Method for producing laminate, and laminate

Abstract

The invention relates to a method for manufacturing a laminate and the laminate. The invention provides a method for producing a laminate, the laminate, and a coating liquid used in the production of the laminate. Disclosed is a method for producing a laminate having both high wear resistance and alkali resistance and high ultraviolet transmittance by using inorganic fine particles such as silica having excellent moisture resistance or by wet coating which enables simple large-area coating without using the inorganic fine particles. A method for producing a laminate having a base material and a coating film applied to at least one main surface of the base material, the method comprising: a step for applying an inorganic fine particle dispersion on the base material; the inorganic fine particle dispersion liquid contains inorganic fine particles and a liquid dispersion medium A having a boiling point of more than 121 DEG C and less than 190 DEG C, and the weight ratio of the liquid dispersion medium A is 0.5% by mass or more and less than 15% by mass when the total amount of the inorganic fine particle dispersion liquid is taken as 100% by mass; and a step for performing a heat treatment for more than 10 minutes at a temperature of 200-1000 DEG C (inclusive).

Description

Technical Field

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

[0002] Previously, research has been conducted on laminated bodies for UV devices, using sputtering or vapor deposition to form an antireflection layer containing a fluoride on a substrate. For example, Patent Document 1 describes an optical element characterized by having a first thin film containing an oxide or nitride doped with a fluoride and a second thin film containing a fluoride material formed on the first thin film as the antireflection layer.

[0003] Prior art literature

[0004] Patent Literature

[0005] Patent Document 1: Japanese Patent Application Laid-Open No. 2005-345826 Summary of the Invention

[0006] Problems to be solved by the invention

[0007] Antireflection layers made of inorganic fluorides do not have excellent moisture resistance. In addition, sputtering and vapor deposition methods are difficult to easily apply to large areas compared to coating film formation methods such as wet coating.

[0008] The object of the present invention is to provide a method for manufacturing a laminate, a laminate, and a coating liquid used in the manufacture of the laminate, wherein the method for manufacturing the laminate uses inorganic particles such as silica with excellent moisture resistance, or does not use such inorganic particles and manufactures a laminate having high wear resistance / alkali resistance and high ultraviolet transmittance by wet coating that can easily be applied to a large area.

[0009] Means used to solve problems

[0010] The present inventors conducted intensive studies in view of such background and, as a result, completed the present invention.

[0011] That is, the present invention (method for producing a laminate) and its preferred aspects or embodiments relate to the following, but are not limited thereto.

[0012] [1] A method for producing a laminate comprising a substrate and a coating film applied to at least one main surface of the substrate, the method comprising the following steps:

[0013] The process of coating a substrate with an inorganic fine particle dispersion, wherein the inorganic fine particle dispersion comprises inorganic fine 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 greater than or equal to 0.5% by mass and less than 15% by mass when the total amount of the inorganic fine particle dispersion is set to 100% by mass; and

[0014] A step of performing heat treatment at a temperature of 200°C to 1000°C for more than 10 minutes.

[0015] [2] The method for producing a laminate according to [1], wherein the substrate is quartz glass.

[0016] [3] The method for producing a laminate according to [1] or [2], wherein the thickness of the coating film is 20 nm to 200 nm.

[0017] [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.

[0018] [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.

[0019] [6] The method for producing a laminate according to any one of [1] to [5], wherein the inorganic fine particle dispersion contains water.

[0020] [7] The method for producing a laminate according to any one of [1] to [6], wherein the inorganic fine particle dispersion contains alkoxysilane.

[0021] [8] The method for producing a laminate according to [7], wherein the alkoxysilane includes a condensate of alkoxysilane represented by the following general formula (1).

[0022] General formula (1)

[0023]

[0024] (In formula (1), each R independently represents an alkyl group having 1 to 6 carbon atoms, and n is an integer of 2 to 1000.)

[0025] [9] The method for producing a laminate according to [7] or [8], wherein in the inorganic particle dispersion, the ratio of the weight of SiO2 contained in the alkoxysilane to the weight of the inorganic particles ([the weight of SiO2 contained in the alkoxysilane] / [the weight of the inorganic particles]) is greater than 0.005.

[0026]

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

[0027] The present invention (laminated body) and its preferred aspects or embodiments relate to the following

[11] to

[12] , but are not limited thereto.

[0028]

[11] A laminated body, wherein the laminated body can be obtained by a method for producing a laminated body, the laminated body comprising a substrate and a coating film applied to at least one main surface of the substrate, the method for producing the laminated body comprising the following steps:

[0029] The process of coating a substrate with an inorganic fine particle dispersion, wherein the inorganic fine particle dispersion comprises inorganic fine 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 greater than or equal to 0.5% by mass and less than 15% by mass when the total amount of the inorganic fine particle dispersion is set to 100% by mass; and

[0030] A step of performing heat treatment at a temperature of 200°C to 1000°C for more than 10 minutes.

