Laminate manufacturing method and laminate

Abstract

To provide a laminate manufacturing method that achieves both of high wear resistance / alkali resistance and high ultraviolet transmittance by wet coating capable of easily coating a large area with use inorganic fine particles such as silica having excellent humidity resistance or without use of the inorganic fine particles, a laminate, and a coating liquid used for manufacture of the laminate.SOLUTION: A manufacturing method for a laminate having a base material and a coating film applied to at least one of main surfaces thereof includes: a process in which an inorganic particle dispersion liquid containing a liquid dispersion medium A having a boiling point more than 121°C and less than 190°C, in which a weight ratio of the liquid dispersion medium A is 0.5% by mass or more and less than 15% by mass as the total amount of the inorganic fine particle dispersion liquid is 100% by mass, is coated to a base material; and a heat treatment process longer than 10 minutes at a temperature of 200°C or more and 1000°C or less.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a method for producing a laminate, a laminate, and a coating liquid. [Background technology]

[0002] Conventionally, laminates for UV devices have been studied, which are fabricated by forming an antireflection layer containing a fluoride on a substrate by sputtering or vapor deposition. For example, Patent Document 1 describes an optical element having, as an antireflection layer, a first thin film made of an oxide or nitride doped with fluoride, and a second thin film made of a fluoride material formed on the first thin film. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2005-345826 Summary of the Invention [Problem to be solved by the invention]

[0004] Antireflection layers containing inorganic fluorides have poor moisture resistance, and sputtering and vapor deposition methods are difficult to apply to large areas easily compared to coating methods such as wet coating.

[0005] The present invention aims to provide a method for producing a laminate that combines high abrasion resistance and alkali resistance with high ultraviolet transmittance by using inorganic fine particles such as silica that have excellent moisture resistance, or by using wet coating that allows for easy coating over large areas without using inorganic fine particles, as well as a laminate and a coating liquid used in producing the laminate. [Means for solving the problem]

[0006] The present inventors have conducted extensive research in light of the above background and have completed the present invention. That is, the present invention (a method for producing a laminate) and its preferred aspects or embodiments relate to, but are not limited to, the following. [1] A method for producing a laminate having a substrate and a coating film applied to at least one of its main surfaces, the method comprising the steps of: applying to a substrate an inorganic particle dispersion liquid containing inorganic particles and a liquid dispersion medium A having a boiling point greater than 121°C and less than 190°C, wherein the weight ratio of the liquid dispersion medium A is 0.5% by mass or more and less than 15% by mass, with the total amount of the inorganic particle dispersion liquid being 100% by mass; and a heat treatment step at a temperature of 200°C or more and 1000°C or less for a period of 10 minutes or longer. [2] The method for producing a laminate according to [1], wherein the substrate is quartz glass. [3] The method for producing a laminate according to [1] or [2], wherein the thickness of the coating film is 20 nm or more and 200 nm or less. [4] The method for producing a laminate according to any one of [1] to [3], wherein the inorganic fine particles are inorganic fine particles containing silica particles. [5] The method for producing a laminate according to any one of [1] to [4], wherein the inorganic fine particle dispersion contains a liquid dispersion medium B having a boiling point of less than 100°C. [6] The method for producing a laminate according to any one of [1] to [5], wherein the inorganic fine particle dispersion contains water. [7] The method for producing a laminate according to any one of [1] to [6], wherein the inorganic fine particle dispersion contains an alkoxysilane. [8] The method for producing a laminate according to [7], wherein the alkoxysilane contains a condensate of an alkoxysilane represented by the following general formula (1): General formula (1) [ka] (In the formula, each R independently represents an alkyl group having 1 to 6 carbon atoms, and n is an integer of 2 to 1000.) [9] The method for producing a laminate according to [7] or [8], wherein in the inorganic microparticle dispersion, the ratio of the weight of SiO2 contained in the alkoxysilane to the weight of the inorganic microparticles ([weight of SiO2 contained in the alkoxysilane] / [weight of inorganic microparticles]) exceeds 0.005.

[10] The method for producing a laminate according to any one of [1] to [9], wherein the inorganic fine particles have a primary particle diameter of 1 nm or more and less than 50 nm.

[0007] Furthermore, the present invention (laminate) and its preferred aspects or embodiments relate to the following items

[11] to

[12] , but are not limited thereto.

[11] A laminate obtainable by a method for producing a laminate having a substrate and a coating film applied to at least one of its main surfaces, the method comprising the steps of: applying to a substrate an inorganic particle dispersion liquid containing inorganic particles and a liquid dispersion medium A having a boiling point of more than 121°C and less than 190°C, wherein the weight ratio of the liquid dispersion medium A is 0.5% by mass or more and less than 15% by mass, with the total amount of the inorganic particle dispersion liquid being 100% by mass; and a heat treatment step at a temperature of 200°C or more and 1000°C or less for a period of more than 10 minutes.

[12] A laminate having a substrate and a coating film applied to at least one of its main surfaces, the coating film having a thickness of 20 nm or more and less than 75 nm, The average transmittance in the wavelength range of 185 nm or more and 300 nm or less is The laminate has an average transmittance that is 0.5 points or more higher than the average transmittance of the substrate not having the coating film.

[0008] The present inventors have further accomplished the following invention. That is, the present invention (laminate) and its preferred aspects or embodiments relate to the following items

[13] to

[25] , but are not limited thereto.

[13] A laminate having a substrate and a coating film applied to at least one of its main surfaces, the coating film has a porous structure and a thickness of 20 nm or more and less than 100 nm, The laminate is characterized in that the transmittance at any wavelength of 150 nm or more and less than 300 nm is 80.0% or more.

[14] The laminate according to

[13] , characterized in that the transmittance of the laminate at a wavelength of 185 nm is 91.0% or more.

[15] The laminate according to any one of

[13] to

[14] , wherein the coating film has a ratio of the number of carbon atoms to the total number of sodium, potassium, magnesium, calcium, aluminum and silicon atoms on the surface of the coating film of 1.00 or less.

[16] The laminate according to any one of

[13] to

[15] , wherein the coating film contains inorganic fine particles.

[17] The laminate according to

[16] , wherein the inorganic fine particles are inorganic fine particles containing silica.

[18] The laminate according to

[16] or

[17] , wherein the inorganic fine particles have a primary particle diameter of 1 nm or more and less than 50 nm.

[19] The laminate according to any one of

[13] to

[18] , obtainable by a production method including: a step of applying a coating liquid containing an alkoxysilane, water, an acid catalyst, and a pore-forming agent to a substrate; and a heat treatment step at a temperature of 200°C or higher and 1000°C or lower for longer than 10 minutes.

[20] The laminate according to any one of

[11] to

[19] , wherein the coating film has a kurtosis of 0.320 or less in brightness distribution in a cross-sectional image taken by a scanning electron microscope. [twenty one] The laminate according to any one of

[11] to

[20] , wherein the arithmetic mean roughness of the coating film is 0.1 nm or more and 10.0 nm or less. [twenty two] The laminate according to any one of

[11] to

[21] , wherein the substrate is quartz glass or sapphire glass. [twenty three] The laminate according to any one of

[11] to

[22] , wherein the thickness of the substrate is 0.1 mm or more and 100 mm or less. [twenty four] The laminate according to any one of

[12] to

[23] , obtainable by a production method including: a step of applying a coating agent to a substrate; and a step of heat treating the substrate at a temperature of 200°C or higher and 1000°C or lower for more than 10 minutes. [twenty five] A laminate obtainable by a method for producing a laminate having a substrate and a coating film applied to at least one of its main surfaces, the method comprising the steps of: applying a coating agent to a substrate; and heat treating the substrate at a temperature of 200°C or higher and 1000°C or lower for more than 10 minutes.

[0009] Furthermore, the present invention (coating liquid) and its preferred aspects or embodiments relate to the following items

[26] to

[31] , but are not limited thereto.

[26] A coating liquid containing an alkoxysilane, water, an acid catalyst, a pore-forming agent, and a liquid dispersion medium A having a boiling point of more than 121°C and less than 190°C, wherein the weight ratio of the liquid dispersion medium A is 0.5% by mass or more and less than 15% by mass, where the total amount of the coating liquid is 100% by mass.

[27] The coating liquid according to

[26] , comprising the following alkoxysilanes C01 and C02 as alkoxysilanes, wherein the ratio of the weight of SiO2 contained in alkoxysilane C02 to the total weight of SiO2 contained in the alkoxysilanes ([weight of SiO2 contained in alkoxysilane C02] / [total weight of SiO2 contained in alkoxysilanes]) is 0.00 or more and 0.50 or less. Alkoxysilane C01: At least one alkoxysilane selected from tetraalkoxysilanes and alkoxysilane condensates represented by the following general formula (01): General formula (01) [ka] (In the formula, each R independently represents an alkyl group having 1 to 6 carbon atoms, and n is an integer of 2 to 1000.) Alkoxysilane C02: At least one alkoxysilane selected from alkoxysilanes represented by the following general formula (02) and condensates thereof: Si(R a ) q (R b ) 4-q (02) In formula (02), R a represents a hydrogen atom or a non-hydrolyzable organic group, and R b represents a hydrolyzable group, and q represents an integer of 1 to 2.

[28] The coating liquid according to

[26] or

[27] , characterized in that the coating liquid contains a liquid dispersion medium B having a boiling point of less than 100°C.

[29] The coating liquid according to any one of

[26] to

[28] , wherein the pore-forming agent is an organic ammonium salt.

[30] The coating liquid according to any one of

[26] to

[29] , wherein the acid catalyst comprises at least one selected from the group consisting of formic acid, acetic acid, propionic acid, butanoic acid, oxalic acid, maleic acid, phthalic acid, fumaric acid, hydrochloric acid, nitric acid, sulfuric acid, and phosphoric acid.

[31] The coating liquid according to any one of

[26] to

[30] , wherein the ratio of the weight of the pore-forming agent to the total weight of SiO2 contained in the alkoxysilane ([weight of pore-forming agent] / [total weight of SiO2 contained in the alkoxysilane]) is 0.10 or more. [Effects of the Invention]

[0010] According to the present invention, it is possible to provide a method for producing a laminate that combines high abrasion resistance and alkali resistance with high ultraviolet transmittance, a laminate, and a coating liquid used in producing the laminate. DETAILED DESCRIPTION OF THE INVENTION

[0011] One embodiment of the present invention is described in detail below.

[0012] <Inorganic fine particle dispersion> The inorganic fine particle dispersion used in the method for producing a laminate of the present invention is The inorganic microparticle dispersion liquid contains inorganic microparticles and a liquid dispersion medium A having a boiling point of more than 121°C and less than 190°C, and the weight ratio of the liquid dispersion medium A is 0.5 mass% or more and less than 15 mass% when the total amount of the inorganic microparticle dispersion liquid is 100 mass%.

[0013] [Inorganic fine particles] In the present invention, the inorganic fine particles may be inorganic fine particles containing silica particles. The primary particle diameter of the inorganic fine particles may be 1 nm or more and less than 50 nm. The inorganic fine particles may be inorganic fine particles X having a primary particle diameter of 1 nm or more and less than 50 nm, or inorganic fine particles Y consisting of a plurality of inorganic fine particles having a primary particle diameter of 1 nm or more and less than 50 nm connected together. The shape of the secondary particles of the inorganic fine particles Y is not particularly limited. The inorganic fine particles may be either inorganic fine particles X or inorganic fine particles Y, and both may be used together. As the inorganic fine particles X, one or more types of inorganic fine particles may be used, and as the inorganic fine particles Y, one or more types of inorganic fine particles may be used.

[0014] The primary particle size of the inorganic fine particles is evaluated as the number average of particle sizes of 50 or more particles obtained by observation with a transmission electron microscope. The state of "multiple inorganic fine particles connected together" in the inorganic fine particles Y can also be determined by observation with a transmission electron microscope. <Primary particle size of inorganic fine particles> The primary particle diameter of the inorganic fine particles was measured before they were formed into a coating film. Therefore, in the present invention, the predetermined primary particle diameter means the primary particle diameter of the inorganic fine particles used as a raw material or the primary particle diameter up to the step of applying the inorganic fine particles to a substrate before they are formed into a coating film.

[0015] Examples of materials for inorganic fine particles include silicon oxide (silica), titanium oxide, aluminum oxide, zinc oxide, tin oxide, calcium carbonate, barium sulfate, talc, and kaolin, and one or more of these can be used. From the viewpoint of dispersibility in the inorganic fine particle dispersion and ultraviolet transmittance of the coating film, silica is preferred, and among silica, colloidal silica and fumed silica are more preferred, with colloidal silica being particularly preferred. Colloidal silica can be a dispersion containing colloidal silica particles at a solid content concentration of 5% to 50% by mass, preferably 5% to 40% by mass, and more preferably 10% to 30% by mass. Colloidal silica dispersed in various solvents can be used, and examples of such solvents include: Alcohol solvents such as methanol, ethanol, isopropanol, ethylene glycol, and ethylene glycol mono-n-propyl ether, Amide solvents such as dimethylacetamide and N-methylpyrrolidone, aromatic solvents such as toluene, Ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ester solvents such as ethyl acetate, water, These solvents can also be used in combination. Preferred are alcohol solvents such as methanol, ethanol, isopropanol, ethylene glycol, and ethylene glycol mono-n-propyl ether, and water, more preferred are methanol, ethanol, isopropanol, and water, more preferred are ethanol, isopropanol, and water, and more preferred is water.

[0016] From the viewpoint of achieving both transmittance and coating strength, the primary particle diameter of the inorganic fine particles X is preferably 1 nm or more and less than 50 nm, more preferably 1 nm or more and 30 nm or less, even more preferably 1 nm or more and 20 nm or less, and particularly preferably 3 nm or more and 10 nm or less.

[0017] The primary particle diameter of the inorganic fine particles Y, which are composed of a plurality of inorganic fine particles each having a primary particle diameter of 1 nm or more and less than 50 nm, is preferably 1 nm or more and less than 50 nm, more preferably 1 nm or more and 45 nm or less, even more preferably 1 nm or more and 30 nm or less, and particularly preferably 3 nm or more and 20 nm or less, from the viewpoint of achieving both transmittance and coating strength.

[0018] The weight ratio of the inorganic fine particles is not particularly limited, but from the viewpoint of the transparency of the resulting coating film and dispersibility in the inorganic fine particle dispersion, it is preferably 0.05% by mass to 10% by mass, more preferably 0.1% by mass to 7.5% by mass, even more preferably 0.2% by mass to 5.0% by mass, and particularly preferably 0.5% by mass to 2.0% by mass, where the total weight of the inorganic fine particle dispersion is 100% by mass. The "weight ratio of inorganic fine particles" means the sum of the weight ratio of inorganic fine particles X and the weight ratio of inorganic fine particles Y.

[0019] The inorganic fine particles in the inorganic fine particle dispersion may be surface-treated from the viewpoint of dispersibility in the dispersion, coating, and film formation. A known method can be used for the surface treatment, and examples thereof include treatment with an appropriate additive. The surface treatment of the inorganic fine particles can be performed, for example, by mixing a liquid containing inorganic fine particles, an additive, and a solvent.

