Method for manufacturing antireflection film-bearing substrate, and antireflection film-bearing substrate

Abstract

Provided are: a method for manufacturing an antireflection film-bearing substrate, wherein the method can provide an antireflection film-bearing substrate that can suppress liquid accumulation at an outer peripheral edge of the substrate; and an antireflection film-bearing substrate provided by this manufacturing method.　The method for manufacturing an antireflection film-bearing substrate comprises: a step (1) for forming a coating film by applying the following coating liquid (P) to the following substrate (A); and a step (2) for curing the coating film by firing.　Coating liquid (P): a coating liquid containing a polysiloxane (P) as a polymer component, wherein the coating liquid has a viscosity of 0.3 to 100 mPa·s and a surface tension of 20 to 40 mN / m.　Substrate (A): the substrate has a chamfering treatment R executed at a first corner angle that is formed between a substrate end surface and a substrate main surface on which the coating film is formed, wherein the radius of the chamfering treatment R is 0.2 to 3.0 mm, the distance from the outermost peripheral portion of the substrate, where the chamfering treatment R has been performed, is 0.1 to 2.0 mm, and the contact point between the chamfered surface R and the substrate main surface on which the coating film is formed does not have an angle due to a level difference.

Description

Method for manufacturing substrate with anti-reflection film, and substrate with anti-reflection film

[0001] The present invention relates to a method for producing a substrate with an antireflective film, which uses a film-forming coating liquid that mainly contains a polysiloxane obtained by polycondensing a specific alkoxysilane and further has a specific liquid composition, and a substrate having a specific configuration, and to a substrate with an antireflective film obtained by the production method.

[0002] It has been known that forming a coating having a refractive index lower than that of the substrate on the surface of a substrate reduces the reflectance of light reflected from the coating surface. Low-refractive-index coatings exhibiting such reduced reflectance are used as anti-reflection coatings and are applied to various substrate surfaces. Generally, wet and dry processes are known as methods for forming low-refractive-index coatings on substrates, such as glass substrates. Dry processes include vacuum deposition and CVD, but these methods pose problems such as productivity and cost. Wet processes include well-known techniques such as spin coating, dip coating, and spray coating. Among these, spray coating has attracted attention as a coating method that is less dependent on the substrate and takes productivity and cost into consideration. Spray coating involves dropping fine droplets onto a substrate and forming a film by wetting and spreading the liquid. It has the advantages of being independent of the substrate and minimizing waste of the coating liquid. Therefore, it is expected to reduce the cost of low-refractive-index glass and improve production efficiency. Patent Document 1 discloses a coating liquid for forming a film to be spray-coated, which contains a specific polysiloxane and a solvent component.

[0003] WO2011 / 136370 publication

[0004] In recent years, display elements to which low-reflection coatings are applied are mainly large-screen, high-resolution display elements. These display elements often use substrates with curved edges to enhance their design. The inventors' investigations revealed that when a conventional coating liquid for forming a film is applied to a curved substrate, a liquid pool forms around the outer edge of the substrate.

[0005] In view of the above, an object of the present invention is to provide a method for manufacturing a substrate with an anti-reflection film, which can obtain a substrate with an anti-reflection film that can suppress liquid pooling at the outer peripheral edge of the substrate, and a substrate with an anti-reflection film obtained by the manufacturing method.

[0006] As a result of intensive research into achieving the above-mentioned object, the inventors have found that using a coating liquid having a specific liquid composition and a substrate having a specific configuration is extremely effective in achieving the above-mentioned object, and have completed the present invention.

[0007] The present invention encompasses the following aspects: A method for producing a substrate with an anti-reflection film, comprising: a step (1) of applying the following coating liquid (P) to the following substrate (A) to form a coating film; and a step (2) of curing the coating film by baking. Coating liquid (P): A coating liquid containing polysiloxane (P) as a polymer component, the coating liquid having a viscosity of 0.3 to 100 mPa·s and a surface tension of 20 to 40 mN / m. Substrate (A): A substrate having a first edge angle formed between a main surface on which a coating film is formed and an edge face of the substrate, the radius of the R-chamfering being 0.2 to 3.0 mm, the distance from the outermost periphery of the R-chamfered substrate being 0.1 to 2.0 mm, and the contact point between the R-chamfered surface and the main surface on which a coating film is formed of the substrate having no corner due to a step.

[0008] Throughout this specification, examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, and * represents a bond in all cases.

[0009] According to the present invention, it is possible to obtain a substrate with an anti-reflection film in which liquid pooling at the outer peripheral edge of the substrate is suppressed, and a display element with high designability and excellent display quality can be obtained.

[0010] FIG. 2 is a local cross-sectional view of the outer periphery of a substrate according to one embodiment of substrate (A). FIG. 3 is a schematic perspective view of the substrate 11 according to FIG. 1. FIG. 4 is an optical microscope photograph of the cross-sectional shape of the end of substrate I in Example 1. FIG. 5 is a schematic cross-sectional view of the end of substrate I in Example 1. FIG. 6 is an optical microscope photograph of the cross-sectional shape of the end of substrate II in Comparative Example 1. FIG. 7 is a schematic cross-sectional view of the end of substrate II in Comparative Example 1. FIG. 8 is a schematic cross-sectional view of the end of substrate III in Comparative Example 2. FIG. 9 is an optical microscope photograph of the end of a coating film in Example 1. FIG. 10 is an optical microscope photograph of the end of a coating film in Comparative Example 1.

