.

[0097] The method for polycondensing polysiloxane (P) used in this invention is not particularly limited. Examples include hydrolysis / condensation of alkoxysilane compounds in organic solvents such as alcohols and glycols. In this case, the hydrolysis / condensation reaction can be either partial or complete hydrolysis. In the case of complete hydrolysis, water at least 0.5 times the molar ratio of all alkoxy groups in the alkoxysilane compound can be added.

[0098] In this invention, the amount of water used in the above reaction can be appropriately selected as desired, typically 0.1 to 2.5 times the molar amount of all alkoxy groups in the alkoxysilane compound, preferably 0.1 to 2.0 times the molar amount.

[0099] In addition, acids or bases are often added as catalysts to promote hydrolysis / condensation reactions. Examples of acid catalysts include inorganic acids such as hydrochloric acid, sulfuric acid, and nitric acid; and organic acids such as acetic acid, oxalic acid, or formic acid. Examples of base catalysts include inorganic salts such as sodium and potassium; and various amines (for example, methylamine, ethylamine, ethanolamine, triethylamine, and ammonia).

[0100] In this case, the amount of catalyst used in the reaction is preferably 0.001 to 0.05 moles of all alkoxy groups in the alkoxysilane compound, more preferably 0.01 to 0.03 moles. Furthermore, the hydrolysis / condensation reaction can be promoted by heating the solution containing the alkoxysilane compound.

[0101] At this point, the heating temperature can be appropriately selected as desired, preferably 50°C or higher, and more preferably 180°C or lower. Furthermore, the heating time can be appropriately selected as desired, preferably 10 minutes or more, and more preferably within 24 hours. As more preferred reaction conditions, examples include methods such as heating at 50°C for 24 hours while stirring, and heating under reflux for 2 to 10 hours while stirring.

[0102] In addition, another method can be listed, for example, as heating a mixture of an alkoxysilane compound, a solvent, and an acid. Specifically, this involves first adding an acid to an alcoholic solvent to prepare an alcoholic solution of the acid, then mixing the solution with an alkoxysilane and heating it.

[0103] At this point, the amount of acid is preferably set to 0.2 to 2 moles relative to 1 mole of all the alkoxy groups in the alkoxysilane compound, more preferably 0.5 to 2 moles.

[0104] In this method, the heating temperature is preferably set to 50°C or higher, and more preferably 180°C or lower, using a liquid thermometer. The reaction time is preferably 10 minutes or more, and more preferably within 24 hours.

[0105] In the above methods, when using multiple alkoxysilane compounds, the multiple alkoxysilane compounds can be mixed in advance for use, or multiple alkoxysilane compounds can be added sequentially.

[0106] When polycondensing alkoxysilane compounds using the method described above, the concentration of SiO2 (hereinafter referred to as SiO2 equivalent concentration) of the total stoichiometry of silicon atoms in the alkoxysilane compound used in the reaction is preferably 20% by mass or less, more preferably 15% by mass or less. Selecting any concentration within such a range is preferable from the viewpoint of suppressing gel formation and obtaining a homogeneous polysiloxane solution.

[0107] The solvent used for polycondensation of alkoxysilane compounds is not particularly limited as long as it can dissolve the alkoxysilane compound shown in formula (1), the alkoxysilane compound shown in formula (2a), the alkoxysilane compound shown in formula (2b), and the alkoxysilane compounds shown in formulas (3) to (5). Alcohols or organic solvents with good compatibility with alcohols are preferred.

[0108] Specific examples of organic solvents used in the polycondensation of alkoxysilane compounds include: alcohols such as methanol, ethanol, propanol, butanol, or 2-methyl-2,4-pentanediol (also known as hexanediol); ethers such as ethylene glycol monobutyl ether, propylene glycol monomethyl ether, and propylene glycol monobutyl ether; and ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone.

[0109] In this invention, a variety of the above-mentioned organic solvents can be used in combination.