[0020] Specific examples of inorganic fine particles X include Snowtex (registered trademark) ST-XS, ST-OXS, ST-NXS, ST-CXS, ST-S, ST-OS, ST-NS, ST-30, ST-O, ST-N, ST-C, ST-AK, ST-50-T, ST-O-40, ST-N-40, ST-CM, ST-30L, ST-OL, and ST-AK-L, which are commercially available products in the form of an aqueous dispersion; Methanol Silica Sol (registered trademark) MA-ST-M and MA-ST-L, which are commercially available products in the form of a methanol dispersion; IPA-ST and IPA-ST-L, which are commercially available products in the form of an isopropyl alcohol dispersion; and NPC, which is a commercially available product in the form of an ethylene glycol monopropyl ether dispersion. -ST-30, TOL-ST, which is a commercially available product in the form of a toluene dispersion, MEK-ST-40, MEK-ST-L, MEK-EC-2130Y, MEK-AC-2140Z, and MEK-AC-4130Y, which are commercially available products in the form of a 2-butanone dispersion, MIBK-ST, MIBK-ST-L, MIBK-AC-2140Z, and MIBK-SD-L, which are commercially available products in the form of a 4-methyl-2-pentanone dispersion, CHO-ST-M, which is a commercially available product in the form of a cyclohexanone dispersion, EAC-ST, which is a commercially available product in the form of an ethyl acetate dispersion, and PMA-ST, which is a commercially available product in the form of a propylene glycol 1-monomethyl ether 2-acetate dispersion. Among these, those in the form of an aqueous dispersion are preferred, and in particular, ST-OXS, ST-NXS, ST-CXS, ST-OS, ST-NS, ST-O, ST-N, ST-C, ST-O-40, ST-N-40, ST-CM, and ST-OL are preferred, with ST-OXS, ST-OS, ST-O, ST-O-40, and ST-OL being more preferred.

[0021] Specific examples of inorganic fine particles Y include Snowtex (registered trademark) ST-UP, ST-OUP, ST-PS-S, ST-PS-SO, ST-PS-M, and ST-PS-MO, which are commercially available products in the form of an aqueous dispersion, IPA-ST-UP, which is a commercially available product in the form of an isopropyl alcohol dispersion, and MEK-ST-UP, which is a commercially available product in the form of a 2-butanone dispersion. Among these, those in the form of an aqueous dispersion are preferred, and ST-OUP, ST-PS-SO, and ST-PS-MO are particularly preferred, with ST-OUP being more preferred.

[0022] The method for synthesizing the inorganic fine particles X and the inorganic fine particles Y is not particularly limited, and examples thereof include hydrolysis and / or condensation of metal alkoxides, thermal decomposition of metal salts, pulverization and / or crushing of metal oxides, precipitation of aqueous metal salt solutions, and hydrothermal treatment of aqueous metal salt solutions.

[0023] Silica that is preferable from the viewpoint of dispersibility can be synthesized by known methods such as a method in which an aqueous sodium silicate solution is ion-exchanged with an ion exchange resin or the like, followed by particle growth and concentration (sometimes called the water glass method), a method in which an aqueous sodium silicate solution is neutralized by adding an aqueous sulfuric acid solution, followed by particle growth and concentration (sometimes called the precipitation method), a method in which silicon tetrachloride is thermally decomposed, or a method in which alkoxysilane is hydrolyzed and condensed (sometimes called the sol-gel method).

[0024] In the case of the method of synthesizing the silica sol by ion-exchanging an aqueous sodium silicate solution, the weight ratio of sodium ions in the silica sol, expressed as the amount of NaO, is preferably 0.5% by mass or less, more preferably 0.05% by mass or less, and even more preferably 0.03% by mass or less, when the total amount of the inorganic fine particle dispersion is taken as 100% by mass, from the viewpoint of forming a coating film with high transmittance.

[0025] [Liquid dispersion medium A] In the present invention, the liquid dispersion medium A is a liquid having a boiling point under atmospheric pressure (1013.25 hPa) of more than 121° C. and less than 190° C. When the entire inorganic fine particle dispersion liquid is taken as 100% by mass, the weight ratio of the liquid dispersion medium A is 0.5% by mass or more and less than 15% by mass.

[0026] The boiling point range of the liquid dispersion medium A is preferably 125°C or higher but lower than 190°C, more preferably 135°C or higher but lower than 190°C, even more preferably 150°C or higher but lower than 190°C, even more preferably 155°C or higher but lower than 190°C, even more preferably 155°C or higher but lower than 180°C, even more preferably 160°C or higher but lower than 180°C, and even more preferably 170°C or higher but lower than 180°C.

[0027] The lower limit of the weight ratio of the liquid dispersion medium A is preferably 0.7% by mass or more, and more preferably 0.8% by mass or more, when the total inorganic particle dispersion is 100% by mass, because the use of the liquid dispersion medium A suppresses aggregation of the inorganic particles when the coating film dries and improves transmittance and coating film strength. The upper limit of the weight ratio of the liquid dispersion medium A is preferably 13% by mass or less, and more preferably 12% by mass or less, and even more preferably 8% by mass or less, when the total inorganic particle dispersion is 100% by mass, because an excessive amount of the liquid dispersion medium A deteriorates storage stability due to gelation of the inorganic particle dispersion.

[0028] Liquid dispersion medium A has a δtA of 20 MPa, as defined by the following formula: 0.5 More than 40Mpa 0.5 The following is exemplified as a good example: δtA ={4(δDA-15.6) 2 +(δPA-16.0) 2 +(δHA-42.0) 2} 0.5 (1) (Wherein, δDA, δPA, and δHA are the dispersion terms (MPa) in the Hansen solubility parameters for liquid dispersion medium A. 0.5 ), polarity term (Mpa 0.5 ), hydrogen bond term (Mpa 0.5) respectively. The above δDA, δPA, and δHA are calculated using the commercially available software "HSPiP 5th 5.2.06" by applying a method called Y-MB in the software. The preferred range of δtA is 39 MPa. 0.5 It is preferable that it is less than 35.5Mpa 0.5 It is more preferable that it is less than 34Mpa 0.5 It is more preferable that the lower limit is 25 MPa. 0.5 It is preferable that it is 29Mpa or more. 0.5 More preferably, it is 30Mpa or more. 0.5 A liquid dispersion medium A having a ΔtA within this range has high affinity with inorganic fine particles and exhibits good coatability.

[0029] From the viewpoint of coatability, the lower limit of the molecular weight of the liquid dispersion medium A is preferably 60 or more, more preferably 70 or more, even more preferably 90 or more, and particularly preferably 100 or more. The upper limit is preferably 300 or less, more preferably 200 or less, even more preferably 170 or less, and particularly preferably 140 or less.

[0030] Examples of the liquid dispersion medium A include, but are not limited to, ethers, esters, alcohols, ketones, amines, amides, sulfoxides, etc. Specific examples of the liquid dispersion medium A include, but are not limited to, the following: 2-Methoxyethyl acetate, isoamyl acetate, propylene glycol 1-monomethyl ether 2-acetate, 1-propoxy-2-propanol, N,N-dimethylformamide, 2-ethoxyethyl acetate, dimethyl sulfoxide, dipropylene glycol dimethyl ether, n-pentyl acetate, ethyl acetoacetate, acetylacetone (2,4-pentanedione), 1-hexanol, furfuryl alcohol, 1-pentanol, dibutyl ether, 2-butoxyethanol (ethylene glycol monobutyl ether), 2-methoxyethanol (ethylene glycol monomethyl ether), 2-ethoxyethanol (ethylene glycol monoethyl ether), 2-ethylhexanol, N,N-dimethylacetate amide, ethyl lactate, diethylene glycol ethyl methyl ether, 3-methoxybutyl acetate, 1,2-propanediol, 3-methoxy-3-methylbutanol, propylene glycol 1-monobutyl ether, 1-ethoxy-2-propanol, 3-methoxy-1-propanol, 3-methoxy-1-butanol, ethylene glycol mono-t-butyl ether, 2-isopropoxyethanol, 2-propoxyethanol, 2-isobutoxyethanol, 2-allyloxyethanol, tetrahydrofurfuryl alcohol, 2-hydroxyethyl acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, 1,2-diacetoxypropane, and 3-methoxy-3-methylbutyl acetate.

[0031] Preferred liquid dispersion medium A includes those which are alcohols, have an ether bond, or have an ester bond. More preferred are those which are alcohols, have an ether bond, or have an ester bond, and do not contain a nitrogen atom. Use of such a liquid dispersion medium A improves coating properties.

[0032] In one embodiment of the inorganic fine particle dispersion, the liquid dispersion medium A is preferably an alcohol. When the liquid dispersion medium A is an alcohol, the compatibility between the inorganic fine particle component and the alkoxysilane described below during coating is improved, resulting in good coatability and a laminate having high coating strength.

[0033] When the liquid dispersion medium A is an alcohol, a preferred example is a monohydric alcohol. Furthermore, those having at least one of an ether bond and an ester bond are preferred. Such alcohols improve the dispersibility and coating properties of inorganic fine particles. Specific examples include 1-propoxy-2-propanol, furfuryl alcohol, 2-butoxyethanol (ethylene glycol monobutyl ether), 2-methoxyethanol (ethylene glycol monomethyl ether), 2-ethoxyethanol (ethylene glycol monoethyl ether), ethyl lactate, 3-methoxy-3-methylbutanol, propylene glycol 1-monobutyl ether, 1-ethoxy-2-propanol, 3-methoxy-1-propanol, 3-methoxy-1-butanol, ethylene glycol mono-t-butyl ether, 2-isopropoxyethanol, 2-propoxyethanol, 2-isobutoxyethanol, 2-allyloxyethanol, tetrahydrofurfuryl alcohol, and 2-hydroxyethyl acetate.

[0034] The liquid dispersion medium A is a monohydric alcohol having one or more of an ether bond and an ester bond, and from the viewpoint of dispersibility and coatability of inorganic fine particles, more preferably, the liquid dispersion medium A is a monohydric alcohol having an ether bond. Specific examples of such a liquid dispersion medium include: Examples include 1-propoxy-2-propanol, furfuryl alcohol, 2-butoxyethanol (ethylene glycol monobutyl ether), 2-methoxyethanol (ethylene glycol monomethyl ether), 2-ethoxyethanol (ethylene glycol monoethyl ether), 3-methoxy-3-methylbutanol, propylene glycol 1-monobutyl ether, 1-ethoxy-2-propanol, 3-methoxy-1-propanol, 3-methoxy-1-butanol, ethylene glycol mono-t-butyl ether, 2-isopropoxyethanol, 2-propoxyethanol, 2-isobutoxyethanol, 2-allyloxyethanol, and tetrahydrofurfuryl alcohol. More preferred examples include 1-propoxy-2-propanol, 2-butoxyethanol (ethylene glycol monobutyl ether), 3-methoxy-3-methylbutanol, propylene glycol 1-monobutyl ether, 3-methoxy-1-propanol, 3-methoxy-1-butanol, ethylene glycol mono-t-butyl ether, 2-isopropoxyethanol, 2-propoxyethanol, 2-isobutoxyethanol, 2-allyloxyethanol, and tetrahydrofurfuryl alcohol; even more preferred examples include 2-butoxyethanol (ethylene glycol monobutyl ether), 3-methoxy-3-methylbutanol, propylene glycol 1-monobutyl ether, 3-methoxy-1-propanol, 3-methoxy-1-butanol, ethylene glycol mono-t-butyl ether, 2-propoxyethanol, 2-isobutoxyethanol, and tetrahydrofurfuryl alcohol; and even more preferred examples include 3-methoxy-3-methylbutanol and 3-methoxy-1-butanol. Even more preferred is 3-methoxy-3-methylbutanol.

[0035] [Liquid dispersion medium B] In the present invention, the inorganic fine particle dispersion preferably contains a liquid dispersion medium B having a boiling point of less than 100°C.

[0036] The liquid dispersion medium B has a δtB of 15 MPa, as defined by the following formula: 0.5 Over 39Mpa 0.5 The following is exemplified as a good example: δtB ={4(δDB-15.6) 2 +(δPB-16.0) 2 +(δHB-42.0) 2} 0.5 (2) (Wherein, δDB, δPB, and δHB are the dispersion terms (MPa) in the Hansen solubility parameters for liquid dispersion medium B. 0.5 ), polarity term (Mpa 0.5 ), hydrogen bond term (Mpa 0.5 ) respectively. The above δDB, δPB, and δHB are calculated using the commonly available commercially available software "HSPiP 5th 5.2.06" by applying a method called Y-MB in the software. The preferred range of δtB is 32 MPa. 0.5 It is preferable that it is less than 31Mpa 0.5 It is preferable that it is less than 27Mpa 0.5 It is more preferable that the pressure is less than 18 MPa. 0.5 It is preferable that it is 23Mpa or more. 0.5 More preferably, it is 25Mpa or more. 0.5 A liquid dispersion medium B having a ΔtB within this range has a high affinity with inorganic fine particles and exhibits good coatability.

[0037] Examples of the liquid dispersion medium B include ethers, esters, and alcohols, and examples of the ethers include diethyl ether, examples of the esters include methyl acetate and ethyl acetate, and examples of the alcohols include methanol, ethanol, tertiary butyl alcohol, sec-butyl alcohol, isopropyl alcohol, and normal propyl alcohol. From the viewpoint of dispersibility of inorganic fine particles in the inorganic fine particle dispersion, alcohols are preferred, with methanol, ethanol, and isopropyl alcohol being more preferred, and ethanol and isopropyl alcohol being particularly preferred, with ethanol being even more preferred from the viewpoint of safety.

[0038] The weight ratio of the liquid dispersion medium B is not particularly limited, but from the viewpoint of coatability and storage stability, when the entire inorganic microparticle dispersion liquid is taken as 100% by mass, it is preferably contained in an amount of 20% by mass or more, more preferably 30% by mass or more, even more preferably 40% by mass or more, even more preferably 60% by mass or more, and even more preferably 95% by mass or less, even more preferably 90% by mass or less, even more preferably 85% by mass or less, even more preferably 80% by mass or less.

[0039] [water] In one embodiment of the present invention, the inorganic particle dispersion preferably contains water. From the viewpoint of coatability and storage stability, the lower limit of the water weight ratio is preferably 1% by mass or more, more preferably 3% by mass or more, even more preferably 5% by mass or more, even more preferably 8% by mass or more, and even more preferably 10% by mass or more, when the entire inorganic particle dispersion is taken as 100% by mass. Furthermore, from the viewpoint of transmittance, the upper limit of the water weight ratio is preferably 55% by mass or less, even more preferably 50% by mass or less, even more preferably 45% by mass or less, even more preferably 35% by mass or less, even more preferably 25% by mass or less, and even more preferably 20% by mass or less.

[0040] [Alkoxysilane (Component C)] In one embodiment of the present invention, the inorganic fine particle dispersion preferably contains an alkoxysilane (component C). The alkoxysilane may be a condensate of an alkoxysilane. The alkoxysilane may have a partially hydrolyzed alkoxy group, and may further be condensed at the hydrolyzed portion. In this specification, "hydrolyzable" refers to the property of generating a silanol group by reaction with water. Examples of the alkoxysilane include tetraalkoxysilane and silicon compounds represented by the following formula (3). Si(R a ) q (R b ) 4-q (3) In formula (3), R a represents a hydrogen atom or a non-hydrolyzable organic group, and R b represents a hydrolyzable group, and q represents an integer of 1 to 2.

[0041] In one embodiment, the tetraalkoxysilane is represented by the following formula: Si(OR)4 (wherein each of the four R's independently represents an alkyl group having 1 to 6 carbon atoms). Examples of the tetraalkoxysilane include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetrabutoxysilane, with tetramethoxysilane and tetraethoxysilane being preferred. These tetraalkoxysilanes may be partially hydrolyzed at the alkoxy group sites, and may further be condensed at the hydrolyzed sites.