[0011] <Polysiloxane (P)> The anti-reflection coated substrate of the present invention is obtained using a coating liquid containing polysiloxane (P) as a polymer component. The structure of the polysiloxane (P) is not particularly limited. The polysiloxane (P) can be obtained, for example, by polycondensation of an alkoxysilane compound component containing an alkoxysilane compound. The polysiloxane (P) may be composed of one or more types of polymers. The polysiloxane (P) may be, for example, a polysiloxane having a ureido group and / or a urea bond. By having such a configuration, an effect is achieved in that a coating film with high hardness can be obtained even when fired at a relatively low temperature.

[0012] The polysiloxane having the ureido group and / or urea bond can be obtained, for example, by polycondensing an alkoxysilane compound component containing an alkoxysilane compound represented by the following formula (1): １ {Si(OR １’ ) ３} ｐ (1) In formula (1), p represents an integer of 1 or 2. １ is a p-valent organic group having 2 to 13 carbon atoms and a ureido group and / or a urea bond, and more preferably a p-valent organic group having 2 to 7 carbon atoms. When p is 1, R １ is preferably a monovalent organic group in which any hydrogen atom of a hydrocarbon group having 1 to 12 carbon atoms has been substituted with a ureido group, and more preferably a monovalent organic group in which any hydrogen atom of a hydrocarbon group having 1 to 6 carbon atoms has been substituted with a ureido group. １is preferably a divalent organic group in which a urea bond is inserted between any carbon-carbon bond of a hydrocarbon group having 2 to 12 carbon atoms, and more preferably a divalent organic group in which a urea bond is inserted between any carbon-carbon bond of a hydrocarbon group having 2 to 6 carbon atoms. １’ is an alkyl group having 1 to 5 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group or an ethyl group. １’ may be the same or different. １ , R １’ may have a linear or branched structure.

[0013] In the alkoxysilane compound represented by formula (1), when p is 1, it is an alkoxysilane compound represented by formula (1-1). １ Si(OR １’ ) ３ (1-1)

[0014] When p is 2, the alkoxysilane compound is represented by formula (1-2). (R １’ O) ３ Si-R １ -Si(OR １’ ) ３ (1-2)

[0015] Specific examples of the alkoxysilane compound represented by formula (1-1) include, but are not limited to, the following. Examples include γ-ureidopropyltriethoxysilane, γ-ureidopropyltrimethoxysilane, γ-ureidopropyltripropoxysilane, (R)-N-1-phenylethyl-N'-triethoxysilylpropylurea, and (R)-N-1-phenylethyl-N'-trimethoxysilylpropylurea. Of these, γ-ureidopropyltriethoxysilane and γ-ureidopropyltrimethoxysilane are particularly preferred because they are readily available as commercial products.

[0016] Specific examples of the alkoxysilane compound represented by formula (1-2) include, but are not limited to, 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-(trippropoxysilyl)propyl]urea. Of these, 1,3-bis[3-(triethoxysilyl)propyl]urea is particularly preferred because it is readily available as a commercially available product.

[0017] 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, based on the total amount of alkoxysilanes used to obtain the polysiloxane (P), from the viewpoint of favorably achieving the effects of the present invention. Also, from the viewpoint of favorably achieving the effects of the present invention, the amount is preferably 60 mol% or less, more preferably 50 mol% or less, and even more preferably 40 mol% or less.

[0018] From the viewpoint of obtaining a low refractive index coating, the polysiloxane (P) may be a polysiloxane having a fluorine-containing organic group. Such a fluorine-containing organic group 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. Specific examples thereof include a trifluoropropyl group, a tridecafluorooctyl group, a heptadecafluorodecyl group, and a pentafluorophenyl group. Among these, a perfluoroalkyl group is preferred because it is easy to obtain a highly transparent coating. More preferred is a perfluoroalkyl group having 3 to 15 carbon atoms. Specific examples include a perfluoropropyl group, a perfluorooctyl group, and a perfluorodecyl group.

[0019] In the present invention, multiple types of polysiloxanes having a fluorine-containing organic group on the side chain may be used in combination. The method for obtaining the polysiloxane having the above-mentioned fluorine-containing organic group on the side chain is not particularly limited. In general, it is obtained by polycondensing an alkoxysilane having the above-mentioned organic group on the side chain. Among them, polysiloxanes obtained by polycondensing an alkoxysilane component containing an alkoxysilane compound represented by formula (2a) are preferred. R ２ Si(OR ２’ ) ３ (2a)

[0020] The alkoxysilane compound represented by formula (2a) is an alkoxysilane having the above-mentioned fluorine-containing organic group in the side chain. ２ represents the above-mentioned fluorine-containing organic group, but the number of fluorine atoms contained in this organic group is not particularly limited. ２’ represents a hydrocarbon group having 1 to 5 carbon atoms, preferably a saturated hydrocarbon group having 1 to 5 carbon atoms, more preferably a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a t-butyl group, or an s-butyl group. Here, n- means normal, i- means iso, s- means secondary, and t- means tertiary. ２’ may be the same or different.

[0021] Among such alkoxysilane compounds represented by formula (2a), R ２ an alkoxysilane compound in which R is a perfluoroalkyl group, or ２ is an organic group represented by the following formula (2F): ３ (CF ２ ) ｋ CH ２ CH ２-* (2F) In formula (2F), k represents an integer of 0 to 12, and from the viewpoint of suitably achieving the effects of the present invention, k is preferably an integer of 0 to 8. Specific preferred examples of the alkoxysilane compound represented by formula (2a) include 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, (1H,1H,2H,2H-tridecafluorooctyl)trimethoxysilane, (1H,1H,2H,2H-tridecafluorooctyl)triethoxysilane, (1H,1H,2H,2H-heptadecafluorodecyl)trimethoxysilane, and (1H,1H,2H,2H-heptadecafluorodecyl)triethoxysilane. In the present invention, at least one of the alkoxysilane compounds represented by formula (2a) may be used, but multiple types may also be used if necessary. The total molar amount of the alkoxysilane compound represented by formula (2a) is preferably 5 mol % or more, more preferably 10 mol % or more, based on the total molar amount of silicon atoms contained in the alkoxysilane compound used in synthesizing the polysiloxane (P), and from the viewpoint of obtaining a homogeneous coating solution, it is preferably 40 mol % or less, more preferably 30 mol % or less.