[0110] <Molecular weight of polysiloxane (P)>

[0111] The weight-average molecular weight (Mw) of the polysiloxane (P) converted from polystyrene by gel permeation chromatography (GPC) is preferably 500 to 500,000, more preferably 1,000 to 300,000. Furthermore, the molecular weight distribution (Mw / Mn) expressed as the ratio of Mw to the number-average molecular weight (Mn) of polystyrene determined by GPC is preferably 15 or less, more preferably 10 or less. From the viewpoint of appropriately obtaining the effects of the present invention, this molecular weight range is preferred.

[0112] <Coating Liquid (P)>

[0113] The coating liquid (P) of the present invention contains polysiloxane (P) as a polymer component, has a viscosity of 0.3 to 100 mPa·s, and a surface tension of 20 to 40 mN / m. Here, the viscosity of the coating liquid is the value measured using an E-type viscometer at a temperature of 25°C, and the surface tension of the coating liquid is the value measured by the droplet method at a temperature of 25°C.

[0114] The viscosity of the coating liquid (P) is more preferably 0.5 mPa·s or more, and even more preferably 0.8 mPa·s or more. Furthermore, it is more preferably 80 mPa·s or less, and even more preferably 50 mPa·s or less.

[0115] The surface tension of the coating liquid (P) is more preferably 21 mN / m or more, and even more preferably 23 mN / m or more. Furthermore, it is more preferably 37 mN / m or less, and even more preferably 35 mN / m or less.

[0116] The coating liquid (P) of the present invention is preferably a coating liquid containing polysiloxane (P) and a solvent.

[0117] The following solvents can be listed as specific examples of solvents that can be used in coating liquid (P).

[0118] Examples include: methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-methyl-2-propanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, diacetone alcohol, etc.; cyclic alcohols such as cyclopropanol, cyclobutanol, cyclopentanol, cyclohexanol, 2-methylcyclohexanol, cycloheptanol, cyclooctanol, cyclononanol, cyclodecanol, etc.; and diols such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, butanediol (1,3-butanediol, 2,3-butanediol, etc.), 2-methyl-2,4-pentanediol, pentanediol, hexanediol, heptanediol, etc.

[0119] Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, ethylene glycol dibutyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether, propylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether (ethyl carbitol), diethylene glycol monopropyl ether, diethylene glycol monobutyl ether (butyl carbitol), diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, or tetrahydrofuran, 1,4-dioxane and other ethers;

[0120] Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; esters such as methyl acetate, ethyl acetate, and ethyl lactate; lactams such as N-methyl-2-pyrrolidone; amides such as N,N-dimethylformamide, N,N-dimethylacetamide, tetramethylurea, or hexamethylphosphoric triamine; lactones such as γ-butyrolactone; and dimethyl sulfoxide, etc.

[0121] Regarding the solvent that can be used in the coating liquid (P), it is preferable to include one or more solvents selected from the group consisting of cyclic alcohols having 3 to 10 carbon atoms and diols having 3 to 10 carbon atoms (e.g., ethylene glycol, propylene glycol, 2-methyl-2,4-pentanediol, etc.).

[0122] Regarding the solvent that can be used in the coating liquid (P), it is preferable to include one or more glycol ethers having 4 to 8 carbon atoms (for example, solvents with 4 to 8 carbon atoms are preferred among the above-mentioned ethers, such as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, and propylene glycol monobutyl ether).

[0123] There are no particular limitations on the method for preparing the coating solution (P). For example, it is simple to use a polymerization solution containing polysiloxane (P) as is (hereinafter referred to as polymerization solution (P)) by mixing and diluting with solvents. Alternatively, the polymerization solution (P) can be concentrated and diluted with solvents as needed, or diluted by mixing with solvents after replacing with other solvents.

[0124] Regarding the content of polysiloxane (P) in the coating solution (P), it is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, based on the concentration of SiO2 converted from the total amount of silicon atoms in the polysiloxane (P) (SiO2 equivalent concentration). Furthermore, from the viewpoint of improving the storage stability of the solution, it is preferably 15% by mass or less, more preferably 8% by mass or less.

[0125] From the viewpoint of properly obtaining the effects of this disclosure, the content of polysiloxane (P) in the coating liquid (P) is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, relative to 100 parts by mass of all components in the coating liquid (P) excluding the solvent.