[0042] One embodiment of the alkoxysilane is a silicon compound represented by the following formula (3). Si(R a ) q (R b ) 4-q (3) In formula (3), R a represents a hydrogen atom or a non-hydrolyzable organic group, and R b represents a hydrolyzable group, and q represents an integer of 1 to 2.

[0043] R aExamples of the non-hydrolyzable organic group include alkyl groups having 1 to 10 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, tert-amyl (1,1-dimethylpropyl), 1,1-dimethyl-3,3-dimethylbutyl, heptyl, octyl, nonyl, and decyl groups; cycloalkyl groups having 3 to 10 carbon atoms, such as cyclopentyl and cyclohexyl groups; and aromatic groups having 6 to 15 carbon atoms, such as phenyl, naphthyl, and anthracenyl groups.

[0044] R b Examples of the hydrolyzable group include alkoxy groups having 1 to 5 carbon atoms, such as a methoxy group, an ethoxy group, and a propoxy group.

[0045] q represents an integer of 1 to 2, and is preferably 1.

[0046] In the silicon compound represented by formula (3), the hydrolyzable group may be hydrolyzed, and further, the hydrolyzed portion may be condensed.

[0047] Examples of the silicon compound represented by formula (3) include silicon compounds in which q is 1, such as methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltriisopropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, phenyltrimethoxysilane, and phenyltriethoxysilane; and silicon compounds in which q is 2, such as dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, and methylphenyldimethoxysilane.

[0048] Examples of the alkoxysilane condensate include the above-mentioned tetraalkoxysilane and a siloxane compound in which the alkoxy groups in the silicon compound represented by the above formula (3) are partially hydrolyzed and condensed at the hydrolyzed portions. The alkoxysilane condensate may further be partially hydrolyzed at the alkoxy group sites, and may further be condensed at the hydrolyzed portions.

[0049] In one embodiment, the tetraalkoxysilane condensate is Examples of the silicon compound include those having a structure represented by the following general formula (1). General formula (1) [ka] (In the formula, each R independently represents an alkyl group having 1 to 6 carbon atoms. n is an integer of 2 to 1000, and in one embodiment, n is 2 to 100.) Examples of R, an alkyl group having 1 to 6 carbon atoms, include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, a tert-amyl group (1,1-dimethylpropyl group), etc. Preferred examples include a methyl group, an ethyl group, and a butyl group, and more preferred examples include a methyl group and an ethyl group. In the above general formula (1), n ​​represents an integer of 2 to 1000, preferably 2 to 100, more preferably 3 to 50, and still more preferably 3 to 30. The weight average molecular weight of the silicon compound having the structure represented by the above general formula (1) is preferably 170 or more and 500,000 or less, more preferably 170 or more and 30,000 or less, more preferably 200 or more and 10,000 or less, more preferably 240 or more and 8,000 or less, and more preferably 240 or more and 5,000 or less. Furthermore, the silicon compound having the structure represented by general formula (1) may have a partially hydrolyzed alkoxy group site, and may further be condensed at the hydrolyzed site.

[0050] Commercially available alkoxysilane condensates include, for example, Methyl Silicate 51, Methyl Silicate 53A, Ethyl Silicate 40, Ethyl Silicate 48, and EMS-485 (all manufactured by Colcoat Co., Ltd.). Among the alkoxysilane condensates, commercially available products of hydrolysis condensates of methyl silicate include, for example, MS51, MS56, MS57, and MS56S (all manufactured by Mitsubishi Chemical Corporation).

[0051] Among the alkoxysilane condensates, commercially available products of hydrolysis condensates of ethyl silicate include, for example, HAS-1, HAS-6, and HAS-10 (all manufactured by Colcoat Co., Ltd.).

[0052] The inorganic fine particle dispersion may contain only one type of alkoxysilane or two or more types of alkoxysilane. Also, the alkoxysilane and its condensate may be contained alone or both. The alkoxysilane preferably contains a condensate of an alkoxysilane represented by the following general formula (1). General formula (1) [ka] (In the formula, each R independently represents an alkyl group having 1 to 6 carbon atoms. n is an integer of 2 to 1000, and in one embodiment, n is 2 to 100.) Such an inorganic fine particle dispersion liquid has superior coating strength.

[0053] The amount of component C in the inorganic microparticle dispersion is not particularly limited, but is preferably 0.0001 to 2 mass%, more preferably 0.0005 to 1 mass%, and even more preferably 0.001 to 0.5 mass%, with the total weight of the inorganic microparticle dispersion being 100 mass%.

[0054] In the inorganic fine particle dispersion of the present invention, the ratio of the weight of SiO2 contained in the alkoxysilane to the weight of the inorganic fine particles ([weight of SiO2 contained in the alkoxysilane] / [weight of inorganic fine particles]) is preferably greater than 0.005, more preferably 0.005 to 0.6, more preferably 0.005 to 0.2, even more preferably 0.007 to 0.15, and particularly preferably 0.01 to 0.12.

[0055] A liquid containing Component C and a solvent may be used as a raw material liquid when producing an inorganic fine particle dispersion. The raw material liquid containing Component C may contain an additive that promotes hydrolysis and dehydration condensation, inhibits aggregation of the condensate, or controls adhesion to the substrate. An example of the additive is an acrylic-urethane resin.

[0056] [Surfactants] In one embodiment, the inorganic particle dispersion preferably contains a surfactant from the viewpoint of the smoothness of the coating film. When the inorganic particle dispersion contains a surfactant, the weight ratio of the surfactant is preferably 0.01% by mass or more and 0.5% by mass or less, and in a more preferred embodiment, 0.1% by mass or more and 0.45% by mass or less, and in another more preferred embodiment, more than 0.3% by mass and 0.45% by mass or less, when the total inorganic particle dispersion is taken as 100% by mass. The surfactant used is not particularly limited, and examples thereof include anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants. A preferred surfactant is a nonionic surfactant.

[0057] Examples of anionic surfactants include alkali metal salts of carboxylic acids and alkali metal salts of sulfonic acids, and specific examples include sodium caprylate, potassium caprylate, sodium decanoate, sodium caproate, sodium myristate, potassium oleate, sodium stearate, sodium dodecyl sulfate, sodium tetradecyl sulfate, and sodium 1-hexadecanesulfonate.

[0058] Examples of cationic surfactants include cetyltrimethylammonium chloride, dioctadecyldimethylammonium chloride, N-octadecylpyridinium bromide, and cetyltriethylphosphonium bromide.

[0059] Examples of nonionic surfactants include polyether-modified siloxanes. The siloxane chain of the main chain of the polyether-modified siloxane may be linear or branched, the ether chain of the side chain of the polyether-modified siloxane may be linear or branched, and a portion of the side chain of the polyether-modified siloxane may be modified with an alkyl group or the like. Commercially available polyether-modified siloxanes can be used, such as KF-6015, KF-6017, KF-6017P, KF-6028, KF-6028P, KF-6038, KF-6043, and KF-6048 (all manufactured by Shin-Etsu Chemical Co., Ltd.), BYK-306, BYK-307, BYK-310, BYK-333, BYK-344, and BYK- 345, BYK-346, BYK-347, BYK-348, BYK-349, BYK-378 (all manufactured by BYK-Chemie Japan Co., Ltd.), DOWSIL (trademark) 501W Additive, DOWSIL (trademark) FZ-2104 Fluid, DOWSIL (trademark) FZ-2110, DOWSIL (trademark) FZ-2123, DOWSIL (trademark) FZ-21 64, DOWSIL™ FZ-2191, DOWSIL™ FZ-5609 Fluid, DOWSIL™ L-7001, DOWSIL™ L-7002, DOWSIL™ L-7604, DOWSIL™ SH3746 Fluid, DOWSIL™ SH3771 Fluid, DOWSIL™ SH8400 Fluid, DOWSIL™ SF8410 Fluid, DOWSIL™ SF8700 Fluid, SYLGARD™ OFX-0309 Fluid, XIAMETER™ OFX-0193 Fluid, XIAMETER™ OFX-5211 Fluid, DOWSIL™ Y-7006 (all manufactured by Dow-Toray Industries, Inc.), and the like.

[0060] Examples of amphoteric surfactants include 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine and lauric acid amidopropyl betaine.

[0061] [Other ingredients] The inorganic fine particle dispersion may contain silica other than the inorganic fine particles X and the inorganic fine particles Y. In addition, depending on the application and method of use, the dispersion may contain a thickener, a thixotropy agent, an antifoaming agent, a light stabilizer, a pigment, an antifungal agent, a dustproofing agent, an antifreeze performance improver, a weathering agent, an ultraviolet stabilizer, and the like.

[0062] When the inorganic particle dispersion contains an additive, the inorganic particles can be surface-treated with an appropriate additive. Examples of additives include those containing polar groups such as hydroxyl, oxy, carbonyl, carboxy, and epoxy groups, which can form hydrogen bonds or covalent bonds with the inorganic particles via these polar groups. Examples of additives include polycarboxylic acids and their salts, polymeric unsaturated acid esters, modified or unmodified polyurethanes, modified or unmodified polyesters, modified or unmodified poly(methacrylates), (meth)acrylic acid copolymers, polyoxyethylene alkyl phosphate esters, alkoxysilanes and alkoxysilane condensates, which are listed as component C, and acrylic-urethane resins. Polymeric additives adsorb to the surface of inorganic particles and act to prevent re-agglomeration, so those with anchoring sites on the particle surface are preferred. Preferred structures include terminally modified polymers, graft polymers, and block polymers. Surface treatment of inorganic particles can be achieved, for example, by mixing a liquid containing inorganic particles, additives, and a solvent.

[0063] <Method of manufacturing inorganic fine particle dispersion> The inorganic fine particle dispersion can be prepared by, for example, combining some or all of the following steps [Step 1] to [Step 10] in any order, but is not limited to these methods. [Step 1] A step of obtaining a dispersion of inorganic fine particles X. The dispersion of inorganic fine particles X can be obtained, for example, by hydrolysis and / or condensation of a metal alkoxide, hydrolysis of a metal salt, pulverization and / or crushing of a metal oxide, precipitation of an aqueous metal salt solution, hydrothermal treatment of an aqueous metal salt solution, and a process of mixing, stirring, and dispersing inorganic fine particles X in a liquid dispersion medium. Alternatively, a commercially available dispersion of inorganic fine particles X can be used. [Step 2] A step of obtaining a dispersion of inorganic fine particles Y. The dispersion of inorganic fine particles Y can be obtained, for example, by hydrolysis and / or condensation of a metal alkoxide, hydrolysis of a metal salt, pulverization and / or crushing of a metal oxide, precipitation of an aqueous metal salt solution, hydrothermal treatment of the aqueous metal salt solution, and a process of mixing, stirring, and dispersing inorganic fine particles Y in a liquid dispersion medium. Alternatively, a commercially available dispersion of inorganic fine particles Y can be used. [Step 3] A step of obtaining a first dispersion. The first dispersion contains inorganic fine particles X and a first liquid dispersion medium. The first dispersion may optionally contain inorganic fine particles Y, liquid dispersion medium A, liquid dispersion medium B, water, component C, a surfactant, or other components contained in the inorganic fine particle dispersion. In this case, the weight ratio of these components may be the total amount contained in the inorganic fine particle dispersion, or may be a partial amount. The first liquid dispersion medium may consist of a single liquid dispersion medium or a mixture of multiple liquid dispersion media. [Step 4] A step of obtaining a second dispersion. The second dispersion comprises inorganic fine particles Y and a second liquid dispersion medium. The second dispersion may optionally contain inorganic fine particles X, liquid dispersion medium A, liquid dispersion medium B, water, component C, a surfactant, or other components contained in the inorganic fine particle dispersion. In this case, the weight ratio of these components may be the total amount contained in the inorganic fine particle dispersion, or may be a partial amount. The second liquid dispersion medium may consist of a single liquid dispersion medium or a mixture of multiple liquid dispersion media. [Step 5] A step of obtaining a third dispersion. The third dispersion comprises component C and a third liquid dispersion medium. The third dispersion may optionally contain inorganic fine particles X, inorganic fine particles Y, liquid dispersion medium A, liquid dispersion medium B, water, a surfactant, or other components contained in the inorganic fine particle dispersion. In this case, the weight ratio of these components may be the total amount contained in the inorganic fine particle dispersion, or may be a partial amount. The third liquid dispersion medium may consist of a single liquid dispersion medium or a mixture of multiple liquid dispersion mediums. [Step 6] A step of obtaining a fourth dispersion. The fourth dispersion comprises a surfactant and a fourth liquid dispersion medium. The fourth dispersion may optionally contain inorganic fine particles X, inorganic fine particles Y, liquid dispersion medium A, liquid dispersion medium B, water, component C, or other components contained in the inorganic fine particle dispersion. In this case, the weight ratio of these components may be the total amount contained in the inorganic fine particle dispersion, or may be a partial amount. The fourth liquid dispersion medium may consist of a single liquid dispersion medium or a mixture of multiple liquid dispersion mediums. [Step 7] A step of obtaining a fifth dispersion. The fifth dispersion comprises liquid dispersion medium A and a fifth liquid dispersion medium. The fifth dispersion may optionally contain inorganic fine particles X, inorganic fine particles Y, liquid dispersion medium B, water, component C, a surfactant, or other components contained in the inorganic fine particle dispersion. In this case, the weight ratio of these components may be the entire amount contained in the inorganic fine particle dispersion, or a partial amount. The fifth liquid dispersion medium may consist of a single liquid dispersion medium or a mixture of multiple liquid dispersion mediums. [Step 8] A step of obtaining a sixth dispersion. The sixth dispersion comprises liquid dispersion medium B and the sixth liquid dispersion medium. The sixth dispersion may optionally contain inorganic fine particles X, inorganic fine particles Y, liquid dispersion medium A, water, component C, a surfactant, or other components contained in the inorganic fine particle dispersion. In this case, the weight ratio of these components may be the entire amount contained in the inorganic fine particle dispersion, or may be a partial amount. The sixth liquid dispersion medium may consist of a single liquid dispersion medium or a mixture of multiple liquid dispersion mediums. [Step 9] A step of obtaining a seventh dispersion. The seventh dispersion comprises water and a seventh liquid dispersion medium. The seventh dispersion may optionally contain inorganic fine particles X, inorganic fine particles Y, liquid dispersion medium A, liquid dispersion medium B, component C, a surfactant, or other components contained in the inorganic fine particle dispersion. In this case, the weight ratio of these components may be the total amount contained in the inorganic fine particle dispersion, or may be a partial amount. The seventh liquid dispersion medium may consist of a single liquid dispersion medium or a mixture of multiple liquid dispersion mediums. [Step 10] A step of obtaining an eighth dispersion. The eighth dispersion contains an eighth liquid dispersion medium and other components contained in the inorganic fine particle dispersion. The eighth dispersion may contain inorganic fine particles X, inorganic fine particles Y, liquid dispersion medium A, liquid dispersion medium B, water, component C, or a surfactant, as necessary. In this case, the weight ratio of these components may be the total amount contained in the inorganic fine particle dispersion, or may be a partial amount. The eighth liquid dispersion medium may consist of a single liquid dispersion medium or a mixture of multiple liquid dispersion mediums.