[0022] The polysiloxane (P) may be a polysiloxane having a fluorine-containing organic group in the main chain direction of the polysiloxane. As a monomer component for synthesizing such a polysiloxane (P), for example, an alkoxysilane compound in which two trialkoxysilyl groups are bonded to a divalent organic group having a fluorine atom may be used. Specific examples of the alkoxysilane compound include alkoxysilane compounds represented by the following formula (2b): (OR ２ｂ’ ) ３ Si-R ２ｂ -Si(OR ２ｂ’ ) ３ (2b) where R in formula (2b) ２ｂ represents the above-mentioned fluorine-containing organic group, but the number of fluorine atoms contained in this organic group is not particularly limited. ２ｂ is preferably a divalent perfluoroalkyl chain or *-CH ２ -CH ２ -(CF ２ ) ｐ-CH ２ -CH ２ -* (p is an integer of 1 to 12). ２ｂ’ are each independently a hydrocarbon group having 1 to 5 carbon atoms, preferably a saturated hydrocarbon group having 1 to 5 carbon atoms, more preferably a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a t-butyl group, or an s-butyl group. ２ｂ’ may be the same or different. Specific examples of formula (2b) include 1,6-bis(2-trimethoxysilylethyl)dodecafluorohexane and 1,6-bis(2-triethoxysilylethyl)dodecafluorohexane.

[0023] In addition, as a monomer component for obtaining polysiloxane (P), other alkoxysilane compounds may be used in addition to the alkoxysilane compounds represented by the above formula (1) and the alkoxysilane compounds represented by the above formula (2a) or (2b) used as needed. Furthermore, polysiloxane (P) may be a polymer obtained by polycondensation of an alkoxysilane compound component containing only other alkoxysilane compounds. One or more types of the above other alkoxysilane compounds may be used. Preferred specific examples of the other alkoxysilane compounds include, but are not limited to, alkoxysilane compounds represented by the following formula (3), alkoxysilane compounds represented by the following formula (4), and alkoxysilane compounds represented by the following formula (5). R ３ ｎ Si(OR ３’ ) ４－ｎ (3) (In formula (3), R ３ represents a monovalent organic group that does not have a ureido group, a urea bond, or a fluorine atom, and R ３’ represents a hydrocarbon group having 1 to 5 carbon atoms, and n represents an integer of 1 to 3. ４ ) ４ (4) (R in formula (4) ４ represents a hydrocarbon group. ５’ O) ３ Si-R ５ -Si(OR５’ ) ３ (5) (In formula (5), R ５ represents a divalent organic group having 1 to 20 carbon atoms that does not contain a ureido group, a urea bond, or a fluorine atom, and R ５’ represents a hydrocarbon group having 1 to 5 carbon atoms.

[0024] R in the above formula (3) ３ The number of carbon atoms in R is preferably 1 to 20, more preferably 1 to 15. When n is 2 or 3, R ３ may be the same or different. ３’ In the formula, when n is 1 or 2, R ３’ may be the same or different. Specific examples of the alkoxysilane represented by formula (3) are shown below, but are not limited to these: methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, pentyltrimethoxysilane, pentyltriethoxysilane, heptyltrimethoxysilane, heptyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, hexadecyltrimethoxysilane, hexadecyltriethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxy ... 3-isocyanatepropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane; 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane; γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane; γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane; trialkoxysilanes such as 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, and γ-methacryloxypropyltriethoxysilane.

[0025] The amount of the alkoxysilane compound represented by 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, based on the total alkoxysilane compounds used to obtain the polysiloxane (P), from the viewpoint of favorably achieving the effects of the present invention. Also, from the viewpoint of favorably achieving the effects of the present invention, the amount is preferably 60 mol% or less, more preferably 50 mol% or less, and even more preferably 40 mol% or less.

[0026] R in formula (4) ４ represents a hydrocarbon group, and from the viewpoint of increasing reactivity, a saturated hydrocarbon group having 1 to 5 carbon atoms is preferred, and a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a t-butyl group, or an s-butyl group is more preferred. ４ may be the same or different. Specific examples of the tetraalkoxysilane compound of formula (4) include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, etc., which are readily available as commercial products. In the present invention, at least one of the alkoxysilane compounds represented by formula (4) may be used, but multiple types may be used as necessary. The amount of the alkoxysilane compound of formula (4) used is preferably 40 mol% or more, and 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, and more preferably 96 mol% or less.

[0027] In the alkoxysilane compound of formula (5), R ５’ is a hydrocarbon group having 1 to 5 carbon atoms, preferably a saturated hydrocarbon group having 1 to 4 carbon atoms, and more preferably a saturated hydrocarbon group having 1 to 3 carbon atoms. ５’ may be the same or different. ５is a divalent organic group having 1 to 20 carbon atoms that does not contain a ureido group, a urea bond, or a fluorine atom, and the divalent organic group may contain a double bond, a triple bond, or a cyclic structure or a branched structure such as a phenyl group. The divalent organic group may also contain a heteroatom such as a nitrogen atom, an oxygen atom, or a fluorine atom. In the present invention, multiple types of alkoxysilane compounds represented by formula (5) can be used as needed.