[0126] When the coating liquid (P) contains other components described later, the content of polysiloxane (P) is preferably 99.9 parts by mass or less, more preferably 99 parts by mass or less, relative to 100 parts by mass of all components in the coating liquid (P) excluding solvent.

[0127] <Other Ingredients>

[0128] In this invention, the coating liquid (P) may also contain other components besides polysiloxane (P) and solvent. Specific examples of other components include inorganic microparticles, fillers, leveling agents, surface modifiers, or surfactants.

[0129] The content of other components relative to 100 parts by mass of all components in the coating liquid (P), excluding the solvent, may be 0.1 parts by mass or more, or 1 part by mass or more. Alternatively, it may be 90 parts by mass or less, or 80 parts by mass or less.

[0130] As inorganic particles, examples include: metal oxide particles, metal composite oxide particles, magnesium fluoride particles, etc.

[0131] Examples of metal oxide particles include silicon dioxide, aluminum oxide, titanium oxide, zirconium oxide, tin oxide, and zinc oxide. Furthermore, they can also exist in a beaded form.

[0132] Examples of metal composite oxide microparticles include: ITO (Indium Tin Oxide), ATO (Antimony Trioxide), AZO (Zinc Aluminium Oxide), and zinc antimonate.

[0133] In addition, examples can be given of hollow silica particles, porous silica particles, etc. The aforementioned hollow silica particles can also be in a beaded form.

[0134] Inorganic microparticles can be either powders or colloidal solutions, but colloidal solutions are preferred due to their ease of handling. The colloidal solution can be a solution obtained by dispersing inorganic microparticle powder in a dispersion medium, or it can be a commercially available colloidal solution. Examples of commercially available inorganic microparticles include organosilicon sols manufactured by Nissan Chemical Co., Ltd. (methanol silica sol, MA-ST-S, MA-ST-M, MA-ST-L, MEK-ST-40, TOL-ST, MA-ST-UP, IPA-ST, IPA-ST-UP, MEK-ST-UP, EG-ST, NPC-ST-30, etc.). One type of inorganic microparticle can be used alone, or two or more can be used in combination.

[0135] In this invention, by including inorganic microparticles, it is possible to impart surface shape and other functions to the cured film to be formed.

[0136] The inorganic microparticles preferably have an average particle size of 0.001 to 0.2 μm, more preferably 0.001 to 0.1 μm. When the average particle size of the inorganic microparticles exceeds 0.2 μm, the transparency of the cured film formed by the prepared coating liquid is sometimes reduced.

[0137] Here, "average particle size" can be expressed as the value obtained by observing and measuring the average primary particle size of inorganic particles using the BET method (based on the specific surface area obtained by nitrogen adsorption) and by transmission electron microscopy. In this invention, it is expressed by the BET method (based on the specific surface area obtained by nitrogen adsorption).

[0138] Water and organic solvents can be listed as dispersion media for inorganic particles. As a colloidal solution, from the viewpoint of the stability of the coating solution used for film formation, the pH or pKa is preferably adjusted to 2–10, more preferably 3–7.

[0139] Organic solvents used as dispersion media in colloidal solutions include: alcohols such as methanol, ethanol, propanol, and butanol; diols such as ethylene glycol; ketones such as methyl ethyl ketone and methyl isobutyl ketone; aromatic hydrocarbons such as toluene and xylene; amides such as dimethylformamide and dimethylacetamide; lactams such as N-methylpyrrolidone; esters such as ethyl acetate and butyl acetate; lactones such as γ-butyrolactone; and ethers such as ethylene glycol monopropyl ether, tetrahydrofuran, and 1,4-dioxane.

[0140] Alcohols and ketones are preferred. These organic solvents can be used as dispersion media, either alone or in combination of two or more.

[0141] In addition, fillers, leveling agents, surface modifiers, surfactants, etc., can be well-known substances, and commercially available products are preferred.

[0142] <Manufacturing of substrates with anti-reflective coating>

[0143] The substrate with an anti-reflective film of the present invention has an anti-reflective film. Furthermore, the anti-reflective film of the present invention is formed using the above-described coating liquid (P).

[0144] One embodiment of the antireflective film of the present invention is obtained by the following manufacturing method, the manufacturing method comprising: step (1), coating the above-mentioned coating liquid (P) onto the substrate (A) to form a coating film; and step (2), curing the coating film by firing.