[0031]

[12] A laminate comprising a substrate and a coating film applied to at least one main surface of the substrate, characterized in that:

[0032] The coating film has a thickness of greater than or equal to 20 nm and less than 75 nm,

[0033] The average transmittance of the laminate in the wavelength range of 185 nm to 300 nm is higher by 0.5 percentage points or more than the average transmittance of a substrate having no coating film in the wavelength range of 185 nm to 300 nm.

[0034] The present inventors have further completed the present invention as described below.

[0035] That is, the present invention (laminated body) and its preferred aspects or embodiments relate to the following

[13] to

[25] , but are not limited thereto.

[0036]

[13] A laminate comprising a substrate and a coating film applied to at least one main surface of the substrate, characterized in that:

[0037] The coating film has a porous structure and a thickness greater than or equal to 20 nm and less than 100 nm.

[0038] The transmittance of the laminated body at any wavelength of 150 nm or more and less than 300 nm is 80.0% or more.

[0039]

[14] The laminate according to

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

[0040]

[15] The laminate according to any one of

[13] to

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

[0041]

[16] The laminate according to any one of

[13] to

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

[0042]

[17] The laminate according to

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

[0043]

[18] The laminate according to

[16] or

[17] , wherein the primary particle size of the inorganic fine particles is greater than or equal to 1 nm and less than 50 nm.

[0044]

[19] The laminate according to any one of

[13] to

[18] , wherein the laminate can be obtained by the following production method, the production method comprising the following steps:

[0045] A step of applying a coating solution comprising alkoxysilane, water, an acid catalyst and a pore-forming agent onto a substrate; and

[0046] A step of performing heat treatment at a temperature of 200°C to 1000°C for more than 10 minutes.

[0047]

[20] The laminate according to any one of

[11] to

[19] , wherein the kurtosis of the distribution of brightness in a cross-sectional image of the coating film taken with a scanning electron microscope is 0.320 or less.

[0048]

[21] The laminate according to any one of

[11] to

[20] , wherein the coating film has an arithmetic mean roughness of 0.1 nm to 10.0 nm.

[0049]

[22] The laminate according to any one of

[11] to

[21] , wherein the substrate is quartz glass or sapphire glass.

[0050]

[23] The laminate according to any one of

[11] to

[22] , wherein the thickness of the substrate is 0.1 mm to 100 mm.

[0051]

[24] The laminate according to any one of

[12] to

[23] , wherein the laminate can be obtained by the following manufacturing method, the manufacturing method comprising the following steps:

[0052] The process of applying a coating agent to a substrate; and

[0053] A step of performing heat treatment at a temperature of 200°C to 1000°C for more than 10 minutes.

[0054]

[25] A laminated body, wherein the laminated body can be obtained by a method for producing a laminated body, the laminated body comprising a substrate and a coating film applied to at least one main surface of the substrate, the method for producing the laminated body comprising the following steps:

[0055] The process of applying a coating agent to a substrate; and

[0056] A step of performing heat treatment at a temperature of 200°C to 1000°C for more than 10 minutes.

[0057] In addition, the present invention (coating liquid) and its preferred embodiments or implementations relate to the following

[26] to

[31] , but are not limited thereto.

[0058]

[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 greater than 121°C and less than 190°C, wherein the weight ratio of the liquid dispersion medium A is greater than or equal to 0.5% by mass and less than 15% by mass when the total amount of the coating liquid is set to 100% by mass.

[0059]

[27] The coating liquid according to

[26] , wherein the coating liquid contains the following alkoxysilane C01 and alkoxysilane C02 as alkoxysilanes, and the ratio of the weight of SiO2 contained in the alkoxysilane C02 to the total weight of SiO2 contained in the alkoxysilane ([the weight of SiO2 contained in the alkoxysilane C02] / [the total weight of SiO2 contained in the alkoxysilane]) is greater than 0.00 and less than 0.50.

[0060] Alkoxysilane C01: at least one alkoxysilane selected from the group consisting of tetraalkoxysilane and a condensate of an alkoxysilane represented by the following general formula (01).

[0061] General formula (01)

[0062]

[0063] (In formula (01), each R independently represents an alkyl group having 1 to 6 carbon atoms, and n is an integer of 2 to 1000.)

[0064] Alkoxysilane C02: at least one alkoxysilane selected from the group consisting of alkoxysilanes represented by the following general formula (02) and condensates thereof.