[0028] Preferred examples of the alkoxysilane compound represented by formula (5) include dimethyldimethoxysilane and dimethyldiethoxysilane. The amount of the alkoxysilane compound represented by formula (5) used is preferably 1 mol% or more, more preferably 2 mol% or more, of the total amount of the alkoxysilane compounds used in the synthesis of polysiloxane (P). Also, it is preferably 30 mol% or less, more preferably 20 mol% or less.

[0029] The method for polycondensing the polysiloxane (P) used in the present invention is not particularly limited, but examples include a method in which an alkoxysilane compound is hydrolyzed and condensed in an organic solvent such as an alcohol or a glycol. In this case, the hydrolysis and condensation reaction may be either partial hydrolysis or complete hydrolysis. In the case of complete hydrolysis, water may be added in an amount of 0.5 or more times by mole the total alkoxy groups in the alkoxysilane compound. 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 2.5 times by mole, preferably 0.1 to 2.0 times by mole the total alkoxy groups in the alkoxysilane compound.

[0030] In addition, typically, an acid or alkali may be added as a catalyst to promote the hydrolysis and condensation reaction. Examples of such acid catalysts include inorganic acids such as hydrochloric acid, sulfuric acid, and nitric acid; and organic acids such as acetic acid, oxalic acid, and formic acid. Examples of alkali catalysts include inorganic salts such as sodium and potassium; and various amines (e.g., methylamine, ethylamine, ethanolamine, triethylamine, and ammonia). In this case, the amount of catalyst used in the reaction is preferably 0.001 to 0.05 times the molar amount of all alkoxy groups in the alkoxysilane compound, and more preferably 0.01 to 0.03 times the molar amount. Furthermore, the hydrolysis and condensation reaction may be promoted by heating a solution in which the alkoxysilane compound is dissolved. The heating temperature can be selected as desired, and the reaction system is preferably 50°C or higher and preferably 180°C or lower. The heating time can be selected as desired, and is preferably 10 minutes or longer, and more preferably within 24 hours. More preferred reaction conditions include, for example, a method in which the mixture is stirred while being heated at 50° C. for 24 hours, or a method in which the mixture is stirred while being heated under reflux for 2 to 10 hours.

[0031] Another example of an alternative method is to heat a mixture of an alkoxysilane compound, a solvent, and an acid. Specifically, an acid is first added to an alcoholic solvent to prepare an alcoholic solution of the acid, and then the solution is mixed with an alkoxysilane and heated. The amount of acid is preferably 0.2 to 2 moles, more preferably 0.5 to 2 moles, per mole of all alkoxy groups in the alkoxysilane compound. Heating in this method is preferably performed at a liquid temperature of 50°C or higher, and preferably 180°C or lower. The reaction time is preferably 10 minutes or longer, and preferably within 24 hours.

[0032] In each of the above methods, when a plurality of alkoxysilane compounds are used, the plurality of alkoxysilane compounds may be mixed in advance or may be added sequentially.

[0033] When polycondensing an alkoxysilane compound by the above method, the total amount of silicon atoms in the alkoxysilane compound used in the reaction is adjusted to SiO２ (hereinafter referred to as SiO ２ The concentration (referred to as the converted concentration) is preferably 20% by mass or less, and more preferably 15% by mass or less. Selecting any concentration within this concentration range is preferable from the viewpoint of suppressing gel formation and obtaining a homogeneous polysiloxane solution. The solvent used in polycondensing the alkoxysilane compound is not particularly limited as long as it dissolves the alkoxysilane compound represented by formula (1), the alkoxysilane compound represented by formula (2a), the alkoxysilane compound represented by formula (2b), and the alkoxysilane compounds represented by formulas (3) to (5). Preferably, alcohols or organic solvents having good compatibility with alcohols are used.

[0034] Specific examples of organic solvents used in polycondensing alkoxysilane compounds include alcohols such as methanol, ethanol, propanol, butanol, and 2-methyl-2,4-pentanediol (also known as hexylene glycol); 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. In the present invention, a mixture of two or more of the above organic solvents may be used.

[0035] <Molecular Weight of Polysiloxane (P)> The polysiloxane (P) has a weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC) of preferably 500 to 500,000, and more preferably 1,000 to 300,000. The molecular weight distribution (Mw / Mn), expressed as the ratio of Mw to the number average molecular weight (Mn) in terms of polystyrene measured by GPC, is preferably 15 or less, and more preferably 10 or less. A molecular weight within this range is preferred from the viewpoint of suitably achieving the effects of the present invention.

[0036] <Coating Liquid (P)> The coating liquid (P) of the present invention contains polysiloxane (P) as a polymer component, and 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 a value measured using an E-type viscometer at a temperature of 25°C, and the surface tension of the coating liquid is a value measured by the sessile drop method at a temperature of 25°C. 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. Also, it is more preferably 80 mPa·s or less, and even more preferably 50 mPa·s or less. 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. Also, it is more preferably 37 mN / m or less, and even more preferably 35 mN / m or less.