[0064] In the above steps [Step 1] to [Step 10], as well as any other steps for preparing the inorganic microparticle dispersion, by applying a strong dispersion method such as ultrasonic dispersion or ultra-high pressure dispersion, the inorganic microparticles can be dispersed particularly uniformly in the inorganic microparticle dispersion. To achieve a more uniform dispersion, it is preferable that the inorganic particles are in a colloidal state in the dispersion of inorganic particles X or inorganic particles Y used to prepare the inorganic particle dispersion, or in the final inorganic particle dispersion. Water or a volatile organic solvent can be used as the dispersion medium.

[0065] Furthermore, in the above-mentioned steps [Step 1] to [Step 10] and any other steps for preparing an inorganic particle dispersion, when the dispersion of inorganic particle X, the dispersion of inorganic particle Y, or both the dispersions of inorganic particle X and inorganic particle Y are colloidal alumina, it is preferable to add anions such as chloride ions, sulfate ions, acetate ions, etc. to the colloidal alumina as counter anions to stabilize the positively charged alumina particles. The pH of the colloidal alumina is not particularly limited, but is preferably pH 2 to 6 from the viewpoint of the stability of the inorganic particle dispersion.

[0066] In addition, in the above-mentioned steps [Step 1] to [Step 10] and any other steps for preparing an inorganic fine particle dispersion, when at least one of the inorganic fine particles X and the inorganic fine particles Y is alumina and the dispersion or the inorganic fine particle dispersion of the inorganic fine particles X or the inorganic fine particles Y is in a colloidal state, it is preferable to add an anion such as a chloride ion, a sulfate ion, or an acetate ion to the dispersion.

[0067] Furthermore, in the above-mentioned steps [Step 1] to [Step 10] and any other steps for preparing an inorganic particle dispersion, when the dispersion of inorganic particle X, the dispersion of inorganic particle Y, or both the dispersions of inorganic particle X and inorganic particle Y are dispersions of colloidal silica, a cation such as an ammonium ion may be added to the colloidal silica as a counter cation to stabilize the negatively charged silica particles. The pH of the colloidal silica is not particularly limited.

[0068] Furthermore, in the above-mentioned steps [Step 1] to [Step 10] and any other steps for preparing an inorganic fine particle dispersion, when at least one of the inorganic fine particles X and the inorganic fine particles Y is silica and the dispersion of the inorganic fine particles X or the inorganic fine particles Y or the inorganic fine particle dispersion is in a colloidal state, a cation such as an ammonium ion may be added to the dispersion.

[0069] In a preferred embodiment when the inorganic particle dispersion contains component C, from the viewpoint of stably storing and managing the coating agent over the long term, the inorganic particle dispersion is prepared by dividing it into the following components A and B, and then mixing the components A and B immediately before coating to prepare the inorganic particle dispersion. [Agent A]: Contains inorganic fine particles and water, and may optionally contain liquid dispersion medium A, liquid dispersion medium B, a surfactant, and other components. [Agent B]: Contains ingredient C, It may contain liquid dispersion medium A, liquid dispersion medium B, water, a surfactant, and other ingredients as appropriate.

[0070] The agent A contains inorganic fine particles and water, and may also contain liquid dispersion medium A, liquid dispersion medium B, a surfactant, and other components as appropriate. The weight ratio of the inorganic fine particles contained in Agent A is preferably 0.05% by mass or more and 30% by mass or less, more preferably 0.1% by mass or more and 20% by mass or less, and even more preferably 0.5% by mass or more and 15% by mass or less, when the total weight of Agent A is 100% by mass. The weight ratio of water contained in agent A, when the total weight of agent A is taken as 100% by mass, is preferably 1% by mass or more, more preferably 5% by mass or more, even more preferably 10% by mass or more, and even more preferably 15% by mass or more, as a lower limit. Furthermore, the upper limit is preferably 90% by mass or less, more preferably 80% by mass or less, even more preferably 60% by mass or less, even more preferably 50% by mass or less, even more preferably 40% by mass or less, and even more preferably 30% by mass or less.

[0071] The agent B contains component C and may contain liquid dispersion medium A, liquid dispersion medium B, water, a surfactant, and other components as appropriate. As for agent B, component C alone may be used as agent B. The weight ratio of water contained in agent B is preferably small, and when the total weight of agent B is taken as 100% by mass, it is preferably 5% by mass or less, more preferably 3% by mass or less, more preferably 1% by mass or less, and particularly preferably 0.8% by mass or less.

[0072] <Method of manufacturing laminate> The method for producing a laminate of the present invention is a method for producing a laminate having a substrate and a coating film applied to at least one of its main surfaces, and includes a step of applying the above-mentioned inorganic microparticle dispersion to a substrate (application step); and a heat treatment step (heat treatment step) at a temperature of 200°C or higher and 1000°C or lower for more than 10 minutes. Preferably, the method for producing a laminate having a substrate and a coating film applied to at least one of its main surfaces includes the steps of: applying the inorganic microparticle dispersion liquid to a substrate (coating step); removing the liquid dispersion medium from the inorganic microparticle dispersion liquid applied to the substrate by an appropriate means to form a pre-heat-treatment coating film on the substrate (dispersion medium removal step); and a heat treatment step at a temperature of 200°C or higher and 1000°C or lower for more than 10 minutes (heat treatment step).

[0073] [Coating process] The method for applying the inorganic fine particle dispersion to the substrate is not particularly limited, and examples thereof include gravure coating, reverse coating, brush roll coating, spray coating, kiss coating, die coating, dipping, and bar coating.

[0074] The shape of the substrate is not particularly limited, but examples thereof include a film, a sheet, a plate, and a tube. The material of the substrate is not particularly limited, and examples thereof include plastic and glass. Specific examples of plastic substrates include films, sheets, plates, and tubes made of polyethylene terephthalate, polyethylene, polypropylene, cellophane, triacetyl cellulose, diacetyl cellulose, acetyl cellulose butyrate, polymethyl methacrylate, polycarbonate, polystyrene, MS resin, SAN resin, and silicone resin. Optical components such as polarizing plates, diffusion plates, light guide plates, brightness enhancement films, and reflective polarizing plates can also be used as the substrate. The substrate may have a surface layer formed of a hard coat layer made of an ultraviolet-curable resin or an antistatic layer containing conductive fine particles. A glass substrate is preferred because it has high heat resistance and transmittance.

[0075] When glass is used as the substrate, there are no particular limitations on the composition of the glass that can be used, the manufacturing method, etc. Examples of glass that can be used include soda glass, crystal glass, borosilicate glass, quartz glass, sapphire glass, aluminosilicate glass, borate glass, phosphate glass, alkali-free glass, and composite glass with ceramics. Quartz glass or sapphire glass is preferred because it has high transmittance over a wide wavelength range. Quartz glass or sapphire glass is also preferred because it has high ultraviolet transmittance. Quartz glass is particularly preferred. Examples of quartz glass include fused silica glass and synthetic quartz glass, and it is more preferred to use synthetic quartz glass as the substrate.

[0076] Before applying the inorganic fine particle dispersion to the substrate, the surface of the substrate may be subjected to pretreatment such as corona treatment, ozone treatment, plasma treatment, flame treatment, electron beam treatment, anchor coating treatment, or cleaning treatment.

[0077] [Dispersion medium removal process] and [Heat treatment process] A pre-heat treatment coating film can be formed on the surface of the substrate by removing the liquid dispersion medium from the inorganic fine particle dispersion liquid applied to the surface of the substrate (dispersion medium removing step). In one embodiment, the liquid dispersion medium can be removed by natural drying at room temperature, and in another embodiment, by heating under normal pressure or reduced pressure. In another embodiment, the liquid dispersion medium can be removed by natural drying at room temperature and then heating under normal pressure or reduced pressure. When air-drying at room temperature, the drying time is not particularly limited, but in one embodiment, it is preferably less than 24 hours, and in one embodiment, it is preferably 60 minutes or less, or in one embodiment, it can be 24 hours or more. When heating under normal pressure or reduced pressure, the pressure and heating temperature for removing the liquid dispersion medium by heating can be appropriately selected depending on the materials used (i.e., inorganic fine particles X, inorganic fine particles Y, and liquid dispersion medium). For example, drying can generally be performed at 50°C or higher but lower than 200°C, preferably 50°C or higher but lower than 120°C, and more preferably 60°C or higher but lower than 110°C. In one embodiment, drying can be performed at 50°C or higher but lower than 80°C, and in one embodiment, drying can be performed at 20°C or higher but lower than 50°C. The heating time is not particularly limited, but in one embodiment, it is preferably less than 24 hours, and in one embodiment, it is preferably 60 minutes or less. Alternatively, in one embodiment, it can be 24 hours or longer.

[0078] After removing the liquid dispersion medium in the dispersion medium removal step, the substrate on which the pre-heat-treatment coating film is formed can be heat-treated to improve the adhesion between the substrate and the pre-heat-treatment coating film (heat treatment step). In this specification, the pre-heat-treatment coating film after heat treatment is referred to as a "coating film." The heat treatment method in the heat treatment step is not particularly limited, but examples include heating in a heat treatment furnace and local heating of the pre-heat-treatment coating film by electromagnetic wave irradiation. Examples of heat treatment furnaces include a muffle furnace, a bell furnace, and a mesh belt furnace.

[0079] In the heat treatment step, the substrate is preferably maintained at a temperature of 200°C or higher and 1000°C or lower for a time longer than 10 minutes, and more preferably for a time longer than 60 minutes. Such a heat treatment step is preferred from the viewpoint of improving the abrasion resistance of the coating film. Although the reason why the abrasion resistance of the coating film is improved is not clear, it is speculated that such a heat treatment step realizes a stable arrangement of the aggregated structure of the inorganic fine particles, resulting in high abrasion resistance. In one embodiment, the substrate is held within a temperature range of 200° C. to 1000° C. for a time period greater than 720 minutes. The maximum temperature in the heat treatment step is preferably 200°C or higher and 1000°C or lower, more preferably 300°C or higher and 900°C or lower, even more preferably 300°C or higher and 800°C or lower, still more preferably 400°C or higher and 800°C or lower, still more preferably 500°C or higher and 800°C or lower, and even more preferably 500°C or higher and 720°C or lower. In the heat treatment step, preferably the substrate is held within a temperature range of 200°C to 1000°C for a time period longer than 10 minutes, more preferably the substrate is held within a temperature range of 200°C to 1000°C for a time period longer than 60 minutes, more preferably the substrate is held within a temperature range of 200°C to 1000°C for a time period longer than 180 minutes, more preferably the substrate is held within a temperature range of 200°C to 1000°C for a time period longer than 360 minutes, and more preferably the substrate is held within a temperature range of 200°C to 1000°C for a time period longer than 720 minutes. In the heat treatment step, preferably the substrate is held within a temperature range of 300°C to 900°C for a time period longer than 10 minutes, more preferably the substrate is held within a temperature range of 300°C to 900°C for a time period longer than 60 minutes, more preferably the substrate is held within a temperature range of 300°C to 900°C for a time period longer than 180 minutes, more preferably the substrate is held within a temperature range of 300°C to 900°C for a time period longer than 360 minutes, and more preferably the substrate is held within a temperature range of 300°C to 900°C for a time period longer than 720 minutes. In the heat treatment step, preferably the substrate is held within a temperature range of 300°C to 800°C for a time period longer than 10 minutes, more preferably the substrate is held within a temperature range of 300°C to 800°C for a time period longer than 60 minutes, more preferably the substrate is held within a temperature range of 300°C to 800°C for a time period longer than 180 minutes, more preferably the substrate is held within a temperature range of 300°C to 800°C for a time period longer than 360 minutes, and more preferably the substrate is held within a temperature range of 300°C to 800°C for a time period longer than 720 minutes. In the heat treatment step, preferably the substrate is held within a temperature range of 400°C to 800°C for a time period longer than 10 minutes, more preferably the substrate is held within a temperature range of 400°C to 800°C for a time period longer than 60 minutes, more preferably the substrate is held within a temperature range of 400°C to 800°C for a time period longer than 180 minutes, more preferably the substrate is held within a temperature range of 400°C to 800°C for a time period longer than 360 minutes, and more preferably the substrate is held within a temperature range of 400°C to 800°C for a time period longer than 720 minutes. In the heat treatment step, preferably the substrate is held within a temperature range of 500°C to 800°C for a time period longer than 10 minutes, more preferably the substrate is held within a temperature range of 500°C to 800°C for a time period longer than 60 minutes, more preferably the substrate is held within a temperature range of 500°C to 800°C for a time period longer than 180 minutes, more preferably the substrate is held within a temperature range of 500°C to 800°C for a time period longer than 360 minutes, and more preferably the substrate is held within a temperature range of 500°C to 800°C for a time period longer than 720 minutes. In the heat treatment step, preferably the substrate is held within a temperature range of 500°C to 720°C for a time period longer than 10 minutes, more preferably the substrate is held within a temperature range of 500°C to 720°C for a time period longer than 60 minutes, more preferably the substrate is held within a temperature range of 500°C to 720°C for a time period longer than 180 minutes, more preferably the substrate is held within a temperature range of 500°C to 720°C for a time period longer than 360 minutes, and more preferably the substrate is held within a temperature range of 500°C to 720°C for a time period longer than 720 minutes.

[0080] The temperature at which the substrate is maintained in the heat treatment step can be considered to be the temperature of the heat treatment furnace in the case of heating in a heat treatment furnace, or the temperature at which the substrate is maintained in the heat treatment step in the case of local heating by electromagnetic wave irradiation or the like is the temperature of the substrate itself.

[0081] The temperature rise rate in the heat treatment step is not particularly limited, but is preferably 10° C. / min or less, more preferably 5° C. / min or less. The atmosphere during heating is not particularly limited, but air is preferred.

[0082] In one embodiment, the heat treatment process comprises a step of raising the temperature to a target temperature (heating step), a step of maintaining the temperature at the target temperature (temperature holding step), and a step of lowering the temperature (cooling step). In the heating step, the temperature before raising the temperature is not particularly limited, but in one embodiment, it is 0°C or higher and 40°C or lower. The heating rate in the heating step is preferably 10°C / min or lower, more preferably 5°C / min or lower. The target temperature is 200°C or higher and 1000°C or lower, preferably 300°C or higher and 900°C or lower, more preferably 300°C or higher and 800°C or lower, more preferably 400°C or higher and 800°C or lower, more preferably 500°C or higher and 800°C or lower, and more preferably 500°C or higher and 720°C or lower. The holding time in the temperature holding step is longer than 10 minutes, preferably longer than 15 minutes, and even more preferably longer than 20 minutes. The cooling method in the cooling step is not particularly limited, and cooling may be achieved by stopping heating and allowing the material to cool naturally.

[0083] The heat treatment step forms a coating film on at least one of the main surfaces of the substrate. Alternatively, the coating film may be formed on both main surfaces of the substrate, or on all surfaces of the substrate.

[0084] In one embodiment, the method for producing a laminate may include two or more coating steps, a dispersion medium removal step, or a heat treatment step, and in one embodiment, the method for producing a laminate may include two or more coating steps. A laminate obtainable by a production method including two or more coating steps has a higher transmittance than a laminate obtainable by a production method including only one coating step. In one embodiment, after the coating step, the dispersion medium removal step, or the heat treatment step, a step (coating step) of applying an inorganic fine particle dispersion or a coating liquid described below to the substrate may be performed again. For example, a two-layer coating film can be formed on the substrate by performing the coating step and the dispersion medium removal step, then performing the coating step and the dispersion medium removal step again, and then performing the heat treatment step. Alternatively, a three-layer coating film can be formed on the substrate by performing the coating step and the dispersion medium removal step, then performing the coating step and the dispersion medium removal step again, then performing the coating step and the dispersion medium removal step again, and then performing the heat treatment step.