[0065] Si(R a ) q (R b ) 4-q (02)

[0066] In formula (02), R a represents a hydrogen atom or a non-hydrolyzable organic group, R b represents a hydrolyzable group. q represents an integer of 1 to 2.

[0067]

[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.

[0068]

[29] The coating solution according to any one of

[26] to

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

[0069]

[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, butyric acid, oxalic acid, maleic acid, phthalic acid, fumaric acid, hydrochloric acid, nitric acid, sulfuric acid and phosphoric acid.

[0070]

[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 the pore-forming agent] / [total weight of SiO2 contained in the alkoxysilane]) is 0.10 or more.

[0071] Effects of the Invention

[0072] According to the present invention, a method for producing a laminate having both high abrasion resistance and alkali resistance and high ultraviolet transmittance, a laminate, and a coating liquid used for producing the laminate can be provided. DETAILED DESCRIPTION

[0073] An embodiment of the present invention is described in detail below.

[0074] <Inorganic fine particle dispersion>

[0075] The inorganic particle dispersion used in the method for manufacturing a laminate of the present invention is an inorganic particle dispersion comprising 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 greater than or equal to 0.5% by mass and less than 15% by mass when the total amount of the inorganic particle dispersion is set to 100% by mass.

[0076] [Inorganic particles]

[0077] In the present invention, the inorganic particles may be inorganic particles comprising silica particles. The primary particle size of the inorganic particles may be greater than or equal to 1 nm and less than 50 nm. The inorganic particles may be inorganic particles X having a primary particle size greater than or equal to 1 nm and less than 50 nm, or inorganic particles Y formed by connecting a plurality of inorganic particles having a primary particle size greater than or equal to 1 nm and less than 50 nm. The shape of the secondary particles of the inorganic particles Y is not particularly limited.

[0078] Regarding the inorganic fine particles, the inorganic fine particles X and the inorganic fine particles Y may be used alone or in combination. As the inorganic fine particles X, one or more inorganic fine particles may be used, and as the inorganic fine particles Y, one or more inorganic fine particles may be used.

[0079] The primary particle size of the inorganic fine particles is evaluated as the number average of the particle sizes of 50 or more particles observed with a transmission microscope. The state of "a plurality of inorganic fine particles connected" in the inorganic fine particles Y can also be determined by observation with a transmission microscope.

[0080] <Regarding the primary particle size of inorganic fine particles>

[0081] The primary particle size of the inorganic fine particles is measured before forming a coating film. Therefore, in the present invention, the specified primary particle size refers to the primary particle size of the inorganic fine particles used in the raw material or the primary particle size until the step of coating on the substrate before forming a coating film.

[0082] Regarding the material of the inorganic fine particles, for example, silicon oxide (silicon dioxide), titanium oxide, aluminum oxide, zinc oxide, tin oxide, calcium carbonate, barium sulfate, talc, kaolin, etc., and one or more kinds thereof can be used. From the viewpoint of dispersibility in the inorganic fine particle dispersion and ultraviolet transmittance of the coating film, silicon dioxide is preferred. Among silicon dioxides, colloidal silicon dioxide and fumed silicon dioxide are more preferred, and colloidal silicon dioxide is particularly preferred. Colloidal silicon dioxide can be a dispersion containing colloidal silicon dioxide 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 can be used dispersed in various solvents. 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; and water. A mixture of these solvents may also be used. Preferred solvents include alcohol solvents such as methanol, ethanol, isopropanol, ethylene glycol, and ethylene glycol mono-n-propyl ether and water. More preferred solvents include methanol, ethanol, isopropanol, and water. More preferred solvents include ethanol, isopropanol, and water. Furthermore, more preferred solvents include water.

[0083] From the viewpoint of achieving both transmittance and coating strength, the primary particle size 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, further preferably 1 nm or more and 20 nm or less, and particularly preferably 3 nm or more and 10 nm or less.

[0084] From the perspective of both transmittance and coating strength, the primary particle size of the inorganic microparticle Y formed by connecting multiple inorganic microparticles with a primary particle size greater than or equal to 1 nm and less than 50 nm is preferably greater than or equal to 1 nm and less than 50 nm, more preferably greater than or equal to 1 nm and less than 45 nm, further preferably greater than or equal to 1 nm and less than 30 nm, and particularly preferably greater than or equal to 3 nm and less than 20 nm.

[0085] The weight ratio of inorganic particles is not particularly limited, from the transparency of the resulting film and the dispersibility viewpoint in the inorganic particle dispersion, when the gross weight of the inorganic particle dispersion is set to 100 mass %, the weight ratio of inorganic particles is preferably more than 0.05 mass % and below 10 mass %, more preferably more than 0.1 mass % and below 7.5 mass %, further preferably more than 0.2 mass % and below 5.0 mass %, particularly preferably more than 0.5 mass % and below 2.0 mass %. " weight ratio of inorganic particles " refers to the total value of the weight ratio of inorganic particles X and the weight ratio of inorganic particles Y.