[0037] The coating liquid (P) of the present invention is preferably a coating liquid containing polysiloxane (P) and a solvent. Specific examples of the solvent that can be used in the coating liquid (P) include the following solvents. Alcohols such as 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, and diacetone alcohol; cyclic alcohols such as cyclopropanol, cyclobutanol, cyclopentanol, cyclohexanol, 2-methylcyclohexanol, cycloheptanol, cyclooctanol, cyclononanol, and cyclodecanol; glycols such as ethylene glycol, propanediol, diethylene glycol, dipropylene glycol, butanediol (such as 1,3-butanediol and 2,3-butanediol), 2-methyl-2,4-pentanediol, pentanediol, hexanediol, and heptanediol;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 ethers such as tetrahydrofuran and 1,4-dioxane; Examples of suitable ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; esters include methyl acetate, ethyl acetate, and ethyl lactate; lactams such as N-methyl-2-pyrrolidone; amides such as N,N-dimethylformamide, N,N-dimethylacetamide, tetramethylurea, and hexamethylphosphotriamide; lactones such as γ-butyrolactone; and dimethyl sulfoxide.

[0038] Among the solvents 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 glycols having 3 to 10 carbon atoms (for example, ethylene glycol, propanediol, 2-methyl-2,4-pentanediol, etc.). Among the solvents 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, the above-mentioned ethers having 4 to 8 carbon atoms are preferred, 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).

[0039] The method for preparing the coating liquid (P) is not particularly limited. For example, a simple method is to use a polymerization solution containing polysiloxane (P) (hereinafter referred to as polymerization solution (P)) as it is and dilute it by mixing with a solvent. Furthermore, if necessary, the polymerization solution (P) may be concentrated and diluted by adding a solvent, or may be substituted with another solvent and then diluted by mixing with a solvent.

[0040] The content of polysiloxane (P) in the coating liquid (P) is determined by dividing the total amount of silicon atoms contained in polysiloxane (P) by the total amount of silicon atoms contained in SiO ２ Concentration converted to SiO ２ In terms of improving the storage stability of the solution, the concentration is preferably 15% by mass or less, more preferably 8% by mass or less.

[0041] From the viewpoint of suitably obtaining the effects of the present 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 excluding the solvent in the coating liquid (P). When the coating liquid (P) contains other components described below, 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 excluding the solvent in the coating liquid (P).

[0042] <Other Components> In the present invention, the coating liquid (P) may contain other components in addition to the polysiloxane (P) and the solvent. Specific examples of other components include inorganic fine particles, fillers, leveling agents, surface modifiers, surfactants, etc. The content of the other components may be 0.1 parts by mass or more, or 1 part by mass or more, relative to 100 parts by mass of all components in the coating liquid (P) excluding the solvent. The content may also be 90 parts by mass or less, or 80 parts by mass or less.

[0043] Examples of inorganic fine particles include metal oxide fine particles, metal double oxide fine particles, and magnesium fluoride fine particles.

[0044] Examples of metal oxide fine particles include fine particles of silica, alumina, titanium oxide, zirconium oxide, tin oxide, zinc oxide, etc. These may also be in a beaded form. Examples of metal double oxide fine particles include fine particles of ITO (indium tin oxide), ATO (antimony trioxide), AZO (zinc aluminum oxide), zinc antimonate, etc. Other examples include hollow silica fine particles and porous silica fine particles. The hollow silica fine particles may also be in a beaded form.

[0045] The inorganic fine particles may be in the form of either a powder or a colloidal solution, with a colloidal solution being preferred due to its ease of handling. This colloidal solution may be a dispersion of inorganic fine particle powder in a dispersion medium, or may be a commercially available colloidal solution. Commercially available inorganic fine particles include organosilica sol manufactured by Nissan Chemical Industries, 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 fine particle may be used alone, or two or more types may be used in combination.

[0046] In the present invention, by incorporating inorganic fine particles, it becomes possible to impart a desired surface shape and other functions to the cured coating film that is formed.

[0047] 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 from the prepared coating liquid may decrease. Here, the "average particle size" may refer to the average primary particle size of the inorganic fine particles measured by a method (BET method) based on the converted particle size from the specific surface area using a nitrogen gas adsorption method or by observation using a transmission electron microscope. In the present invention, the average particle size is measured by a method (BET method) based on the converted particle size from the specific surface area using a nitrogen gas adsorption method.

[0048] 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 film, the pH or pKa of the colloidal solution is preferably adjusted to 2 to 10, more preferably 3 to 7.

[0049] Examples of organic solvents used as dispersion media for colloidal solutions include alcohols such as methanol, ethanol, propanol, and butanol; glycols 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. Among these, alcohols and ketones are preferred. These organic solvents can be used alone or in combination as a dispersion medium. Furthermore, known fillers, leveling agents, surface modifiers, surfactants, and the like can be used, with commercially available products being particularly preferred due to their ease of availability.

[0050] <Production of Antireflection Coated Substrate> The antireflection coated substrate of the present invention includes an antireflection film. The antireflection film of the present invention is formed using the coating liquid (P) described above. One embodiment of the antireflection film of the present invention is obtained by a production method including: a step (1) of applying the coating liquid (P) described above to the substrate (A) described below to form a coating film; and a step (2) of curing the coating film by baking. Substrate (A): A substrate having a first edge angle formed by a main surface on which a coating film of the substrate is formed and an edge face of the substrate, the radius of the R-chamfering being 0.2 to 3.0 mm, and the distance from the outermost periphery of the substrate where the R-chamfering has been performed being 0.1 to 2.0 mm.

[0051] <Substrate (A)> The substrate (A) of the present invention has the above-described configuration. According to the above configuration, by chamfering the first edge angle formed by the main surface on which the coating film of the substrate is formed and the substrate edge face, it is possible to obtain a substrate with an anti-reflection film that can suppress liquid pooling at the outer peripheral edge of the substrate. Furthermore, according to the above configuration, only one of the first and second edge angles formed by both main surfaces and the substrate edge face of the substrate is round-chamfered, which has the advantage of reducing the number of manufacturing steps for the substrate compared to when round-chamfering both edge angles.