[0085] <Laminate> The thickness of the coating film in the laminate having a substrate and a coating film obtained by the above method is not particularly limited. In one embodiment, the thickness of the coating film is 20 nm or more and 200 nm or less, in another embodiment, the thickness of the coating film is 20 nm or more and 100 nm or less, in yet another embodiment, the thickness of the coating film is 20 nm or more and 75 nm or less, and in yet another embodiment, the thickness of the coating film is 25 nm or more and 60 nm or less. From the viewpoint of improving the transmittance of the laminate in the ultraviolet region (wavelength region of 185 nm or more and 300 nm or less), the thickness of the coating film is preferably 20 nm or more and less than 75 nm, and more preferably 25 nm or more and 60 nm or less. The thickness of the coating film can be measured from an image of the cross section of the coating film obtained by observation with a scanning electron microscope (SEM).

[0086] The present invention also relates to the following laminate: A laminate that can be obtained by the laminate manufacturing method including the various embodiments described above.

[0087] The present invention also relates to the following laminate: A laminate having a substrate and a coating film applied to at least one of its main surfaces, the coating film having a thickness of 20 nm or more and less than 75 nm, The average transmittance in the wavelength range of 185 nm or more and 300 nm or less is The laminate has an average transmittance that is 0.5 points or more higher than the average transmittance of the substrate not having the coating film. The coating may be formed on both major surfaces of the substrate, or on all surfaces of the substrate. The coating thickness is 20 nm or more and less than 75 nm, in another embodiment, 25 nm or more and less than 75 nm, and in another embodiment, 25 nm or more and less than 60 nm. The increase in average transmittance in the wavelength range of 185 nm to 300 nm relative to the average transmittance of a substrate without the coating is 0.5 points or more, preferably 1.0 points or more, and more preferably 1.5 points or more. The increase in transmittance is achieved by the coating not absorbing light in the wavelength range of 185 nm to 300 nm and having an anti-reflection effect. The anti-reflection effect occurs when light reflected from the coating surface and light reflected from the substrate surface cancel each other out, and the magnitude of this effect depends on the refractive index and film thickness of the coating. In the case of a coating with two or more layers, the magnitude of the anti-reflection effect depends on the refractive index and thickness of each layer. The increase in the average transmittance can be achieved by adjusting the refractive index and film thickness of the coating film formed on the substrate. The increase in the average transmittance is calculated by the method described in the Examples. The increase in the average transmittance in a specific wavelength range can be calculated by measuring the transmittance of each wavelength in the specific wavelength range for the laminate and the uncoated substrate, calculating the average value, and then subtracting the average transmittance of the uncoated substrate from the average transmittance of the laminate. The laminate can be obtained by the laminate manufacturing method including the various embodiments described above.

[0088] The thickness of the coating film can be adjusted by changing the weight ratio of inorganic fine particles X and inorganic fine particles Y in the inorganic fine particle dispersion and the coating amount of the inorganic fine particle dispersion.

[0089] The present invention also relates to the following laminate. A laminate having a substrate and a coating film applied to at least one of its main surfaces, the coating film has a porous structure and a thickness of 20 nm or more and less than 100 nm, The laminate is characterized in that the transmittance at any wavelength of 150 nm or more and less than 300 nm is 80.0% or more. The substrate can be the same as that described above, and the preferred substrates are also as described above. The coating can be the same coating as those described above and below.

[0090] A porous structure refers to a structure that contains many nanometer-sized micropores or voids. When the surface or cross section of a coating film with such a structure is observed with a scanning electron microscope (SEM), the micropores can be confirmed. On the other hand, coating films formed on substrates by dry coating (sputtering, vapor deposition, etc.) are generally dense films without micropores or voids and do not have a porous structure.

[0091] The laminate preferably has a transmittance of 80.0% or more at any wavelength between 150 nm and 300 nm, more preferably 85.0% or more, even more preferably 90.0% or more, and still more preferably 92.0% or more. The laminate preferably has a transmittance of 80.0% or more at any wavelength between 160 nm and 300 nm, more preferably 85.0% or more, even more preferably 90.0% or more, and still more preferably 92.0% or more. The laminate preferably has a transmittance of 80.0% or more at any wavelength between 185 nm and less than 300 nm, more preferably 85.0% or more, even more preferably 90.0% or more, and still more preferably 92.0% or more. The laminate preferably has a transmittance of 80.0% or more at any wavelength between 150 nm and less than 280 nm, more preferably 85.0% or more, even more preferably 90.0% or more, and even more preferably 92.0% or more. The laminate preferably has a transmittance of 80.0% or more at any wavelength between 160 nm and 280 nm, more preferably 85.0% or more, even more preferably 90.0% or more, and still more preferably 92.0% or more. The laminate preferably has a transmittance of 80.0% or more at any wavelength between 185 nm and 280 nm, more preferably 85.0% or more, even more preferably 90.0% or more, and even more preferably 92.0% or more. In one embodiment, the laminate preferably has a transmittance at a wavelength of 254 nm of 80.0% or more, more preferably 85.0% or more, even more preferably 90.0% or more, even more preferably 92.0% or more, and even more preferably 94.0% or more. In one embodiment, the laminate preferably has a transmittance at a wavelength of 222 nm of 80.0% or more, more preferably 85.0% or more, even more preferably 90.0% or more, even more preferably 92.0% or more, and even more preferably 94.0% or more. In one embodiment, the laminate preferably has a transmittance at a wavelength of 185 nm of 80.0% or more, more preferably 85.0% or more, even more preferably 90.0% or more, even more preferably 91.0% or more, and even more preferably 91.5% or more. In one embodiment, the laminate preferably has an average transmittance of 80.0% or more at wavelengths of 185 nm or more and 300 nm or less, more preferably 85.0% or more, even more preferably 90.0% or more, even more preferably 92.0% or more, and even more preferably 93.0% or more. In one embodiment, the laminate preferably has an average transmittance of 80.0% or more at wavelengths of 185 nm or more and 280 nm or less, more preferably 85.0% or more, even more preferably 90.0% or more, even more preferably 92.0% or more, and even more preferably 93.0% or more. In one embodiment, the laminate preferably satisfies any one of the following: "transmittance at a wavelength of 254 nm of 94.0% or more," "transmittance at a wavelength of 222 nm of 94.0% or more," and "transmittance at a wavelength of 185 nm of 91.5% or more."

[0092] The fact that the laminate has the above transmittance means that the substrate and coating film constituting the laminate have high transmittance for deep ultraviolet light. The high transmittance for deep ultraviolet light is presumably due to (1) a low silanol content and progressed condensation of silanol groups, (2) a low content of metal impurities, (3) a low amount of remaining organic components, or (4) low roughness of the coating film surface. It is presumed that the laminate achieves excellent alkali resistance and / or abrasion resistance due to at least one of the above reasons (1) to (4).

[0093] The laminate has a substrate and a coating applied to at least one of its major surfaces. The coating may be applied to both major surfaces of the substrate, or may be applied to all surfaces of the substrate. The coating thickness is 20 nm or more and less than 100 nm, and in another embodiment, the coating thickness is 20 nm or more and less than 75 nm, in another embodiment, the coating thickness is 25 nm or more and less than 75 nm, and in another embodiment, the coating thickness is 25 nm or more and less than 60 nm. The laminate can be obtained by a laminate manufacturing method (a method using a coating agent such as an inorganic fine particle dispersion or a coating liquid) including various embodiments described above and described below.

[0094] When the inorganic fine particle dispersion liquid described above is used, the thickness of the coating film can be adjusted by changing the weight ratio of the inorganic fine particles X and the inorganic fine particles Y in the inorganic fine particle dispersion liquid and the coating amount of the inorganic fine particle dispersion liquid. When using a coating liquid described below, the thickness of the coating film can be adjusted by changing the weight ratio of alkoxysilane in the coating liquid and the amount of the coating liquid applied.

[0095] The ratio of the number of carbon atoms to the total number of sodium, potassium, magnesium, calcium, aluminum, and silicon atoms on the surface of the coating film (number of carbon atoms / sum of number of silicon and other atoms) is preferably 1.00 or less, more preferably 0.60 or less, even more preferably 0.50 or less, even more preferably 0.40 or less, even more preferably 0.30 or less, and even more preferably 0.25 or less. In one embodiment, the ratio of the number of carbon atoms to the total number of sodium, potassium, magnesium, calcium, aluminum, and silicon atoms on the surface is preferably 0.20 or less, more preferably 0.15 or less, and even more preferably 0.10 or less. The ratio of the number of carbon atoms to the total number of sodium, potassium, magnesium, calcium, aluminum and silicon atoms on the surface of the coating film can be determined by a method using a photoelectron spectrometer, which will be described later.

[0096] In one embodiment, the coating film preferably contains inorganic fine particles. The inorganic fine particles can be the same as those described above. The inorganic fine particles are preferably inorganic fine particles containing silica. The inorganic fine particles preferably have a primary particle diameter of 1 nm or more and less than 50 nm, more preferably 1 nm or more and 40 nm or less, even more preferably 1 nm or more and 30 nm or less, even more preferably 1 nm or more and 20 nm or less, and particularly preferably 3 nm or more and 10 nm or less.

[0097] In the coating film, the ratio of the number of silicon atoms to the number of oxygen atoms is preferably 2.0 or more and 2.5 or less, and more preferably 2.0 or more and 2.3 or less.

[0098] In the above-described laminate, the coating film preferably has a kurtosis of brightness distribution in a cross-sectional image thereof taken by a scanning electron microscope of 0.320 or less, more preferably 0.200 or less, more preferably 0.150 or less, more preferably 0.130 or less, more preferably 0.120 or less, more preferably 0.110 or less, more preferably 0.100 or less, and more preferably 0.090 or less.

[0099] The coating film (a coating film having a porous structure) also has voids due to gaps between particles, etc., in a cross-sectional image obtained by a scanning electron microscope (SEM) observation method described below, and therefore the coating film has an uneven structure in its cross-section. As a result, a cross-sectional image obtained by a scanning electron microscope (SEM) observation method described below has both bright and dark areas and a brightness distribution. The coating film has a kurtosis of 0.320 or less in the brightness distribution in a cross-sectional image obtained by a scanning electron microscope. The kurtosis of the brightness distribution in a cross-sectional image obtained by a scanning electron microscope can be determined by the method described below. The kurtosis of the brightness distribution is preferably 0.300 or less, more preferably 0.250 or less, more preferably 0.200 or less, more preferably 0.150 or less, more preferably 0.130 or less, more preferably 0.120 or less, more preferably 0.110 or less, more preferably 0.100 or less, and more preferably 0.090 or less. Such a kurtosis in the brightness distribution results in a good porous structure and excellent light transmittance.

[0100] In the laminate, the arithmetic mean roughness of the coating film is preferably 0.1 nm to 10.0 nm, more preferably 0.2 nm to 7.0 nm, even more preferably 0.2 nm to 5.0 nm, and particularly preferably 0.2 nm to 1.5 nm. When the arithmetic mean roughness of the coating film is within the above range, a laminate having excellent deep ultraviolet transmittance and abrasion resistance can be obtained. The arithmetic mean roughness of the coating film can be determined by measurement using a scanning probe microscope (SPM), which will be described later.

[0101] In the laminate, the substrate is preferably quartz glass or sapphire glass, more preferably quartz glass. Examples of quartz glass include fused quartz glass and synthetic quartz glass, and it is more preferable to use synthetic quartz glass as the substrate.

[0102] In the laminate, the thickness of the substrate is preferably 0.1 mm or more and 100 mm or less, more preferably 0.1 mm or more and 50 mm or less, and even more preferably 0.3 mm or more and 30 mm or less.

[0103] The laminate is preferably obtained by a manufacturing method including a step of applying a coating agent to a substrate; and a step of heat treating the substrate at a temperature of 200° C. or higher and 1000° C. or lower for a period of more than 10 minutes. The coating agent may be the same as the inorganic fine particle dispersion liquid described above, or may be the same as the coating liquid described below. The substrate, coating step, and heat treatment step can be the same as those described above or below.

[0104] In one embodiment, the laminate can be obtained by a production method including the steps of: applying a coating liquid containing an alkoxysilane, water, an acid catalyst, and a pore-forming agent to a substrate; and heat-treating the coating liquid at a temperature of 200°C or higher and 1000°C or lower for more than 10 minutes. In the laminate, the alkoxysilane, acid catalyst, and pore-forming agent described below can be used. In the laminate, the coating step and heat treatment step can be the same as those described above or below.

[0105] The present invention also relates to the following laminate. A laminate obtainable by a method for producing a laminate having a substrate and a coating film applied to at least one of its main surfaces, the method comprising the steps of: applying a coating agent to a substrate; and heat treating the substrate at a temperature of 200°C or higher and 1000°C or lower for more than 10 minutes.

[0106] The coating agent may be the same as the inorganic fine particle dispersion liquid described above, or may be the same as the coating liquid described below. The substrate, coating process, heat treatment process, and coating film may be the same as those described above or below.

[0107] The present invention also provides the following coating liquid. A coating liquid containing an alkoxysilane, water, an acid catalyst, a pore-forming agent, and a liquid dispersion medium A having a boiling point of more than 121°C and less than 190°C, wherein the weight ratio of the liquid dispersion medium A is 0.5% by mass or more and less than 15% by mass, where the total amount of the coating liquid is 100% by mass.

[0108] In the coating liquid of the present invention, the weight ratio of water, liquid dispersion medium A, and liquid dispersion medium A can be the same as described above.

[0109] In the coating liquid of the present invention, the alkoxysilane may be the same as that described above. In the coating liquid of the present invention, the alkoxysilane is preferably one of the following. An alkoxysilane containing the following alkoxysilanes C01 and C02, in which the ratio of the weight of SiO2 contained in alkoxysilane C02 to the total weight of SiO2 contained in the alkoxysilanes ([weight of SiO2 contained in alkoxysilane C02] / [total weight of SiO2 contained in alkoxysilanes]) is 0.00 or more and 0.50 or less: Alkoxysilane C01: At least one alkoxysilane selected from tetraalkoxysilanes and alkoxysilane condensates represented by the following general formula (01): General formula (01) [ka] (In the formula, each R independently represents an alkyl group having 1 to 6 carbon atoms, and n is an integer of 2 to 1000.) Examples of R, an alkyl group having 1 to 6 carbon atoms, include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, a tert-amyl group (1,1-dimethylpropyl group), etc. Preferred examples include a methyl group, an ethyl group, and a butyl group, and more preferred examples include a methyl group and an ethyl group. In the above general formula (01), n ​​represents an integer of 2 to 1000, preferably 2 to 100, more preferably 3 to 50, and still more preferably 3 to 30. The weight average molecular weight of the silicon compound having the structure represented by the general formula (01) is preferably 170 or more and 500,000 or less, more preferably 170 or more and 30,000 or less, more preferably 200 or more and 10,000 or less, more preferably 240 or more and 8,000 or less, and more preferably 240 or more and 5,000 or less. In addition, the silicon compound having the structure represented by general formula (01) may have a partially hydrolyzed alkoxy group site, and may further be condensed at the hydrolyzed site.

[0110] Commercially available alkoxysilane condensates include, for example, Methyl Silicate 51, Methyl Silicate 53A, Ethyl Silicate 40, Ethyl Silicate 48, and EMS-485 (all manufactured by Colcoat Co., Ltd.). Among the alkoxysilane condensates, commercially available products of hydrolysis condensates of methyl silicate include, for example, MS51, MS56, MS57, and MS56S (all manufactured by Mitsubishi Chemical Corporation).