[0086] Consider from the viewpoint that the dispersibility in the dispersion liquid, coating and film formation, the inorganic particles in the inorganic particle dispersion liquid can be implemented surface treatment.As the surface treated method, known method can be used, the method utilizing suitable additive to process can be enumerated.The surface treatment of inorganic particles can for example be carried out by mixing the liquid that will comprise inorganic particles, additive and solvent.

[0087] Specific examples of the 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 aqueous dispersions; and METHANOL SILICA, which is a commercially available product in the form of methanol dispersions. SOL (registered trademark) MA-ST-M and MA-ST-L; IPA-ST and IPA-ST-L, which are commercially available products in the form of isopropyl alcohol dispersions; NPC-ST-30, which is commercially available in the form of ethylene glycol monopropyl ether dispersions; TOL-ST, which is commercially available in the form of toluene dispersions; MEK-ST-40, MEK-ST-L, MEK-EC-2130Y, and MEK-AC-2, which are commercially available products in the form of 2-butanone dispersions. Examples of commercially available esters include MIBK-140Z and MEK-AC-4130Y; MIBK-ST, MIBK-ST-L, MIBK-AC-2140Z, and MIBK-SD-L, which are commercially available in the form of 4-methyl-2-pentanone dispersions; CHO-ST-M, which is commercially available in the form of cyclohexanone dispersions; EAC-ST, which is commercially available in the form of ethyl acetate dispersions; and PMA-ST, which is commercially available in the form of propylene glycol 1-monomethyl ether 2-acetate dispersions. Among these, those in the form of aqueous dispersions are preferred, with 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 being particularly preferred, and ST-OXS, ST-OS, ST-O, ST-O-40, and ST-OL being more preferred.

[0088] Specific examples of the 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 in the form of aqueous dispersions; IPA-ST-UP, which is commercially available in the form of an isopropyl alcohol dispersion; and MEK-ST-UP, which is commercially available in the form of a 2-butanone dispersion. Of these, aqueous dispersions are preferred, with ST-OUP, ST-PS-SO, and ST-PS-MO being particularly preferred, and ST-OUP being more preferred.

[0089] The method for synthesizing the inorganic fine particles X and 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 metal salt aqueous solutions, and hydrothermal treatment of metal salt aqueous solutions.

[0090] From the viewpoint of dispersibility, preferred silica is synthesized by a method of carrying out particle growth and concentration after ion exchange of an aqueous sodium silicate solution using an ion exchange resin or the like (sometimes also referred to as a water glass method), a method of adding an aqueous sulfuric acid solution to an aqueous sodium silicate solution and neutralizing it and then carrying out particle growth and concentration (sometimes also referred to as a sedimentation method), a method of thermally decomposing silicon tetrachloride, a method of hydrolyzing and condensing alkoxysilane (sometimes also referred to as a sol-gel method), and the like.

[0091] In the case of the method of synthesizing by ion-exchanging an aqueous sodium silicate solution, from the viewpoint of forming a coating film with high transmittance, the weight ratio of sodium ions in the silica sol as calculated as Na2O 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 entire inorganic fine particle dispersion is taken as 100% by mass.

[0092] [Liquid dispersion medium A]

[0093] In the present invention, liquid dispersion medium A is a liquid having a boiling point at atmospheric pressure (1013.25 hPa) greater than 121° C. and less than 190° C. The weight ratio of liquid dispersion medium A is greater than or equal to 0.5% by mass and less than 15% by mass, based on 100% by mass of the entire inorganic fine particle dispersion.

[0094] The boiling point range of the liquid dispersion medium A is preferably 125°C or higher and lower than 190°C, more preferably 135°C or higher and lower than 190°C, more preferably 150°C or higher and lower than 190°C, more preferably 155°C or higher and lower than 190°C, more preferably 155°C or higher and lower than 180°C, more preferably 160°C or higher and lower than 180°C, and even more preferably 170°C or higher and lower than 180°C.