[0145] Substrate (A): A substrate for which a first corner formed by the main surface of the substrate to which the coating film is formed and the end face of the substrate has been subjected to an R-shaped chamfer treatment, wherein the radius of the R-shaped chamfer treatment is 0.2 to 3.0 mm, and the distance from the outermost periphery of the substrate subjected to the R-shaped chamfer treatment is 0.1 to 2.0 mm.

[0146] <Substrate (A)>

[0147] The substrate (A) of the present invention has the above-described configuration. According to the above configuration, by performing a chamfering treatment on the first angle formed between the main surface of the substrate to which the coating film is formed and the end face of the substrate, a substrate with an anti-reflective film that can suppress liquid accumulation at the outer peripheral edge of the substrate can be obtained.

[0148] Furthermore, according to the above configuration, only one of the first and second angles formed by the two main surfaces of the substrate and the end surface of the substrate is subjected to R-beveling treatment. Therefore, compared with the case where both angles are subjected to R-beveling treatment, there is an advantage of reducing the number of manufacturing steps of the substrate.

[0149] Furthermore, in the above configuration, the first angle formed by one main surface of the substrate and the end face of the substrate, and the second angle formed by the other main surface of the substrate and the end face of the substrate, may be chamfered with a radius of curvature (R). Alternatively, in the above configuration, the first angle and the second angle formed by the two main surfaces of the substrate and the end face of the substrate may be chamfered with different radii of curvature (R).

[0150] Furthermore, in the above configuration, the first corner formed by one main surface of the substrate and the end face of the substrate may be chamfered with an R-angle, and the second corner formed by the other main surface of the substrate and the end face of the substrate may be chamfered with a C-angle.

[0151] Figure 1 This is a partial cross-sectional view of the outer periphery of a substrate (A) according to one embodiment. It should be noted that... Figure 1 In the diagram, the dashed line represents the shape of the edge 15a before the R-beveling process. Furthermore, the upper side of the substrate 11 (including the surface of the edge 15a) is the coating surface 11a side, and the lower side of the substrate 11 is the back surface 11b opposite to the coating surface 11a.

[0152] exist Figure 1 In the example shown, only the corner 15a (the first corner) formed by the coating surface 11a of the substrate 11 and the end face 12 of the substrate is subjected to a radius r1a that is greater than or equal to the thickness t of the substrate 11 and less than twice the thickness t. (t≤r1a<2t)

[0153] Thus, an R-shaped chamfer surface 16a, which is a gently curved surface in the thickness direction of the substrate 11, can be formed only on the edge 15a on the coating surface 11a side. The junction 17a between the R-shaped chamfer surface 16a and the coating surface 11a does not have an angle formed by a height difference. Specifically, the center of the R-shaped chamfer treatment performed on the edge 15a is preferably located on the normal line of the coating surface 11a passing through the junction 17a.

[0154] It should be noted that the center of the R-beveling treatment applied to the edge 15a is located at position C1 on the imaginary single-dotted line T1-T1 in the cross-section of the substrate 11 in the thickness direction, which represents a position above the thickness t of the substrate 11 and less than twice the thickness t.

[0155] Furthermore, the aforementioned R-beveling process is performed in the region at a distance L1 from the outermost periphery of the substrate.

[0156] In one embodiment of the substrate (A), the radius r1a in the substrate is 0.2 to 3.0 mm, and from the viewpoint of properly obtaining the effects of the present invention, it is preferably 0.3 to 2.8 mm, and more preferably 0.5 to 2.6 mm.

[0157] Furthermore, in one embodiment of the substrate (A), the distance L1 from the outermost periphery of the substrate is 0.1 to 2.0 mm, and from the viewpoint of properly obtaining the effects of the present invention, it is preferably 0.1 to 1.8 mm, and more preferably 0.2 to 1.6 mm.

[0158] Figure 2 express Figure 1 A three-dimensional schematic diagram of the substrate 11.

[0159] Alternatively, some or all of the corners of the aforementioned substrate can be chamfered. This configuration allows for the formation of gently curved chamfered surfaces at each corner.