[0111] Among the alkoxysilane condensates, commercially available products of hydrolysis condensates of ethyl silicate include, for example, HAS-1, HAS-6, and HAS-10 (all manufactured by Colcoat Co., Ltd.). Alkoxysilane C02: At least one alkoxysilane selected from alkoxysilanes represented by the following general formula (02) and condensates thereof: Si(R a )q (R b ) 4-q (02) In formula (02), R a represents a hydrogen atom or a non-hydrolyzable organic group, and R b represents a hydrolyzable group, and q represents an integer of 1 to 2.

[0112] R a Examples of the non-hydrolyzable organic group include alkyl groups having 1 to 10 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, tert-amyl (1,1-dimethylpropyl), 1,1-dimethyl-3,3-dimethylbutyl, heptyl, octyl, nonyl, and decyl; cycloalkyl groups having 3 to 10 carbon atoms, such as cyclopentyl and cyclohexyl; and aromatic groups having 6 to 15 carbon atoms, such as phenyl, naphthyl, and anthracenyl. Alkyl groups are preferred, and methyl and ethyl groups are more preferred.

[0113] R b Examples of the hydrolyzable group include alkoxy groups having 1 to 5 carbon atoms, such as a methoxy group, an ethoxy group, and a propoxy group, and preferred are a methoxy group and an ethoxy group.

[0114] The silicon compound represented by formula (02) may have a hydrolyzable group that has been hydrolyzed, and may further be condensed at the hydrolyzed portion.

[0115] Examples of silicon compounds represented by formula (02) include silicon compounds in which q is 1, such as methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltriisopropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, phenyltrimethoxysilane, and phenyltriethoxysilane; and silicon compounds in which q is 2, such as dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, and methylphenyldimethoxysilane. Particularly preferred are methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, and diethyldiethoxysilane.

[0116] The ratio of the weight of SiO2 contained in alkoxysilane C02 to the total weight of SiO2 contained in the alkoxysilanes ([weight of SiO2 contained in alkoxysilane C02] / [total weight of SiO2 contained in alkoxysilanes]) is preferably 0.00 or more and 0.50 or less, more preferably 0.10 or more and 0.50 or less, even more preferably 0.20 or more and 0.50 or less, and even more preferably 0.25 or more and 0.40 or less.

[0117] With the total amount of the coating liquid taken as 100% by mass, the total weight of SiO2 contained in alkoxysilane C01 and alkoxysilane C02 is preferably from 0.05% by mass to 10% by mass, more preferably from 0.1% by mass to 7.5% by mass, even more preferably from 0.2% by mass to 5.0% by mass, and particularly preferably from 0.5% by mass to 2.0% by mass.

[0118] The coating liquid of the present invention preferably contains a liquid dispersion medium B having a boiling point of less than 100° C. The liquid dispersion medium B can be the same as those described above.

[0119] [Porosity-forming agent] The coating solution of the present invention contains a pore-forming agent. As described below, in the present invention, for example, a substrate having a pre-heat-treatment coating film formed on its surface is formed through a coating process using the coating solution and a dispersion medium removal process. The pre-heat-treatment coating film contains a pore-forming agent, and in the subsequent heat treatment process, the pore-forming agent contained in the pre-heat-treatment coating film is thermally decomposed and removed, thereby imparting pores to the coating film. The coating film has voids derived from the pore-forming agent, resulting in a layer with a low refractive index. This is advantageous for improving light transmittance.

[0120] Examples of the pore-forming agent include organic ammonium salts and pyridinium salts, and preferably organic ammonium salts, and preferably organic ammonium salts having a structure represented by the following general formula (4): General formula (4) [ka] (In the formula, L1 to L4 each independently represent a hydrogen atom or an organic group having 1 to 15 carbon atoms, and the total number of carbon atoms contained in the organic groups of L1 to L4 is 1 to 40. E1 represents a monovalent anion.)

[0121] In general formula (4), L1 to L4 each independently represent a hydrogen atom or an organic group having 1 to 15 carbon atoms. Specific examples of the organic group having 1 to 15 carbon atoms include alkyl groups having 1 to 15 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tetradecyl, 2-hydroxyethyl, 3-chloro-2-hydroxypropyl, and 2-chloroethyl; cycloalkyl groups having 3 to 10 carbon atoms, such as cyclopentyl and cyclohexyl; and aromatic groups having 6 to 15 carbon atoms, such as phenyl and benzyl.

[0122] In general formula (4), E1 represents a monovalent anion. Specific examples of E1 include halide ions (fluoride ions, chloride ions, bromide ions, and iodide ions), hydrogen sulfate ions, nitrate ions, bis(trifluoromethanesulfonyl)imide ions, bis(fluorosulfonyl)imide ions, p-toluenesulfonate ions, hexafluorophosphate ions, and tetrafluoroborate ions, and are preferably chloride ions, bromide ions, and hydrogen sulfate ions, more preferably chloride ions and bromide ions, and more preferably chloride ions.

[0123] The organic ammonium salt having the structure represented by the general formula (4) is preferably a secondary ammonium salt, a tertiary ammonium salt, or a quaternary ammonium salt, more preferably a tertiary ammonium salt or a quaternary ammonium salt, and more preferably a quaternary ammonium salt. Specific examples of the quaternary ammonium salt include the following: Tetramethylammonium chloride, trimethyltetradecylammonium chloride, n-octyltrimethylammonium chloride, decyltrimethylammonium chloride, tetraethylammonium chloride, benzyltrimethylammonium chloride, trimethylphenylammonium chloride, benzyltributylammonium chloride, bis(2-hydroxyethyl)dimethylammonium chloride, triethylmethylammonium chloride, (3-chloro-2-hydroxypropyl)trimethylammonium chloride, (2-chloroethyl)trimethylammonium chloride, 2-hydroxypropyltrimethylammonium chloride, tributylmethylammonium chloride, (2-methoxyethoxymethyl)triethylammonium chloride, benzyldimethylphenylammonium chloride, tetrabutylammonium chloride, tetrapropylammonium chloride, dodecyltrimethylammonium chloride, diallyldimethylammonium chloride, dodecyltrimethylammonium chloride, benzyltriethylammonium chloride, (2-hydroxyethyl)trimethyl Ammonium chloride, trimethylpropylammonium bromide, tetramethylammonium bromide, 2-bromoethyltrimethylammonium bromide, n-octyltrimethylammonium bromide, trimethylphenylammonium bromide, hexyldimethyloctylammonium bromide, hexyltrimethylammonium bromide, (3-bromopropyl)trimethylammonium bromide, benzyltriethylammonium bromide, butyltrimethylammonium bromide, tetrahexylammonium bromide, tetrapentylammonium bromide, trimethylnonylammonium bromide, benzyltrimethylammonium bromide, (2-hydroxyethyl)trimethylammonium bromide, tetradecyltrimethylammonium bromide, tetraethylammonium bromide, dodecyltrimethylammonium bromide, decyltrimethylammonium bromide, tetrapropylammonium bromide, tetrabutylammonium bromide, dimethyldioctylammonium bromide, benzyltributylammonium bromide, tetra(decyl)ammonium bromide,Tetraheptylammonium bromide, tetra-n-octylammonium bromide, didecyldimethylammonium bromide, and didodecyldimethylammonium bromide.

[0124] In general formula (4), L1 to L4 each independently represent a hydrogen atom or an organic group having 1 to 15 carbon atoms. The organic group in L1 to L4 preferably has 1 to 12 carbon atoms, more preferably 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and still more preferably 1 to 7 carbon atoms. Such an organic group can exhibit good coatability.

[0125] In the general formula (4), the total number of carbon atoms in the organic groups contained in L1 to L4 is 1 to 40. The total number of carbon atoms in the organic groups in L1 to L4 is preferably 1 to 32, more preferably 1 to 26, more preferably 1 to 24, more preferably 1 to 18, more preferably 4 to 18, more preferably 4 to 16, more preferably 4 to 14, and more preferably 4 to 13. Such a group can exhibit good coatability.

[0126] <Ratio of the weight of the pore-forming agent to the total weight of SiO2 contained in the alkoxysilane> In the coating liquid (applied liquid) of the present invention, the ratio of the weight of the pore-forming agent to the total weight of SiO contained in the alkoxysilane ([pore-forming agent weight] / [total weight of SiO contained in the alkoxysilane]) is 0.10 or more. The lower limit is preferably 0.10 or more, more preferably 0.20 or more, more preferably 0.30 or more, more preferably 0.40 or more, more preferably 0.50 or more, more preferably 0.60 or more, more preferably 0.70 or more, more preferably 1.50 or more, more preferably 1.70 or more, more preferably 2.00 or more, more preferably 2.51 or more, and more preferably 2.60 or more. The upper limit is preferably 8.00 or less, more preferably 5.00 or less, more preferably 4.50 or less, more preferably 4.00 or less, and more preferably 3.00 or less.

[0127] <Ratio of the amount of pore-forming agent to the amount of alkyl groups contained in alkoxysilane C02> In the coating liquid (applied liquid) of the present invention, the ratio of the amount of substance of the pore-forming agent to the amount of substance of alkyl groups contained in alkoxysilane C02 ([amount of substance of alkoxysilane C02] × q (number of alkyl groups in alkoxysilane C02)) is 0.1 or more. The lower limit is preferably 0.1 or more, more preferably 0.3 or more, and even more preferably 0.5 or more.

[0128] [Acid catalyst] The coating liquid of the present invention contains an acid catalyst. Examples of the acid catalyst include organic acids and inorganic acids, and examples of the organic acids include formic acid, acetic acid, propionic acid, butanoic acid, oxalic acid, maleic acid, phthalic acid, and fumaric acid. Examples of the inorganic acids include hydrochloric acid, nitric acid, sulfuric acid, and phosphoric acid. Preferred are formic acid, acetic acid, oxalic acid, hydrochloric acid, nitric acid, sulfuric acid, and phosphoric acid, more preferably formic acid, acetic acid, hydrochloric acid, nitric acid, sulfuric acid, and phosphoric acid, more preferably hydrochloric acid, nitric acid, sulfuric acid, and phosphoric acid, more preferably hydrochloric acid, nitric acid, and sulfuric acid, and more preferably hydrochloric acid and nitric acid.

[0129] [Other ingredients] The coating liquid of the present invention may contain components other than the liquid dispersion medium A, alkoxysilane, water, acid catalyst, and pore-forming agent, as well as thickeners, thixotropy agents, antifoaming agents, light stabilizers, pigments, antifungal agents, dustproofing agents, antifreeze performance improvers, weather resistance agents, UV stabilizers, surfactants, etc., depending on the intended use and method of use.

[0130] [Surfactants] The coating liquid of the present invention may contain a surfactant. When the coating liquid of the present invention contains a surfactant, it may contain the same surfactant as the above-mentioned [Surfactant]. The surfactant that can be contained in the coating liquid of the present invention is preferably a cationic surfactant or a nonionic surfactant.

[0131] Examples of cationic surfactants include cetyltrimethylammonium chloride, dioctadecyldimethylammonium chloride, N-octadecylpyridinium bromide, and cetyltriethylphosphonium bromide.

[0132] Examples of nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene steryl ethers, and polyoxyethylene polyoxypropylene alkyl ethers.

[0133] <How to prepare the coating liquid> The coating liquid of the present invention can be prepared by the same method as described above in "<Method for producing inorganic particle dispersion>" except that it does not contain inorganic particles.

[0134] A preferred embodiment of the method for preparing the coating liquid of the present invention involves preparing the following agent A01 or agent B01 and using it to prepare the coating liquid.

[0135] [A01 agent] Agent A01 contains component C (alkoxysilane), water, and an acid catalyst, and may optionally contain liquid dispersion medium B. When liquid dispersion medium B is contained, agent A01 can be prepared by adding liquid dispersion medium B to component C, followed by adding water and the acid catalyst, and mixing at room temperature or at a temperature of 10°C to 40°C. The amounts of each component added in this preparation method are as follows: Component C: An amount added such that the weight ratio of SiO2 contained in the alkoxysilane is 5% by mass or more and 25% by mass or less when the total weight of agent A01 is 100% by mass. Water: Add an amount that is 2 to 20 times the amount of silicon atoms contained in the alkoxysilane. Acid catalyst: An amount to be added that is 0.001 to 0.1 times the amount of silicon atoms contained in the alkoxysilane. Liquid dispersion medium B: The amount of liquid dispersion medium B added so that the weight ratio is 20% to 80% by mass when the total weight of agent A01 is 100% by mass. It is preferable that agent A01 contains alkoxysilane C01.

[0136] [B01 agent] Agent B01 can be prepared by adding component C to agent A01, and optionally adding liquid dispersion medium B, and mixing them at room temperature or at a temperature of 10° C. to 40° C. The amounts of each component added in this preparation method are as follows: Component C: An amount added such that the weight ratio of SiO2 contained in the alkoxysilane is 7% by mass or more and 30% by mass or less when the total weight of agent B01 is 100% by mass. Water: Add an amount that is 2 to 15 times the amount of silicon atoms contained in the alkoxysilane. Acid catalyst: Amount added that is 0.001 to 0.1 times the amount of silicon atoms contained in the alkoxysilane Liquid dispersion medium B: The amount of liquid dispersion medium B added so that the weight ratio is 20% to 80% by mass when the total weight of B01 agent is 100% by mass.

[0137] [Coating liquid] The coating liquid can be prepared by mixing the above-mentioned agent A01 or B01, liquid dispersion medium A, pore-forming agent, and optionally liquid dispersion medium B, water, an acid catalyst, and the other components described above. The temperature during mixing is not limited, but examples include room temperature and temperatures between 10°C and 40°C. The content of each component can be exemplified by the examples in the coating liquid described above.

[0138] <Method of manufacturing a laminate having a coating film made from a coating liquid> The method for producing a laminate having a coating film made from the coating liquid of the present invention can be the same as the method described above in "<Method for producing a laminate>" except that the coating liquid is used instead of or in addition to the inorganic fine particle dispersion.

[0139] <Laminate> The thickness of the coating film in the laminate having a substrate and a coating film obtained by the above method is not particularly limited, but can be the same as the thickness described above, for example, 20 nm or more and less than 100 nm, in another embodiment, the thickness of the coating film is 20 nm or more and less than 75 nm, in another embodiment, the thickness of the coating film is 25 nm or more and less than 75 nm, and in another embodiment, the thickness of the coating film is 25 nm or more and 60 nm or less. The thickness of the coating film can be adjusted by changing the weight ratio of the alkoxysilane in the coating liquid and the amount of the coating liquid applied. The thickness of the coating film can be measured from an image of the cross section of the coating film obtained by observation with a scanning electron microscope (SEM). [Example]

[0140] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to these examples.

[0141] The main materials used are as follows:

[0142] [Base material] Quartz glass plate (Kenis Co., Ltd.; synthetic quartz glass; average transmittance (wavelength range of 185 nm to 300 nm): 91.0%; width 26 mm, length 76 mm, thickness 1.0 mm). The quartz glass plate with an average transmittance of 91.0% is referred to as substrate-1. Quartz glass plate (manufactured by Tokyo Glass Instruments Co., Ltd.; fused silica glass; average transmittance (wavelength region of 185 nm to 300 nm): 91.5%; width 26 mm, length 76 mm, thickness 1.0 mm). The quartz glass plate with an average transmittance of 91.5% is referred to as substrate-2. Soda lime glass plate (manufactured by AS ONE Corporation; soda lime glass; width 26 mm, length 76 mm, thickness 1.3 mm) The soda lime glass plate is referred to as substrate-3.