[0095] As the lower limit of the weight ratio of the liquid dispersion medium A, from the perspective of suppressing the aggregation of inorganic fine particles during drying of the coating film and improving the transmittance and coating film strength by using the liquid dispersion medium A, it is preferable that the content of the liquid dispersion medium A be 0.7% by mass or more, and more preferably 0.8% by mass or more, based on 100% by mass of the total inorganic fine particle dispersion. Furthermore, as the upper limit of the weight ratio of the liquid dispersion medium A, from the perspective of deteriorating the storage stability of the inorganic fine particle dispersion due to gelation, etc., when the liquid dispersion medium A is excessively contained, it is preferable that the content of the liquid dispersion medium A be 13% by mass or less, more preferably 12% by mass or less, and even more preferably 8% by mass or less, based on 100% by mass of the total inorganic fine particle dispersion.

[0096] Regarding the liquid dispersion medium A, δtA defined by the following formula can be exemplified as 20 MPa: 0.5 Above and 40MPa 0.5 The following liquid dispersion media are preferred examples.

[0097] δtA={4(δDA-15.6) 2 +(δPA-16.0) 2 +(δHA-42.0) 2} 0.5 (1)

[0098] (In formula (1), δDA, δPA, and δHA represent the dispersion terms in the Hansen solubility parameters of the liquid dispersion medium A (MPa) 0.5 ), polarity term (MPa 0.5 ), hydrogen bond term (MPa 0.5 ). )

[0099] The above-mentioned δDA, δPA, and δHA were calculated using "HSPiP 5th 5.2.06," which is a generally available commercial software, and applying a method called Y-MB in the software.

[0100] As a preferred range of δtA, the upper limit is preferably 39 MPa 0.5 Below, more preferably 35.5 MPa 0.5 Below, more preferably 34MPa 0.5 Below. The lower limit is preferably 25 MPa 0.5 More than 29 MPa 0.5 Above, more preferably 30MPa 0.5 The liquid dispersion medium A having δtA within such a range can obtain high affinity with the inorganic fine particles, and thus has good coating properties.

[0101] From the viewpoint of coating properties, the lower limit of the molecular weight of the liquid dispersion medium A is preferably 60 or more, more preferably 70 or more, further preferably 90 or more, and particularly preferably 100 or more. The upper limit is preferably 300 or less, more preferably 200 or less, further preferably 170 or less, and particularly preferably 140 or less.

[0102] Examples of the type of the liquid dispersion medium A include, but are not limited to, ethers, esters, alcohols, ketones, amines, amides, and sulfoxides. Specific examples of the liquid dispersion medium A include, but are not limited to, 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-amyl 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-ethylhexyl alcohol, 1-pentanol, 2-butyl ether ... Hexyl alcohol, N,N-dimethylacetamide, ethyl lactate, diethylene glycol methyl ethyl ether, 3-methoxybutyl acetate, 1,2-propylene glycol, 3-methoxy-3-methylbutanol, propylene glycol 1-monobutyl ether, 1-ethoxy-2-propanol, 3-methoxy-1-propanol, 3-methoxy-1-butanol, ethylene glycol mono-tert-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.

[0103] Preferred liquid dispersion medium A includes any of an alcohol, an ether, and an ester. More preferred liquid dispersion mediums include any of an alcohol, an ether, and an ester that do not contain nitrogen atoms. Using such a liquid dispersion medium A improves coating properties.

[0104] In one embodiment of the inorganic fine particle dispersion, the liquid dispersion medium A is preferably alcohol. When the liquid dispersion medium A is alcohol, the compatibility of the inorganic fine particle component with the alkoxysilane described below during coating is improved, resulting in good coating properties and a laminate with high coating film strength.

[0105] When the liquid dispersion medium A is an alcohol, monohydric alcohols can be cited as preferred examples. In addition, it is preferred to have any one or more alcohols among ether bonds and ester bonds. When the liquid dispersion medium A is such an alcohol, the dispersibility and coating properties of the inorganic particles become good. As such specific examples, 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-tert-butyl ether, 2-isopropoxyethanol, 2-propoxyethanol, 2-isobutoxyethanol, 2-allyloxyethanol, tetrahydrofurfuryl alcohol and 2-hydroxyethyl acetate can be cited.

[0106] As the liquid dispersion medium A, among substances that are monohydric alcohols and have at least one of an ether bond and an ester bond, substances that are monohydric alcohols and have an ether bond are more preferably used from the viewpoint of dispersibility and coating properties of the inorganic fine particles. Specific examples thereof 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-tert-butyl ether, 2-isopropoxyethanol, 2-propoxyethanol, 2-isobutoxyethanol, 2-allyloxyethanol, and tetrahydrofurfuryl alcohol.

[0107] 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-tert-butyl ether, 2-isopropoxyethanol, 2-propoxyethanol, 2-isobutoxyethanol, 2-allyloxyethanol, and tetrahydrofurfuryl alcohol. 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-tert-butyl ether, 2-propoxyethanol, 2-isobutoxyethanol, and tetrahydrofurfuryl alcohol. Even more preferred examples include 3-methoxy-3-methylbutanol and 3-methoxy-1-butanol. Even more preferred examples include 3-methoxy-3-methylbutanol.