[0052] In the above configuration, R-chamfering may be performed on both a first edge angle formed between one main surface of the substrate and the substrate end face and a second edge angle formed between the other main surface of the substrate and the substrate end face. Alternatively, in the above configuration, R-chamfering with different radii may be performed on the first edge angle formed between both main surfaces of the substrate and the substrate end face. In the above configuration, R-chamfering may be performed on the first edge angle formed between one main surface of the substrate and the substrate end face, and C-chamfering may be performed on the second edge angle formed between the other main surface of the substrate and the substrate end face.

[0053] FIG. 1 shows a local cross-sectional view of the outer periphery of one embodiment of the substrate (A). In FIG. 1, the dotted line indicates the shape of the edge angle 15a before the R-chamfering process. The upper side of the substrate 11 (the surface including the edge angle 15a) is the coated surface 11a, and the lower side of the substrate 11 is the back surface 11b opposite the coated surface 11a. In the example shown in FIG. 1, only the edge angle 15a (first edge angle) formed between the coated surface 11a and the substrate edge surface 12 of the substrate 11 is subjected to R-chamfering with a radius r1a equal to or greater than the thickness t of the substrate 11 but less than twice the thickness t (t≦r1a<2t). In this way, only the edge angle 15a on the coated surface 11a side can form an R-chamfered surface 16a with a gentle curve in the thickness direction of the substrate 11. The contact point 17a between the R-chamfered surface 16a and the coated surface 11a does not have a corner due to a step. Specifically, the center of the R-chamfering applied to the corner 15a is preferably positioned on the normal line of the application surface 11a that passes through the contact point 17a. The center of the R-chamfering applied to the corner 15a is at position C1 on the imaginary dashed-dotted line T1-T1, which indicates a position at least equal to the thickness t of the substrate 11 but less than twice the thickness t in the cross section of the substrate 11 in the thickness direction.

[0054] The R-chamfering is performed within a region of a distance L1 from the outermost periphery of the substrate. In one embodiment of the substrate (A), the radius r1a is 0.2 to 3.0 mm, and from the viewpoint of favorably 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. 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 favorably 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.

[0055] FIG. 2 shows a schematic perspective view of the substrate 11 according to FIG.

[0056] Some or all of the corners of the substrate may be rounded, which allows each corner to be rounded with a gentle curve.

[0057] Examples of materials for the substrate (A) include known or well-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, triacetyl cellulose, diacetyl cellulose, triacetyl cellulose (TAC), and acetate butyrate cellulose. Among these, 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.

[0058] The coating liquid (P) can be used to form a coating film by applying a commonly used coating method, such as dip coating, spin coating, spray coating, slit coating, brush coating, roll transfer, screen printing, inkjet printing, or flexographic printing.

[0059] In one embodiment of the present invention, spray coating is used to prepare a substrate with an anti-reflection film. Spray coating is a method in which fine droplets are dropped onto a substrate and a film is formed by the liquid wetting and spreading, and has the advantages of being independent of the substrate and minimizing waste of the coating liquid.

[0060] Spray coating methods include two-fluid spraying, electrostatic spraying, and ultrasonic spraying. Among these, two-fluid spraying is mainly used for display surface treatment due to its simplicity and large-area coating capability. When two-fluid spraying is used in step (1), the thickness of the coating film can be adjusted by adjusting the liquid amount, gas pressure (gas flow rate), nozzle / stage distance (the distance between the nozzle and the stage), coating speed, etc.

[0061] The amount of liquid is a parameter that determines the film thickness, and increasing the amount of liquid makes the film thicker, while decreasing the amount of liquid makes the film thinner. In spray coating, the amount of chemical liquid is, for example, 0.5 to 20 mL (milliliters) / min, and preferably 1 to 12 mL / min.

[0062] The gas pressure or gas flow rate is a parameter for forming fine droplets. Examples of gases that can be used include N ２ Examples of gases that can be used include, but are not limited to, gas pressure and dry air. In spray coating, the gas pressure is, for example, 50 to 800 kPa, and preferably 100 to 700 kPa. Meanwhile, the gas flow rate is, for example, 3 to 80 L (liters) / min, and preferably 8 to 70 L / min. The gas pressure and gas flow rate vary depending on the diameter of the nozzle used, and therefore must be controlled according to the type of nozzle used.

[0063] The nozzle-to-stage distance is a parameter related to film thickness and coatability, and the film thickness increases as the distance decreases, and decreases as the distance increases. From the viewpoint of film thickness and coatability, the nozzle-to-stage distance is, for example, 5 to 200 mm, and preferably 30 to 150 mm.

[0064] The coating speed is a parameter related to the film thickness; a faster speed results in a thinner film thickness, and a slower speed results in a thicker film thickness. In spray coating, the coating speed is, for example, 10 to 2000 mm / s, and preferably 30 to 1500 mm / s.

[0065] The thickness of the coating formed on the substrate can be adjusted by the above-mentioned parameters during coating. ２ It can also be easily adjusted by the converted concentration.

[0066] In step (2), the drying step of removing the solvent is not necessarily required during the baking process. However, it is preferable to include the drying step when the time from coating to baking is not consistent for each substrate, or when baking is not performed immediately after coating. This drying step is sufficient as long as the solvent is removed to an extent that the coating film shape does not deform during transport of the substrate, and the drying method is not particularly limited. For example, a method of drying on a hot 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, can be used. The coating film formed by the above method can be baked to form a cured film. The baking 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 a hot plate, a hot air circulation oven, a far-infrared heating oven (IR oven), or a belt furnace. The coating thus obtained is characterized by good film-forming properties and high transmittance.