[0160] Materials used as substrate (A) include well-known or commonly known materials such as plastics, glass, and ceramics. Examples of plastics include: polycarbonate, poly(meth)acrylate, polyethersulfone, polyarylate, polyurethane, polysulfone, polyether, polyetherketone, trimethylpentene, polyolefin, polyethylene terephthalate, (meth)acrylonitrile, triacetylcellulose, diacetylcellulose, triacetylcellulose (TAC), or cellulose acetate butyrate.

[0161] From the viewpoints of substrate availability, processability, and environmental resistance, glass, polycarbonate, poly(meth)acrylate, polyethylene terephthalate, and triacetyl cellulose are preferred, and glass, polycarbonate, and poly(meth)acrylate are more preferred.

[0162] The coating liquid (P) can be coated using conventional coating methods to form a coating film. Examples of coating methods include dip coating, spin coating, spray coating, slot coating, brush coating, roller transfer printing, screen printing, inkjet printing, or flexographic printing.

[0163] In one embodiment of the invention, spraying is used for coating the substrate used to fabricate the anti-reflective film. Spraying is a method in which fine droplets of liquid are dropped onto the substrate, and the film is formed by the wetting and spreading of the liquid. It has the advantages of being substrate-independent and having less waste of coating liquid.

[0164] Among spraying methods, examples include two-fluid spraying, electrostatic spraying, and ultrasonic spraying. Of these, considering its simplicity and ability to cover large areas, two-fluid spraying is primarily used for surface treatment of displays.

[0165] When using the two-fluid spraying method in process (1), the film thickness of the coating film can be adjusted by liquid volume, gas pressure (gas flow rate), nozzle / worktable distance (distance between nozzle and worktable), coating speed, etc.

[0166] Liquid volume is a parameter that determines film thickness; increasing the liquid volume results in a thicker film, while decreasing the liquid volume results in a thinner film. In spraying, the liquid volume is, for example, 0.5–20 mL / min, preferably 1–12 mL / min.

[0167] Gas pressure or gas flow rate are parameters that determine the formation of fine droplets. Examples of gases used include N2 and dry air, but these are not particularly limited. In spraying, for example, the gas pressure is 50–800 kPa, preferably 100–700 kPa. On the other hand, the gas flow rate is, for example, 3–80 L / min, preferably 8–70 L / min. The gas pressure and gas flow rate vary depending on the diameter of the nozzle used, and therefore need to be managed separately according to the type of nozzle used.

[0168] The nozzle / stage distance is a parameter related to film thickness and coatability; a closer distance results in a thicker film, while a greater distance results in a thinner film. From the viewpoint of film thickness and coatability, the nozzle / stage distance is, for example, 5–200 mm, preferably 30–150 mm.

[0169] Coating speed is a parameter related to film thickness; a faster speed results in a thinner film, and a slower speed results in a thicker film. In spraying, the coating speed is, for example, 10–2000 mm / s, preferably 30–1500 mm / s.

[0170] The thickness of the coating formed on the substrate can be adjusted by the parameters described above during coating, but it can also be easily adjusted by the SiO2 concentration of the coating solution.

[0171] In step (2), a drying step to remove the solvent, which is part of the firing process, is not necessarily required. However, if the time from coating to firing is not fixed for each substrate, or if firing is not performed immediately after coating, a drying step is preferable. The drying process removes the solvent to the extent that the shape of the coating film will not be deformed due to substrate transport, etc., and the drying method is not particularly limited. For example, drying on a heating plate at a drying temperature of 30 to 150°C, preferably 40 to 100°C, for 0.5 to 30 minutes, preferably 1 to 5 minutes, is an example.

[0172] The coating film formed by the above method can be fired to produce a cured film. The firing temperature can be any temperature between 90 and 400°C, preferably 120 to 300°C, more preferably 150 to 270°C, and even more preferably 160 to 250°C. Heating can be performed using conventional methods, such as using a heating plate, a hot air circulating oven, a far-infrared heating furnace (IR oven), or a belt furnace. The resulting coating film has good film-forming properties and high transmittance.

[0173] In the manufacturing of the substrate with the anti-reflective film, a process of exposing the coating film cured in (2) can also be performed after process (2) (hereinafter also referred to as process (3)).