[0108] [Liquid dispersion medium B]

[0109] 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.

[0110] Regarding the liquid dispersion medium B, δtB defined by the following formula can be exemplified as 15 MPa: 0.5 Above and 39MPa 0.5 The following liquid dispersion media are preferred examples.

[0111] δtB={4(δDB-15.6) 2 +(δPB-16.0) 2 +(δHB-42.0) 2} 0.5 (2)

[0112] (In formula (2), δDB, δPB, and δHB represent the dispersion terms in the Hansen solubility parameters of the liquid dispersion medium B (MPa) 0.5 ), polarity term (MPa 0.5 ), hydrogen bond term (MPa 0.5 ). )

[0113] The above-mentioned δDB, δPB, and δHB are calculated using "HSPiP 5th 5.2.06," which is generally available commercial software, and applying a method called Y-MB in the software.

[0114] As a preferred range of δtB, the upper limit is preferably 32 MPa 0.5 Below, preferably 31MPa 0.5 Below, more preferably 27MPa 0.5 The lower limit is preferably 18 MPa 0.5 More than 23 MPa 0.5 More than 25 MPa 0.5 The liquid dispersion medium B having δtB within such a range can obtain high affinity with the inorganic fine particles, and thus improve coating properties.

[0115] Examples of the liquid dispersion medium B include ethers, esters, and alcohols. Examples of ethers include diethyl ether, examples of esters include methyl acetate and ethyl acetate, and examples of alcohols include methanol, ethanol, tert-butanol, sec-butanol, isopropanol, and n-propanol. From the perspective of dispersibility of the inorganic fine particles in the inorganic fine particle dispersion, alcohols are preferred, with methanol, ethanol, and isopropanol being more preferred, and ethanol and isopropanol being particularly preferred. From the perspective of safety, ethanol is further preferred.

[0116] The weight ratio of the liquid dispersion medium B is not particularly limited. From the viewpoint of coating properties and storage stability, when the entire inorganic fine particle dispersion is set to 100% by mass, the liquid dispersion medium B is preferably contained in an amount of 20% by mass or more, more preferably 30% by mass or more, more preferably 40% by mass or more, and even more preferably 60% by mass or more. Furthermore, the liquid dispersion medium B is preferably contained in an amount of 95% by mass or less, more preferably 90% by mass or less, more preferably 85% by mass or less, and even more preferably 80% by mass or less.

[0117] [water]

[0118] In the present invention, as a mode, inorganic particle dispersion liquid also preferably includes water.As the lower limit of the weight ratio of water, from the viewpoint of coating property, storage stability, when the inorganic particle dispersion liquid is entirely set to 100 mass %, preferably include the water of more than 1 mass %, further preferably include the water of more than 3 mass %, further preferably include the water of more than 5 mass %, further preferably include the water of more than 8 mass %, further preferably include the water of more than 10 mass %.In addition, as the upper limit of the weight ratio of water, from the viewpoint of transmittance, preferably include the water of less than 55 mass %, further preferably include the water of less than 50 mass %, further preferably include the water of less than 45 mass %, further preferably include the water of less than 35 mass %, further preferably include the water of less than 25 mass %, further preferably include the water of less than 20 mass %.

[0119] [Alkoxysilane (Component C)]

[0120] In the present invention, as one embodiment, the inorganic particle dispersion preferably includes an alkoxysilane (component C). The alkoxysilane may be a condensate of an alkoxysilane. The alkoxysilane may be partially hydrolyzed at the alkoxy group, or further condensed at the hydrolyzed portion. In this specification, "hydrolyzability" refers to the property of generating a silanol group by reaction with water.

[0121] Examples of the alkoxysilane include tetraalkoxysilane and a silicon compound represented by the following formula (3).

[0122] Si(R a ) q (R b ) 4-q (3)

[0123] In formula (3), R a represents a hydrogen atom or a non-hydrolyzable organic group, R brepresents a hydrolyzable group. q represents an integer of 1 to 2.

[0124] In one embodiment, tetraalkoxysilane is represented by the formula: Si(OR)4 (wherein each of the four Rs independently represents an alkyl group having 1 to 6 carbon atoms). Examples of tetraalkoxysilane include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetrabutoxysilane, with tetramethoxysilane and tetraethoxysilane being preferred. These tetraalkoxysilanes may have their alkoxy moieties partially hydrolyzed, or the hydrolyzed moieties may be further condensed.

[0125] As one embodiment of alkoxysilane, a silicon compound represented by the following formula (3) can be mentioned.