[0143] The average transmittance of the quartz glass plate was measured using a UV-3600 ultraviolet-visible-near-infrared spectrophotometer (Shimadzu Corporation). The transmittance was then read from the obtained transmittance spectrum in the wavelength range of 185 nm to 300 nm, and the average transmittance was calculated.

[0144] [Inorganic fine particles] The following dispersion liquid was used as the inorganic fine particles. Particle-1 (inorganic fine particles X): Snowtex (registered trademark) ST-OXS (manufactured by Nissan Chemical Industries, Ltd.; aqueous dispersion of colloidal silica; average particle diameter of 4 nm to 6 nm; solid content of 10% by mass) The weight ratios of inorganic fine particles in Tables 1-1 and 1-2 are weight ratios calculated from the solid concentration of inorganic fine particles when the total amount of the composition (total amount of inorganic fine particle dispersion) is taken as 100% by mass.

[0145] [Liquid dispersion medium A] The liquid dispersion medium A used was as follows: A-1: 3-Methoxy-3-methylbutanol (boiling point 174°C) A-2: 2-Methoxyethyl acetate (boiling point 143°C)

[0146] [Liquid dispersion medium B] B-1: Ethanol (boiling point 78°C) [Other liquid dispersion media] S-1: n-butanol (boiling point 118°C) [Alkoxysilane] C-1: MKC Silicate (registered trademark) MS56S (manufactured by Mitsubishi Chemical Corporation; polymethoxysiloxane) C-2: Dimethoxydimethylsilane C-3: Tetraethyl orthosilicate C-4: Triethoxymethylsilane [Porosity-forming agent] P-1: Benzyltriethylammonium chloride P-2: Dodecyltrimethylammonium chloride [Acid catalyst] AC-1: Nitric acid

[0147] [Other ingredients] Component 1: BYK (registered trademark)-349 (manufactured by BYK Japan Co., Ltd.; polyether-modified siloxane)

[0148] In the examples and comparative examples, laminates each consisting of a substrate and a coating film were prepared by the following method. Examples 1 to 4 and Comparative Example 1 An inorganic particle dispersion was prepared by adding alkoxysilane to a mixture of inorganic particles, liquid dispersion medium A, liquid dispersion medium B, water, and other ingredients in the weight ratios shown in Tables 1-1 and 1-2 and stirring. Next, one side of the substrate shown in Table 1-1 was masked with masking tape. Substrate-1, Substrate-2, or Substrate-3 was used as the substrate. Using a Micro Speed ​​Dip Coater MD-0408-01 (manufactured by SDI Corporation), the prepared inorganic fine particle dispersion was applied to the unmasked side of the masked substrate at a lifting speed of 1.666 mm / sec. After application, the masking tape was removed from the substrate and it was allowed to dry naturally at room temperature.

[0149] The obtained substrate was heated in an oven at 100°C for 3 minutes in an air atmosphere to remove the solvent, and then heat treatment step-1 or heat treatment step-2 according to the present invention described below was applied to the substrate in a muffle furnace to form a coating film on the substrate, thereby obtaining a laminate consisting of the substrate and the coating film. In heat treatment step-1, the temperature was held in the range of 200°C to 1000°C for 271 minutes, the temperature was held in the range of 300°C to 900°C for 186 minutes, the temperature was held in the range of 300°C to 800°C for 186 minutes, the temperature was held in the range of 400°C to 800°C for 122 minutes, the temperature was held in the range of 500°C to 800°C for 70 minutes, and the temperature was held in the range of 500°C to 720°C for 70 minutes. In the heat treatment step-2, the time for holding the temperature within the temperature range of 200°C or higher and 1000°C or lower was 2 minutes, and the time for holding the temperature within the temperature range of 300°C or higher and 900°C or lower, the time for holding the temperature within the temperature range of 300°C or higher and 800°C or lower, the time for holding the temperature within the temperature range of 400°C or higher and 800°C or lower, the time for holding the temperature within the temperature range of 500°C or higher and 800°C or lower, and the time for holding the temperature within the temperature range of 500°C or higher and 720°C or lower were all 2 minutes. After the heat treatment step, the laminate consisting of the substrate and the coating film was taken out of the muffle furnace and allowed to cool at room temperature. Heat treatment process-1: -In an air atmosphere, the temperature is increased from room temperature to 600°C at a rate of 4°C / min. -Air atmosphere / 600℃ for 30 minutes -In an air atmosphere: Cool naturally by stopping heating from 600℃ to 200℃ Heat treatment process-2: - In an air atmosphere / Keep at a temperature between 650℃ and 710℃ for 2 minutes

[0150] Example 5 A coating liquid was prepared using each component as follows so as to obtain the weight ratio shown in Table 1-2, and the same procedure as in Example 1 was carried out except that a laminate was produced using the coating liquid instead of the inorganic microparticle dispersion liquid. (Preparation of A01 Agent-1) B-1 (49.4 g) and C-1 (25.0 g) were mixed, and an aqueous solution (17.7 g) containing 0.1 mol / L of AC-1 was added thereto. The mixture was mixed at room temperature for 1 hour and then allowed to stand for 1 day to prepare A01 agent-1. (Preparation of B01 Agent-1) C-2 (3.0 g) was added to weighed A01 agent-1 (27.8 g), and the mixture was mixed at room temperature for 1 hour and then allowed to stand for 1 day to prepare B01 agent-1. (Preparation of coating liquid) A coating solution having the weight ratios shown in Table 1-1 was prepared by mixing water (19.3 g), B-1 (109.0 g), A-1 (8.3 g), a solution containing P-1 / B-1 / water at a weight ratio of 50 / 40 / 10 (9.5 g), an aqueous solution containing 1 mol / L of AC-1 (4.2 g), and B01 agent-1 (9.7 g) at room temperature for 1 hour.

[0151] Example 6 An inorganic particle dispersion was prepared by adding alkoxysilane to a mixture of inorganic particles, liquid dispersion medium A, liquid dispersion medium B, water, and other ingredients in the weight ratio shown in Table 1-2 and stirring. Next, one side of a substrate was masked with masking tape. Substrate-1 was used here. Using a Micro Speed ​​Dip Coater MD-0408-01 (manufactured by SDI Corporation), the prepared inorganic particle dispersion was applied to the unmasked side of the masked substrate at a lifting speed of 1.666 mm / sec. After application, the substrate was allowed to air dry at room temperature.

[0152] The resulting substrate was heated in an oven at 100°C for 3 minutes under air to remove the solvent, and the inorganic particle dispersion was then applied to the unmasked side of the substrate again using a Micro Speed ​​Dip Coater MD-0408-01 (manufactured by SDI Corporation) at a lifting speed of 1.666 mm / sec. After the second application, the masking tape was removed from the substrate and it was allowed to dry naturally at room temperature.

[0153] The obtained substrate was heated in an oven under an air atmosphere at 100°C for 3 minutes to remove the solvent, and then the substrate was subjected to the heat treatment process-1 according to the present invention in a muffle furnace in the same manner as in Example 1 to form a coating film on the substrate, thereby obtaining a laminate consisting of the substrate and the coating film. After the heat treatment step, the laminate consisting of the substrate and the coating film was taken out of the muffle furnace and allowed to cool at room temperature.

[0154] Example 7 An inorganic particle dispersion was prepared by adding alkoxysilane to a mixture of inorganic particles, liquid dispersion medium A, liquid dispersion medium B, water, and other ingredients in the weight ratio shown in Table 1-2 and stirring. Next, one side of a substrate was masked with masking tape. Substrate-1 was used here. Using a Micro Speed ​​Dip Coater MD-0408-01 (manufactured by SDI Corporation), the prepared inorganic fine particle dispersion was applied to the unmasked side of the masked substrate at a lifting speed of 1.666 mm / sec. After application, the masking tape was removed from the substrate and it was allowed to dry naturally at room temperature.

[0155] The obtained substrate was heated in an oven at 100°C for 3 minutes in an air atmosphere to remove the solvent, and then the substrate was subjected to the heat treatment process-3 according to the present invention described below in a muffle furnace to form a coating on the substrate, thereby obtaining a laminate consisting of the substrate and the coating. In the heat treatment process-3, the temperature was held for 335 minutes within the temperature range of 200°C to 1000°C, 247 minutes within the temperature range of 300°C to 900°C, 247 minutes within the temperature range of 300°C to 800°C, 180 minutes within the temperature range of 400°C to 800°C, 124 minutes within the temperature range of 500°C to 800°C, and 124 minutes within the temperature range of 500°C to 720°C. After the heat treatment step, the laminate consisting of the substrate and the coating film was taken out of the muffle furnace and allowed to cool at room temperature. Heat treatment process-3: -In an air atmosphere, the temperature is increased from room temperature to 650°C at a rate of 4°C / min. -Air atmosphere / 650℃ for 60 minutes -In an air atmosphere: Cool naturally by stopping heating from 650℃ to 200℃

[0156] Comparative Example 2 Alkoxysilane was added to a mixture of other liquid dispersion media, water, and other components in the weight ratios shown in Table 1-2, and the mixture was allowed to react for two days. Next, one side of the substrate was masked with masking tape to prepare a substrate. Substrate-3 was used here. Using a Micro Speed ​​Dip Coater MD-0408-01 (manufactured by SDI Corporation), the prepared coating solution was applied to the unmasked side of the masked substrate at a lifting speed of 1.666 mm / sec. After application, the masking tape was removed from the substrate and it was allowed to dry naturally at room temperature.

[0157] The obtained substrate was heated in an oven at 80°C for 2 minutes in an air atmosphere, and then heated in an oven at 150°C for 2 minutes in an air atmosphere to remove the solvent. Then, in a muffle furnace, a heat treatment process 4 not according to the present invention was applied to the substrate to attempt to form a coating on the substrate. However, the substrate repelled the coating liquid, and a uniform coating was not formed. In the heat treatment process 4, the time held within the temperature range of 200°C to 1000°C, the time held within the temperature range of 300°C to 900°C, and the time held within the temperature range of 300°C to 800°C were all 2 minutes, and the time held within the temperature range of 400°C to 800°C, the time held within the temperature range of 500°C to 800°C, and the time held within the temperature range of 500°C to 720°C were all 0 minutes. Heat treatment process-4: -Muffle furnace / Air atmosphere / 300℃ for 2 minutes

[0158] The examples and comparative examples were evaluated by the following methods. [Coating thickness] The evaluation was carried out based on the image of the cross section of the coating film obtained by observation with a scanning electron microscope (SEM) shown below. Scanning electron microscope (SEM) observation Scanning electron microscope (SEM) observation was carried out according to the following procedure. The laminate consisting of the substrate and coating was split to expose the cross section of the laminate, and the resulting sample was fixed to the sample stage with carbon tape so that the cross section was facing up. Carbon paste was then applied to the side, and approximately 0.5 nm of Pt-Pd was vapor-deposited using a Hitachi High-Technologies Corporation E1030 ion sputter to provide electrical conductivity. The SEM was a Hitachi High-Technologies HITACHI SU8020, and secondary electron images were taken using an acceleration voltage of 2 kV and SE(U) imaging mode. The measurement magnification was 100,000 times, and 10 fields of view were measured. The thickness of the coating film was evaluated based on the obtained images of the cross section of the coating film, and the average value of the thicknesses in 10 fields of view was used.

[0159] [Kurtosis in the brightness distribution of cross-sectional images taken by a scanning electron microscope] The kurtosis of the brightness distribution in the cross-sectional image of the scanning electron microscope (sometimes referred to as the kurtosis of the brightness distribution) was evaluated using the following method. Grayscale images (10 fields of view) of the cross-section of the laminate obtained by the above-mentioned scanning electron microscope (SEM) observation were cropped to a size of 25 pixels x 1280 pixels, leaving only the coating film portion. The brightness kurtosis K of the cropped portion was calculated using the formula defined by Fisher (X100).

number

number

number

[0160] [Spectral transmittance] The transmittance of the laminate consisting of the substrate and coating was measured using a UV-3600 ultraviolet-visible-near-infrared spectrophotometer (Shimadzu Corporation). The transmittance values ​​in the wavelength range of 185 nm to 300 nm were then read from the obtained transmittance spectrum, and the average transmittance (wavelength 185-300 nm) was calculated. The transmittance values ​​at wavelengths of 185 nm, 222 nm, and 254 nm were also read. The transmittance values ​​in the wavelength range of 185 nm to 280 nm were also read, and the average transmittance (wavelength 185-280 nm) was calculated. The obtained laminate was observed to have an increase in average transmittance and transmittance at wavelengths of 185 nm, 222 nm, and 254 nm compared to an uncoated substrate (a substrate without a coating film). The increase in average transmittance and transmittance at wavelengths of 185 nm, 222 nm, and 254 nm was defined by the following formulas, respectively.

[0161] [Average transmittance increase (points) (wavelength range 185 nm to 300 nm)] = [Average transmittance (%) of laminate (average value of transmittance for each wavelength in the wavelength range of 185 nm to 300 nm)] - [Average transmittance (%) of uncoated substrate (average value of transmittance for each wavelength in the wavelength range of 185 nm to 300 nm)] [Increase in transmittance at wavelength 185 nm (points)] = [Transmittance (%) of laminate at wavelength 185 nm] - [Transmittance (%) of uncoated substrate at wavelength 185 nm] [Increase in transmittance at wavelength 222 nm (points)] = [Transmittance (%) of laminate at wavelength 222 nm] - [Transmittance (%) of uncoated substrate at wavelength 222 nm] [Increase in transmittance at wavelength 254 nm (points)] = [Transmittance (%) of laminate at wavelength 254 nm] - [Transmittance (%) of uncoated substrate at wavelength 254 nm] [Average transmittance increase (points) (wavelength range 185 nm to 280 nm)] = [Average transmittance (%) of laminate (average value of transmittance for each wavelength in the wavelength range of 185 nm to 280 nm)] - [Average transmittance (%) of uncoated substrate (average value of transmittance for each wavelength in the wavelength range of 185 nm to 280 nm)]

[0162] [Number of carbon atoms / total number of silicon atoms] The ratio of the number of carbon atoms to the total number of sodium, potassium, magnesium, calcium, aluminum and silicon atoms on the surface of the coating film (number of carbon atoms / sum of number of silicon and other atoms) was measured as follows. Using a photoelectron spectrometer (product name "AXIS-ULTRA", manufactured by KRATOS), X-ray source: AlKα (monochrome) 15 kV 10 mA, wide scan, pass energy: 160 eV, step: 1 eV, number of accumulations: 3, vacuum degree: approximately 5 × 10 -8 The measurements were carried out at room temperature and pressure of 1000 torr. Among the peaks due to sodium, potassium, magnesium, calcium, aluminum, silicon, oxygen, and carbon, those identified in the wide scan were measured using a narrow scan. The peaks identified in the wide scan were C1s, O1s, Si2p, and Na1s. Na1s was identified only in Comparative Example 1. For narrow scan, a photoelectron spectrometer (product name "AXIS-ULTRA", manufactured by KRATOS) was used, with an X-ray source of AlKα (monochrome) at 15 kV and 10 mA, narrow scan, pass energy of 20 eV, step of 0.1 eV, number of accumulations: C1s 15 times, O1s 3 times, Si2p 10 times, Na1s 15 times, and vacuum level of approximately 5 × 10 -8The measurements were carried out at room temperature and at torr, and the ratio of the number of atoms was obtained by measuring the intensity of escaped photoelectrons on the film surface. When charge-up occurred during measurement, a charge-correcting electron gun was used. Furthermore, when performing charge correction of the chemical shift of the measured spectrum, a standard sample can be used as appropriate. In this case, the C1s spectrum due to C in the CC structure was corrected to an energy standard of 284.8 eV.