[0174] In step (3), the irradiation light can be, for example, ultraviolet light and visible light containing wavelengths of 150 to 800 nm, preferably ultraviolet light containing wavelengths of 300 to 400 nm.

[0175] As a light source for illumination, for example, low-pressure mercury lamps, high-pressure mercury lamps, deep ultraviolet (Deep UV) lamps, deuterium lamps, metal halide lamps, argon resonance lamps, xenon lamps, mercury-xenon lamps, excimer lasers (such as KrF excimer lasers), fluorescent lamps, light-emitting diode (LED) lamps, halogen lamps (such as sodium lamps), microwave-excited electrodeless lamps, etc.

[0176] The preferred light irradiation intensity is 1000–200000 J / m². 2 More preferably, it is 1000 to 100000 J / m 2 .

[0177] When the coating obtained according to the method of the present invention is used as an anti-reflective film, by forming the coating on the surface of a substrate having a refractive index higher than that of the coating, such as ordinary glass or film, according to the method of the present invention, it can be converted into a substrate with anti-reflective capabilities. At this time, it is effective to use the coating as a single coating on the substrate surface, and it is also effective to use it as an anti-reflective laminate on which the coating is formed on a lower coating having a high refractive index.

[0178] The relationship between the thickness of the coating and the wavelength of light is described here.

[0179] It is known that the relationship d = (2b - 1)λ / 4a (where b represents an integer greater than 1) holds between the thickness d (nm) of a coating with refractive index a and the wavelength λ (nm) of light for which the reduction in reflectivity caused by the coating is desired. Therefore, by using this formula to determine the thickness of the coating, the reflection of light of the desired wavelength can be easily prevented.

[0180] The average visible light reflectance of the antireflective film of the present invention to visible light with wavelengths from 380 nm to 800 nm is preferably 3.0% or less, more preferably 2.0% or less.

[0181] The average visible light reflectance is determined from the spectral reflectance curve. Regarding the spectral reflectance curve, it is calculated after applying a black coating to the side of the anti-reflective substrate opposite to the low-refractive-index layer to remove gloss, or after attaching a black film. The incident angle is set to 5 degrees, perpendicular to the surface of the low-refractive-index layer, using a C-light source, and the result is obtained under a 2-degree field of view. The average visible light reflectance is obtained by correcting for the reflectance of each wavelength of visible light using relative visibility and averaging the values. In this case, the relative visibility standard relative visibility is used.

[0182] The width of the liquid accumulation at the outer peripheral edge of the substrate (the width of the liquid accumulation from the outermost periphery of the coating surface) a is more preferably 0.7 mm or less, and even more preferably 0.4 mm or less.

[0183] The coating liquid (P) of the present invention can form an antireflective film with excellent film-forming properties.

[0184] Therefore, it is preferred for use in glass cathode ray tubes; displays for televisions, computers, car navigation systems, mobile phones, etc.; mirrors with glass surfaces; and glass display cases, solar cells, and other fields where light reflection prevention is desired.

[0185] In particular, it is useful for anti-reflective applications in liquid crystal displays, plasma displays, projection displays, electroluminescent (EL) displays, surface-conduction electron-emitter displays (SED), field emission displays (FET), cathode ray tubes (CRT), or solar cells.

[0186] Example

[0187] The following examples illustrate the invention in further detail, but the invention is not limited to these examples. It should be noted that the abbreviations for compounds and solvents are as follows.

[0188] TEOS: Tetraethoxysilane.

[0189] F13: Tridecylfluorooctyltrimethoxysilane.

[0190] UPS: γ-Ureapropyltriethoxysilane.

[0191] MeOH: Methanol.

[0192] PG: Propylene glycol.

[0193] NMP: N-methyl-2-pyrrolidone.

[0194] [Solution viscosity]

[0195] The measurement was performed using an E-type viscometer (Toki Sangyo Co., Ltd., TV-20), with a sample volume of 1.1 mL, using a conical rotor TE-1 (1°34', R24), at a temperature of 25°C.