[0126] Si(R a ) q (R b ) 4-q (3)

[0127] In formula (3), R a represents a hydrogen atom or a non-hydrolyzable organic group, R b represents a hydrolyzable group. q represents an integer of 1 to 2.

[0128] As 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-pentyl (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; aromatic groups having 6 to 15 carbon atoms, such as phenyl, naphthyl, and anthracenyl; and the like.

[0129] As R b Examples of the hydrolyzable group include alkoxy groups having 1 to 5 carbon atoms, such as methoxy, ethoxy, and propoxy.

[0130] q represents an integer of 1 to 2, and is preferably 1.

[0131] The silicon compound represented by formula (3) may undergo hydrolysis of the hydrolyzable group, or may further undergo condensation at the hydrolyzed portion.

[0132] Examples of the silicon compound represented by formula (3) include silicon compounds wherein q is 1, such as methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltriisopropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, phenyltrimethoxysilane, and phenyltriethoxysilane; and silicon compounds wherein q is 2, such as dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, and methylphenyldimethoxysilane.

[0133] Examples of condensates of alkoxysilanes include siloxane compounds obtained by partially hydrolyzing the alkoxy groups in the aforementioned tetraalkoxysilanes and the silicon compound represented by the aforementioned formula (3), followed by condensation of the hydrolyzed portions. The condensates of alkoxysilanes may further comprise partially hydrolyzing the alkoxy groups, or further condensing the hydrolyzed portions.

[0134] As one embodiment of the condensate of tetraalkoxysilane, a silicon compound having a structure represented by the following general formula (1) can be mentioned.

[0135] General formula (1)

[0136]

[0137] (In formula (1), each R independently represents an alkyl group having 1 to 6 carbon atoms, and n is an integer of 2 to 1000. In one embodiment, n is 2 to 100.)

[0138] Examples of R, which is an alkyl group having 1 to 6 carbon atoms, include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, and tert-amyl (1,1-dimethylpropyl). Preferred examples include methyl, ethyl, and butyl, and more preferred examples include methyl and ethyl.

[0139] In the above general formula (1), n represents an integer of 2 to 1000, preferably 2 to 100, more preferably 3 to 50, and even more preferably 3 to 30.

[0140] The weight average molecular weight of the silicon compound having a 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.

[0141] The silicon compound having the structure represented by the general formula (1) may be partially hydrolyzed at the alkoxy portion, or may be further condensed at the hydrolyzed portion.

[0142] Examples of commercially available products of alkoxysilane condensates include Methyl Silicate 51, Methyl Silicate 53A, Ethyl Silicate 40, Ethyl Silicate 48, and EMS-485 (all manufactured by Colcoat Corporation).

[0143] Moreover, as a commercial item of the hydrolysis condensate of methyl silicate among alkoxysilane condensates, MS51, MS56, MS57, and MS56S (all manufactured by Mitsubishi Chemical Corporation) are mentioned, for example.

[0144] Moreover, as a commercial item of the hydrolysis condensate of ethyl silicate among alkoxysilane condensates, HAS-1, HAS-6, and HAS-10 (all manufactured by Colcoat Co., Ltd.) are mentioned, for example.

[0145] The inorganic fine particle dispersion may contain only one type of alkoxysilane or two or more types of alkoxysilanes. In addition, the alkoxysilane and its condensate may be contained alone or in combination.

[0146] The alkoxysilane preferably contains a condensate of alkoxysilane represented by the following general formula (1).

[0147] General formula (1)

[0148]

[0149] (In formula (1), each R independently represents an alkyl group having 1 to 6 carbon atoms, and n is an integer of 2 to 1000. In one embodiment, n is 2 to 100.)

[0150] Such an inorganic fine particle dispersion has more excellent coating film strength.

[0151] The amount of component C in the inorganic fine particle dispersion is not particularly limited. When the total weight of the inorganic fine particle dispersion is set to 100 mass%, the amount of component C is preferably 0.0001 mass % to 2 mass %, more preferably 0.0005 mass % to 1 mass %, and even more preferably 0.001 mass % to 0.5 mass %.

[0152] 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 the inorganic fine particles]) is preferably greater than 0.005. It is more preferably 0.005 to 0.6, more preferably 0.005 to 0.2, further preferably 0.007 to 0.15, and particularly preferably 0.01 to 0.12.

[0153] As the raw material liquid for preparing the inorganic fine particle dispersion, a liquid containing component C and a solvent can be used. The raw material liquid containing component C may contain additives to promote hydrolysis and dehydration condensation, inhibit aggregation of condensates, or control adhesion to the substrate. An example of the additive is an acrylic-urethane resin.