[0067] In the production of the anti-reflection film-coated substrate, after step (2), a step of exposing the coating film cured in step (2) (hereinafter also referred to as step (3)) may be carried out. In step (3), the light to be irradiated may be, for example, ultraviolet light containing light with a wavelength of 150 to 800 nm or visible light, with ultraviolet light containing light with a wavelength of 300 to 400 nm being preferred. Examples of light sources that can be used for the irradiation light include low-pressure mercury lamps, high-pressure mercury lamps, Deep UV lamps, deuterium lamps, metal halide lamps, argon resonance lamps, xenon lamps, mercury-xenon lamps, excimer lasers (e.g., KrF excimer lasers), fluorescent lamps, LED lamps, halogen lamps (e.g., sodium lamps), and microwave-excited electrodeless lamps. The light irradiation dose is preferably 1,000 to 200,000 J / m ２ and more preferably 1,000 to 100,000 J / m ２ is.

[0068] When the coating obtained according to the method of the present invention is used as an antireflection film, the coating can be formed according to the method of the present invention on the surface of a substrate having a refractive index higher than that of the coating, such as ordinary glass or film, thereby converting the substrate into one having antireflection properties. In this case, the coating is effective not only when used as a single coating on the substrate surface, but also when used as an antireflection laminate in which the coating is formed on an underlayer coating having a high refractive index.

[0069] Here, we will discuss the relationship between the thickness of the coating and the wavelength of light. It is known that the relationship between the thickness d (nm) of a coating having a refractive index a and the wavelength λ (nm) of light whose reflectance is desired to be reduced by this coating is d = (2b - 1)λ / 4a (where b is an integer of 1 or greater). Therefore, by determining the thickness of the coating using this formula, it is possible to easily prevent reflection of light of the desired wavelength.

[0070] The antireflection film of the present invention preferably has an average luminous reflectance of 3.0% or less, more preferably 2.0% or less, for visible light with wavelengths of 380 nm to 800 nm. The average luminous reflectance is determined from a spectral reflectance curve. The spectral reflectance curve is obtained after the surface of the antireflection substrate opposite the low refractive index layer is matted with black paint or after a black film is attached, and the angle of incidence from the normal to the low refractive index layer surface is set to 5 degrees, a C light source is used, and a 2-degree visual field is used. The average luminous reflectance is the reflectance value obtained by calibrating the reflectance of each wavelength of visible light using relative luminous efficiency and averaging it. In this case, the relative luminous efficiency is the standard relative luminous efficiency for photopic vision.

[0071] The width a of the liquid pool at the outer peripheral edge of the substrate (the width of the liquid pool from the outermost periphery of the coating surface) is more preferably 0.7 mm or less, and even more preferably 0.4 mm or less.

[0072] The coating liquid (P) of the present invention can form an antireflection film with excellent film-forming properties. Therefore, it can be suitably used in fields where antireflection of light is desired, such as glass cathode ray tubes; displays of televisions, computers, car navigation systems, mobile phones, etc.; mirrors with glass surfaces; glass showcases, solar cells, etc. In particular, it is useful for antireflection applications in liquid crystal displays, plasma displays, projection displays, EL (electroluminescence) displays, SEDs (surface-conduction electron-emitter displays), FETs (field emission displays), CRTs (cathode ray tubes), solar cells, etc.

[0073] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. The abbreviations for compounds and solvents are as follows.

[0074] TEOS: Tetraethoxysilane F13: Tridecafluorooctyltrimethoxysilane UPS: γ-ureidopropyltriethoxysilane MeOH: Methanol PG: Propylene glycol NMP: N-methyl-2-pyrrolidone

[0075] [Solution Viscosity] Measurement was performed using an E-type viscometer (TV-20, manufactured by Toki Sangyo Co., Ltd.) with a sample volume of 1.1 mL and a cone rotor TE-1 (1°34', R24) at a temperature of 25°C. [Surface Tension] Measurement was performed by the sessile drop method using a fully automatic contact angle meter (product name: AUTO DISPENCER AD-3) manufactured by Kyowa Interface Science Co., Ltd. The specific gravity of the solution was measured in accordance with JIS Z 8804:2012, and the surface tension value was calculated by multiplying this by the measurement value by the sessile drop method.

[0076] [Synthesis of Polysiloxane (P)] <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, 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 stirred for 30 minutes in an ice bath at 10°C. The mixture was then stirred at 65°C for 2 hours, after which UPS (0.5 g) and MeOH (0.5 g) were added and reacted at 65°C for another 2 hours. The mixture was then allowed to cool to room temperature to obtain Solution K1.

[0077] [Preparation of Coating Liquid (P)] <Preparation Example 1> PG (5 g), NMP (20 g), and MeOH (63 g) were added to Solution K1 (12 g) and stirred to obtain Coating Liquid KL1. The viscosity and surface tension of Coating Liquid KL1 were 1.1 mPa s and 23 mN / m, respectively, at 25°C.

[0078] [Production of Substrate with Antireflection Film] Example 1 Using the coating solution KL1 obtained in Preparation Example 1, the following substrate I was spray-coated under the following conditions so that the film thickness after baking would be 100 nm, and then baked under the following baking conditions to obtain a substrate S-1 with an antireflection film. Comparative Example 1 Substrate R-1 with an antireflection film was obtained by performing the same procedure as in Example 1, except that the substrate used was changed from substrate I to substrate II. Comparative Example 2 Substrate R-2 with an antireflection film was obtained by performing the same procedure as in Example 1, except that the substrate used was changed from substrate I to substrate III.