[0196] [Surface tension]

[0197] The surface tension was measured using a fully automated contact angle meter (trade name: AUTO DISPENCER AD-3) manufactured by Kyowa Interface Chemical Co., Ltd. Furthermore, the specific gravity of the solution was measured according to JIS Z 8804:2012, and the surface tension value was calculated by multiplying it by the droplet method measurement.

[0198] [Synthesis of polysiloxane (P)]

[0199] <Synthesis example 1>

[0200] TEOS (31.6 g), F13 (6.2 g), and MeOH (30.3 g) were added to a 200 mL four-necked flask equipped with a reflux duct. The mixture was stirred and cooled in an ice bath at 10 °C. Then, MeOH (15.1 g), water (15.0 g), and oxalic acid (0.8 g) were added, and the mixture was stirred in an ice bath at 10 °C for 30 minutes. The mixture was then stirred at 65 °C for 2 hours. Next, UPS (0.5 g) and MeOH (0.5 g) were added, and the mixture was further reacted at 65 °C for 2 hours. Finally, the mixture was cooled to room temperature to obtain solution K1.

[0201] [Preparation of coating solution (P)]

[0202] <Preparation Example 1>

[0203] PG (5g), NMP (20g) and MeOH (63g) were added to solution K1 (12g) and stirred to obtain coating solution KL1.

[0204] The viscosity and surface tension of the coating liquid KL1 at 25℃ are 1.1 mPa·s and 23 mN / m, respectively.

[0205] [Manufacturing of substrates with anti-reflective coating]

[0206] <Example 1>

[0207] Using the coating liquid KL1 obtained in Preparation Example 1, a substrate S-1 with an anti-reflective film was obtained by spraying onto the substrate I with a film thickness of 100 nm after firing under the following conditions and firing under the following firing conditions.

[0208] <Comparative Example 1>

[0209] The substrate used was changed from substrate I to substrate II, except that it was carried out in the same manner as in Example 1, thereby obtaining substrate R-1 with an anti-reflective film.

[0210] <Comparative Example 2>

[0211] The substrate used was changed from substrate I to substrate III, except that it was carried out in the same way as in Example 1, thereby obtaining substrate R-2 with anti-reflective film.

[0212] [Spraying]

[0213] Spraying is performed under the apparatus and conditions described below.

[0214] Device name: API-240-3D spray painting machine manufactured by Apeiros Corporation.

[0215] <Coating Conditions>

[0216] Nozzle model: LPVN45, nozzle height: 100mm, Y-axis spacing: 7mm, air pressure: 470kPa, liquid flow rate: 4.9mL / min, nozzle speed: 170mm / sec.

[0217] [Firing conditions]

[0218] Dry on a heating plate at 40°C for 5 minutes, then fire in a hot air circulating oven at 200°C for 30 minutes.

[0219] [Substrate]

[0220] <Substrate I>

[0221] As substrate I, a soda-lime glass (manufactured by Matsunami Glass Industry Co., Ltd.) with a shape of 76mm × 76mm × thickness of 1.3mm is used.

[0222] Perform chamfering on the ends of substrate I. For chamfering, on the surface, it is performed in an area of ​​1.5 mm (R-surface machining, radius 2.5 mm) from the outermost periphery of the substrate, and on the back side, it is performed in an area of ​​0.1 mm (R-surface machining) from the outermost periphery of the substrate.

[0223] An optical microscope photograph of the cross-sectional shape of the end of substrate I is shown. Figure 3-1 Furthermore, a schematic cross-sectional view of the end of substrate I is shown in the figure. Figure 3-2 .

[0224] <Substrate II>

[0225] As substrate II, a soda-lime glass (manufactured by Nippon Sheet Glass Co., Ltd.) with a shape of 100mm × 100mm × 0.7mm thickness is used.

[0226] Chamfering at the ends (C-surface machining performed on both the front and back surfaces)

[0227] An optical microscope photograph of the cross-sectional shape of the end of substrate II is shown. Figure 4-1 Furthermore, a schematic cross-sectional view of the end of substrate II is shown in the figure. Figure 4-2 .

[0228] <Substrate III>

[0229] Substrate III is a substrate with an R-shaped chamfer at its ends, wherein the center c of the R-shaped chamfer is not located on the normal s passing through the junction of the R-shaped chamfer surface and the coating surface. The cross-sectional shape of the end of substrate III is shown below. Figure 5 .