[0163] [Arithmetic mean roughness of coating film] The arithmetic mean roughness Sa of the coating film was evaluated using a scanning probe microscope (SPM) as follows. [SPM measurement conditions] Equipment: Scanning probe microscope (SPM-9600) (Shimadzu Corporation) Cantilever: NanoWorld NCHR-20 T (thickness): 4μm L (length): 125μm W(width): 30μm f0 (resonance frequency): 320kHz k (spring constant): 42N / m Test conditions: Dynamic mode

[0164] Configuration parameters Observation condition settings JPEG2025123183000010.jpg3992 (Tilt correction) Average value in the X direction Average value in the Y direction Median value in the X direction Median value in the Y direction

[0165] Scanning probe microscope (SPM) measurements were performed according to the following procedure. The laminate sample consisting of the glass substrate and the coating film was fixed to the SPM sample stage with carbon tape, with the coating film facing upward. The SPM used was a Shimadzu scanning probe microscope (SPM-9600) and the cantilever was a NanoWorld NCHR-20. Measurements were performed with a scanning range of 1 μm × 1 μm and a scanning speed of 0.501 Hz. The image obtained was set to 256 pixels x 256 pixels, and the feedback was set to an I gain of 0.001 and a P gain of 500 for measurement. The obtained height image was subjected to tilt correction using the average value in the X direction, the average value in the Y direction, the median value in the X direction, and the median value in the Y direction, and the arithmetic mean height Sa of the contour surface was calculated based on the definitions in ISO 25178-2:2012 and JIS B 0681-2:2018.

[0166] [Wear resistance test 1] A probe with the nonwoven fabric side of a 1cm x 1cm piece of sponge (3M Scotch-Brite Sponge Ace S, yellow) attached to the tip was placed in contact with the laminate. The laminate was then moved back and forth in one direction for 20 seconds at a speed of (41 ± 1) strokes / min in a medium-sized shaker R-10 (Taitec Corporation) under a 1kg load, covering a distance of 35mm. The abrasion resistance of the coating was evaluated by this motion. If no breakage of the coating was observed, the coating was deemed to have sufficient abrasion resistance and was marked "Good." If breakage of the coating was observed, the coating's abrasion resistance was deemed poor and was marked "Poor."

[0167] [Wear resistance test 2] A 1cm x 1cm piece of sponge (3M Scotch-Brite Sponge Ace S, yellow) was attached with the nonwoven fabric side at the tip. A probe with a Kimwipe attached to it was then placed in contact with the laminate. The laminate was then moved back and forth in one direction at a speed of (41 ± 1) strokes / min for 60 seconds using a medium-sized shaker R-10 (Taitec Corporation) with a 1kg load, covering a distance of 35mm. The abrasion resistance of the coating was evaluated by this. When no scratches were observed on the coating surface, the coating was judged to have extremely high abrasion resistance, and this was marked with a "◎." When scratches were observed only on a portion of the probe contact area, the coating was judged to have relatively high abrasion resistance, and this was marked with a "○." When scratches were observed over the entire probe contact area or when the coating was chipped, the coating was judged to have extremely low abrasion resistance, and this was marked with a "×."

[0168] [Alkali resistance test] 80 g of 1 M NaOH aqueous solution was dispensed and the prepared laminate was immersed in this solution. The sodium hydroxide solution on the surface of the laminate was then rinsed off with distilled water and dried in an oven at 100°C for at least 8 hours to remove moisture. Finally, the transmittance of the immersed surface of the laminate was measured using a UV-3600 ultraviolet / visible / near-infrared spectrophotometer (Shimadzu Corporation) in the wavelength range of 185-700 nm, and the resulting spectrum was compared with the transmittance spectrum obtained before immersion. The transmittance change at each wavelength in the wavelength range of 185 nm to 700 nm was calculated. If the average absolute value of the transmittance change (hereinafter referred to as the average transmittance change) was 0.5 points or more, it was determined that the coating had been sufficiently destroyed by the alkali and no longer had anti-reflection properties. An average transmittance change of 0.5 points or less was evaluated as "Good," and an average transmittance change of 0.5 points or more was evaluated as "Poor."

[0169] [Table 1-1]

[0170] [Table 1-2]

[0171] [Table 1-3]

[0172] From the results shown in Table 1-1, in Example 1, the average transmittance in the wavelength range of 185 nm or more and 300 nm or less was 2.1 points higher than the average transmittance of the substrate without a coating film, and a laminate with high ultraviolet transmittance (energy efficiency) was obtained, and a coating film with high abrasion resistance was also obtained.

[0173] Furthermore, from the results shown in Table 1-2, in Examples 2 to 7, the average transmittance in the wavelength range of 185 nm or more and 300 nm or less was 2.4 points or more higher than the average transmittance of the substrate without a coating film. Furthermore, in Examples 2 to 7, the average transmittance in the wavelength range of 185 nm or more and 300 nm or less and the average transmittance in the wavelength range of 185 nm or more and 280 nm or less were 90.0% or more, and the transmittance at a wavelength of 185 nm was 91.0% or more, so laminates with high ultraviolet transmittance (energy efficiency) were obtained. Furthermore, from the results shown in Table 1-3, the laminates of Examples 1 to 7 had higher abrasion resistance than the laminate of Comparative Example 1. In contrast, in Comparative Example 1, in which the transmittance of the laminate did not satisfy the requirements of the present invention, no improvement in average transmittance was observed, and the abrasion resistance of the coating film of the laminate was lower than that of the Examples.

[0174] [Table 2]

[0175] As shown in Table 1-2, the laminates of Examples 1 to 3, 6, and 7, whose transmittances satisfied the requirements of the present invention, had average transmittances of 90.0% or more in the wavelength range of 185 nm to 300 nm and in the wavelength range of 185 nm to 280 nm, and transmittances of 91.0% or more at a wavelength of 185 nm, indicating high ultraviolet transmittance (energy efficiency). Table 2 also shows that the average change in transmittance of these laminates after the alkali resistance test was 0.5 points or less, indicating that the coating film was not easily destroyed by alkali and had high alkali resistance. In contrast, Comparative Example 1, whose laminate transmittance did not satisfy the requirements of the present invention, had an average change in transmittance of more than 0.5 points after the alkali resistance test, indicating that the coating film was destroyed by alkali and had low alkali resistance. Therefore, when the laminate is used in an environment where alkaline substances may adhere, the coating film of the laminate of the present invention will not deteriorate and the anti-reflection effect of the coating film will continue to be obtained, whereas the coating film of a laminate that does not satisfy the requirements of the present invention is expected to be destroyed and the anti-reflection effect of the coating film will no longer be obtained. [Industrial Applicability]

[0176] The present invention provides a method for producing a laminate that combines high ultraviolet transmittance with high environmental resistance (moisture resistance and abrasion resistance) and alkali resistance, a laminate, and a coating solution for use in producing the laminate. These laminates are suitable for use in applications such as optical sensor window materials, mirrors, condenser lenses, irradiation windows for light sources (lamps, lasers, etc.), solar cell cover glass, displays, various housing equipment parts, various industrial parts, various building materials, various parts for home appliances, and various automotive interior and exterior parts, and are highly applicable in various industrial fields such as the building and construction industry, the transportation machinery industry, the electrical and electronics industry, and the household goods industry. These laminates are particularly suitable for use in parts that handle ultraviolet light, including window materials for ultraviolet sensors, ultraviolet condenser lenses, irradiation windows for mercury lamps, and irradiation windows for excimer lasers, and are highly applicable to ultraviolet exposure devices for photolithography, ultraviolet irradiation devices for curing resins, UV lamps for sterilization, air purifiers, UV lamps for water treatment, etc.

Claims

1. A method for producing a laminate having a substrate and a coating film applied to at least one of its main surfaces, the method comprising the steps of: applying to a substrate an inorganic particle dispersion liquid containing inorganic particles and a liquid dispersion medium A having a boiling point greater than 121°C and less than 190°C, wherein the weight ratio of the liquid dispersion medium A is 0.5% by mass or more and less than 15% by mass, with the total amount of the inorganic particle dispersion liquid being 100% by mass; and a heat treatment step at a temperature of 200°C or more and 1000°C or less for a period of 10 minutes or longer.

2. The method for producing a laminate according to claim 1 , wherein the substrate is made of quartz glass.

3. The method for producing a laminate according to claim 1 or 2, wherein the thickness of the coating film is 20 nm or more and 200 nm or less.

4. The method for producing a laminate according to claim 1 or 2, wherein the inorganic fine particles are inorganic fine particles containing silica particles.

5. 3. The method for producing a laminate according to claim 1, wherein the inorganic fine particle dispersion contains a liquid dispersion medium B having a boiling point of less than 100°C.

6. 3. The method for producing a laminate according to claim 1, wherein the inorganic fine particle dispersion contains water.

7. The method for producing a laminate according to claim 6, wherein the inorganic fine particle dispersion contains an alkoxysilane.

8. The method for producing a laminate according to claim 7, wherein the alkoxysilane contains a condensate of an alkoxysilane represented by the following general formula (1): General formula (1) 【Chemical 1】 (In the formula, each R independently represents an alkyl group having 1 to 6 carbon atoms, and n is an integer of 2 to 1,000.)

9. In the inorganic fine particle dispersion, the ratio of the SiO contained in the alkoxysilane to the weight of the inorganic fine particles is ２ The weight ratio (SiO contained in the alkoxysilane) ２ The method for producing a laminate according to claim 7 , wherein the ratio of [weight of the inorganic fine particles] / [weight of the inorganic fine particles] is greater than 0.

005.

10. 3. The method for producing a laminate according to claim 1, wherein the inorganic fine particles have a primary particle diameter of 1 nm or more and less than 50 nm.

11. A laminate obtainable by a method for producing a laminate having a substrate and a coating film applied to at least one of its main surfaces, the method comprising the steps of: applying to a substrate an inorganic particle dispersion liquid containing inorganic particles and a liquid dispersion medium A having a boiling point of more than 121°C and less than 190°C, wherein the weight ratio of the liquid dispersion medium A is 0.5 mass% or more and less than 15 mass%, relative to the total amount of the inorganic particle dispersion liquid being 100 mass%; and heat treating the substrate at a temperature of 200°C or more and 1000°C or less for a period of more than 10 minutes.

12. A laminate having a substrate and a coating film applied to at least one of its main surfaces, wherein the coating film has a thickness of 20 nm or more and less than 75 nm; The average transmittance in the wavelength region of 185 nm or more and 300 nm or less is A laminate characterized in that the average transmittance is 0.5 points or more higher than the average transmittance of a substrate not having the coating film.

13. A laminate having a substrate and a coating film applied to at least one of its main surfaces, the coating film has a porous structure and a thickness of 20 nm or more and less than 100 nm, The laminate is characterized in that the transmittance at any wavelength of 150 nm or more and less than 300 nm is 80.0% or more.

14. 14. The laminate according to claim 13, wherein the laminate has a transmittance of 91.0% or more at a wavelength of 185 nm.

15. 14. The laminate according to claim 13, wherein the coating film has a surface in which the ratio of the number of carbon atoms to the total number of sodium, potassium, magnesium, calcium, aluminum, and silicon atoms is 1.00 or less.

16. The laminate according to claim 13 or 14, wherein the coating film contains inorganic fine particles.

17. The laminate according to claim 16 , wherein the inorganic fine particles are inorganic fine particles containing silica.

18. The laminate according to claim 16, wherein the inorganic fine particles have a primary particle diameter of 1 nm or more and less than 50 nm.

19. 14. The laminate according to claim 13, which can be obtained by a production method comprising: a step of applying a coating liquid containing an alkoxysilane, water, an acid catalyst, and a pore-forming agent to a substrate; and a heat treatment step at a temperature of 200°C or higher and 1000°C or lower for more than 10 minutes.

20. The laminate according to claim 13 or 14, wherein the coating film has a kurtosis of 0.320 or less in brightness distribution in a cross-sectional image thereof taken by a scanning electron microscope.

21. The laminate according to claim 13 or 14, wherein the coating film has an arithmetic mean roughness of 0.1 nm or more and 10.0 nm or less.

22. 15. The laminate according to claim 13, wherein the substrate is made of quartz glass or sapphire glass.

23. 15. The laminate according to claim 13, wherein the thickness of the substrate is 0.1 mm or more and 100 mm or less.

24. The laminate according to claim 13 or 14, obtainable by a production method comprising: a step of applying a coating agent to a substrate; and a step of heat treating the substrate at a temperature of 200°C or higher and 1000°C or lower for more than 10 minutes.

25. A laminate obtainable by a method for producing a laminate having a substrate and a coating film applied to at least one of its main surfaces, the method comprising the steps of: applying a coating agent to a substrate; and heat-treating the substrate at a temperature of 200°C or higher and 1000°C or lower for more than 10 minutes.

26. A coating liquid comprising an alkoxysilane, water, an acid catalyst, a pore-forming agent, and a liquid dispersion medium A having a boiling point of more than 121°C and less than 190°C, wherein the weight ratio of the liquid dispersion medium A is 0.5% by mass or more and less than 15% by mass, with the total amount of the coating liquid being 100% by mass.

27. The alkoxysilane contains the following alkoxysilanes C01 and C02, and the SiO contained in the alkoxysilanes ２ SiO contained in alkoxysilane C02 relative to the total weight of ２ The weight ratio of SiO contained in alkoxysilane CO2 ２ weight of alkoxysilane] / [SiO ２ The coating liquid according to claim 26, wherein the total weight of the components (a) and (b) is 0.00 or more and 0.50 or less. Alkoxysilane C01: At least one alkoxysilane selected from tetraalkoxysilanes and alkoxysilane condensates represented by the following general formula (01): General formula (01) 【Chemical 1】 (In the formula, each R independently represents an alkyl group having 1 to 6 carbon atoms, and n is an integer of 2 to 1,000.) Alkoxysilane C02: At least one alkoxysilane selected from alkoxysilanes represented by the following general formula (02) and condensates thereof: Si(R ａ ) ｑ (R ｂ ) ４－ｑ (02) In formula (02), R ａ represents a hydrogen atom or a non-hydrolyzable organic group, R ｂ represents a hydrolyzable group, and q represents an integer of 1 or 2.

28. 27. The coating liquid according to claim 26, wherein the coating liquid contains a liquid dispersion medium B having a boiling point of less than 100°C.

29. The coating liquid according to claim 26, wherein the pore-forming agent is an organic ammonium salt.

30. 27. The coating liquid according to claim 26, wherein the acid catalyst comprises at least one selected from the group consisting of formic acid, acetic acid, propionic acid, butanoic acid, oxalic acid, maleic acid, phthalic acid, fumaric acid, hydrochloric acid, nitric acid, sulfuric acid, and phosphoric acid.

31. SiO contained in alkoxysilane ２ The ratio of the weight of the pore-forming agent to the total weight of the alkoxysilane ([weight of the pore-forming agent] / [SiO contained in the alkoxysilane]) ２ The coating liquid according to claim 26, wherein the weight ratio of the coating liquid to the total weight of the coating liquid is 0.10 or more.

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