[0079] [Spray Coating] Spray coating was performed using the following equipment and conditions: Equipment name: Spray coater API-240-3D manufactured by Apiros Co., Ltd. <Coating conditions> Nozzle type: LPVN45, nozzle height: 100 mm, Y-axis pitch: 7 mm, air pressure: 470 kPa, chemical flow rate: 4.9 mL / min, nozzle speed: 170 mm / sec

[0080] [Baking Conditions] The coating was dried on a hot plate at 40°C for 5 minutes, and then baked in a hot air circulating oven at 200°C for 30 minutes.

[0081] [Substrate] <Substrate I> Substrate I was made of soda lime glass (manufactured by Matsunami Glass Industry Co., Ltd.) measuring 76 mm x 76 mm x 1.3 mm thick. The edges of Substrate I were chamfered. The chamfering was performed on the front surface in a region 1.5 mm from the outermost edge of the substrate (R-face processing, radius 2.5 mm) and on the back surface in a region 0.1 mm from the outermost edge of the substrate (R-face processing). An optical microscope photograph of the cross-sectional shape of the edge of Substrate I is shown in Figure 3-1. A schematic cross-sectional view of the edge of Substrate I is also shown in Figure 3-2. <Substrate II> Substrate II was made of soda lime glass (manufactured by Nippon Sheet Glass Co., Ltd.) measuring 100 mm x 100 mm x 0.7 mm thick. Edge Chamfering (C-face processing on both the front and back surfaces) An optical microscope photograph of the cross-sectional shape of the edge of Substrate II is shown in Figure 4-1. A schematic cross-sectional view of the edge of Substrate II is also shown in Figure 4-2. <Substrate III> Substrate III is a substrate in which R-chamfering has been performed on the substrate edge, and the center c of the R-chamfering is not positioned on the normal s passing through the contact point between the R-chamfered surface and the coating surface. The cross-sectional shape of the edge of Substrate III is shown in Figure 5.

[0082] [Evaluation of coating film edge unevenness] Using the anti-reflection film-coated substrates S-1, R-1, and R-2 obtained in Example 1, Comparative Example 1, and Comparative Example 2, the width of the liquid pool at the edge was measured using an optical microscope (Keyence Corporation's digital microscope VHX-7000). The results are shown in Table 1. An optical microscope photograph of the coating film edge in Example 1 is shown in FIG. 6, and an optical microscope photograph of the coating film edge in Comparative Example 1 is shown in FIG. 7.

[0083] [Reflectance] A black film (Kukkiri Miel, manufactured by Tomoegawa Paper Co., Ltd.) was attached to the back surface (uncoated surface) of the anti-reflection coated substrate produced in Example 1, and the reflectance was measured in the wavelength range of 380 nm to 800 nm at a light incident angle of 5° using an ultraviolet-visible-near-infrared spectrophotometer UV-3600 manufactured by Shimadzu Corporation, and the average luminous reflectance of one surface (coated surface) was calculated from the obtained spectral reflectance curve in accordance with JIS R 3106. The average luminous reflectance (coated surface) was 1.6%.

[0084] From Table 1, it was found that by applying a coating liquid (P) containing polysiloxane (P) to a substrate (A) having a curved surface on its end face to form a film, a substrate with an anti-reflection film that is uniform within the surface and suppresses liquid accumulation at the end can be obtained.

[0085] The present invention is expected to improve quality because it has excellent anti-reflection performance and improves the visibility of unevenness at the substrate edge, and is therefore expected to be used in display cover lenses and the like.

[0086] 11 Substrate 11a Coated surface 11b Back surface 12 Substrate end surface 15a Edge angle 16a R-chamfered surface

[0087] The entire contents of the specification, claims, drawings and abstract of Japanese Patent Application No. 2023-134905 filed on August 22, 2023 are hereby incorporated by reference as the disclosure of the specification of the present invention.

Claims

1. A method for producing a substrate with an anti-reflective coating, comprising: a step (1) of applying the following coating liquid (P) to the following substrate (A) to form a coating film; and a step (2) of curing the coating film by baking. Coating liquid (P): A coating liquid containing polysiloxane (P) as a polymer component, the coating liquid having a viscosity of 0.3 to 100 mPa·s and a surface tension of 20 to 40 mN / m. Substrate (A): A substrate having a first edge angle formed between a main surface of the substrate on which a coating film is formed and an edge surface of the substrate, the radius of the R-chamfering being 0.2 to 3.0 mm, the distance from the outermost periphery of the substrate on which the R-chamfering is performed being 0.1 to 2.0 mm, and a contact point between the R-chamfered surface and the main surface of the substrate on which a coating film is formed does not have a corner due to a step.

2. The method according to claim 1, wherein the polysiloxane (P) is a polysiloxane having a ureido group and / or a urea bond.

3. The method according to claim 1 or 2, wherein the polysiloxane (P) is a polysiloxane having a fluorine-containing organic group.

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-reflection film, obtained by the method according to claim 1 or 2.

6. A coating liquid (P) used in the method for producing a substrate with an anti-reflection film according to claim 1, said coating liquid having the following characteristics: Coating liquid (P): A coating liquid containing polysiloxane (P) as a polymer component, said coating liquid having a viscosity of 0.3 to 100 mPa·s and a surface tension of 20 to 40 mN / m.

7. The coating liquid according to claim 6, wherein the polysiloxane (P) is a polysiloxane having a ureido group and / or a urea bond.

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

9. An anti-reflection film formed by using the coating liquid according to claim 6 or 7.

Images