[0230] [Evaluation of uneven coating ends]

[0231] Using substrates S-1, R-1, and R-2 with antireflective films obtained in Example 1, Comparative Example 1, and Comparative Example 2, the width of the liquid accumulation at the ends was measured using an optical microscope (Keyence VHX-7000 digital microscope manufactured by Keyence Co., Ltd.). The results are shown in Table 1.

[0232] An optical microscope image of the coating tip from Example 1 is shown below. Figure 6 An optical microscope image of the coating tip in Comparative Example 1 is shown below. Figure 7 .

[0233] [Reflectivity]

[0234] A black film (kukkirimieru, manufactured by Tomoewa Paper Co., Ltd.) was adhered to the back (uncoated side) of the substrate with antireflective film produced in Example 1. The reflectance within the wavelength range of 380 nm to 800 nm at an incident angle of 5° was measured using a UV-3600 UV-Vis-NIR spectrophotometer manufactured by Shimadzu Corporation. Based on the obtained spectral reflectance curve, the average visible light reflectance of one side (coated side) was calculated according to JIS R 3106. The average visible light reflectance (coated side) was 1.6%.

[0235]

[0236] According to Table 1, by coating a substrate (A) with a curved surface on the end face of the substrate with a coating liquid (P) containing polysiloxane (P) and forming a film, a substrate with an anti-reflective film that is uniform in the in-plane and suppresses liquid accumulation at the end can be obtained.

[0237] Industrial availability

[0238] The present invention has excellent anti-reflective properties and improves visibility due to unevenness at the end of the substrate, thus improving quality and is expected to be used in cover lenses for displays, etc. that use this substrate.

[0239] Explanation of reference numerals in the attached figures

[0240] 11: Substrate; 11a: Coated surface; 11b: Back side; 12: Substrate end face; 15a: Edge; 16a: R-shaped chamfered surface.

[0241] It should be noted that the entire contents of the specification, technical solution, drawings and abstract of Japanese Patent Application No. 2023-134905, filed on August 22, 2023, are incorporated herein by reference as a disclosure of the specification of this invention.

Claims

1. A method for manufacturing a substrate with an anti-reflective film, comprising: Step 1: The following coating liquid P is applied to the following substrate A to form a coating film; as well as Step 2 involves curing the coated film through firing. Coating solution P: A coating solution containing polysiloxane P as a polymer component, wherein the viscosity of the coating solution is 0.3–100 mPa·s and the surface tension is 20–40 mN / m. Substrate A: A substrate for which a radius (R) chamfer has been applied to the first angle formed between the main surface of the substrate to which the coating film is formed and the end face of the substrate, wherein the radius of the radius chamfer is 0.2 to 3.0 mm, and the distance from the outermost periphery of the substrate with the radius chamfer is 0.1 to 2.0 mm. The point where the R-shaped chamfered surface meets the main surface of the substrate to which the coating film is applied does not have an angle formed by a height difference.

2. The manufacturing method according to claim 1, wherein, The polysiloxane P is a polysiloxane having urea groups and / or urea bonds.

3. The manufacturing method according to claim 1 or 2, wherein, The polysiloxane P is a polysiloxane having fluorine-containing organic groups.

4. The manufacturing method according to claim 1 or 2, wherein, The coating in step 1 is spray coating.

5. A substrate with an anti-reflective film, obtained by the method as described in claim 1 or 2.

6. A coating liquid, which is a coating liquid P used in the method for manufacturing a substrate with an antireflective film as described in claim 1, said coating liquid having the following characteristics: Coating liquid P: A coating liquid containing polysiloxane P as a polymer component, wherein the viscosity of the coating liquid is 0.3 to 100 mPa·s and the surface tension is 20 to 40 mN / m.

7. The coating liquid according to claim 6, wherein, The polysiloxane P is a polysiloxane having urea groups and / or urea bonds.

8. The coating liquid according to claim 6 or 7, wherein, The polysiloxane P is a polysiloxane having fluorine-containing organic groups.

9. An antireflective film formed using the coating liquid as described in claim 6 or 7.

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