[0154] [Surfactant]

[0155] As a mode, from the viewpoints such as the smoothness of the coating, the inorganic particle dispersion preferably includes a surfactant. In the case where the inorganic particle dispersion includes a surfactant, when the inorganic particle dispersion is entirely set to 100% by mass, the weight ratio of the surfactant is preferably 0.01% by mass and below 0.5% by mass, and as a further preferred mode, the weight ratio of the surfactant is 0.1% by mass and below 0.45% by mass, and as another further preferred mode, the weight ratio of the surfactant is greater than 0.3% by mass and less than or equal to 0.45% by mass. The surfactant used is not particularly limited, and for example, can be enumerated: anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants, etc. As preferred surfactants, can be enumerated: nonionic surfactants.

[0156] Examples of the anionic surfactant include alkali metal salts of carboxylic acids and alkali metal salts of sulfonic acids, and specific examples include sodium octanoate, potassium octanoate, sodium decanoate, sodium caproate, sodium myristate, potassium oleate, sodium stearate, sodium lauryl sulfate, sodium tetradecyl sulfate, and sodium 1-hexadecanesulfonate.

[0157] Examples of the cationic surfactant include hexadecyltrimethylammonium chloride, dioctadecyldimethylammonium chloride, and N-octadecylpyridinium bromide. , hexadecyltriethyl bromide wait.

[0158] Examples of nonionic surfactants include polyether-modified silicones. The siloxane chain of the main chain of the polyether-modified silicone may be a linear structure or a branched structure, the ether chain of the side chain of the polyether-modified silicone may be a linear structure or a branched structure, and a portion of the side chain of the polyether-modified silicone may be modified with an alkyl group or the like. As polyether-modified silicones, commercially available products may be used, for example: KF-6015, KF-6017, KF-6017P, KF-6028, KF-6028P, KF-6038, KF-6043, KF-6048 (all manufactured by Shin-Etsu Chemical Co., Ltd.); BYK-306, BYK-307, BYK-310, BYK-333, BYK-344, BYK-345, BYK-350, BYK-351, BYK-352, BYK-353, BYK-354, BYK-355, BYK-356, BYK-357, BYK-358, BYK-359, BYK-360, BYK-361, BYK-362, BYK-363, BYK-364, BYK-365, BYK-366, BYK-367, BYK-368, BYK-369, BYK-370, BYK-371, BYK-372, BYK-373, BYK-374, BYK-375, BYK-376, BYK-377, BYK-378, BYK-379, BYK-380, BYK-381, BYK-382, BYK-383, BYK-384, BYK-385, BYK-386, BYK-387, BYK-3 YK-346, BYK-347, BYK-348, BYK-349, BYK-378 (all manufactured by BYK Chemical Japan Co., Ltd.); DOWSIL (trademark) 501W Additive, DOWSIL (trademark) FZ-2104 Fluid, DOWSIL (trademark) FZ-2110, DOWSIL (trademark) FZ-2123, DOWSIL (trademark) FZ-2164, DOWSIL (trademark) FZ-2191, DOWSIL (trademark) FZ-5609 Fluid, DOWSIL (trademark) L-7001, DOWSIL (trademark) L-7002, DOWSIL (trademark) L-7604, DOWSIL (trademark) SH3746 Fluid, DOWSIL (trademark) SH3771 Fluid, DOWSIL (trademark) SH8400 Fluid, DOWSIL (trademark) SF8410 Fluid, DOWSIL (trademark) SF8700 Fluid, SYLGARD (trademark) OFX-0309 Fluid, XIAMETER (trademark) OFX-0193 Fluid, XIAMETER (trademark) OFX-5211 Fluid, DOWSIL (trademark) Y-7006 (all manufactured by Dow Toray Industries, Ltd.), etc.

[0159] Examples of the amphoteric surfactant include 2-alkyl-N-carboxymethyl-N-hydroxyethyl imidazoline Betaine, lauroyl propyl betaine, etc.

[0160] [Other ingredients]

[0161] The inorganic fine particle dispersion may contain silica in addition to the inorganic fine particles X and Y. In addition, a thickener, a thixotropic agent, a defoaming agent, a light stabilizer, a pigment, a mildewproofing agent, a dustproofing agent, an antifreeze performance improving agent, a weathering agent, an ultraviolet stabilizer, etc. may be contained depending on the application and usage method.

[0162] When the inorganic particle dispersion contains additives, for example, the surface treatment of the inorganic particles can be performed using appropriate additives. Regarding additives, for example, additives having polar groups such as hydroxyl, oxy, carbonyl, carboxyl, and epoxy groups can be mentioned, which can be hydrogen-bonded or covalently bonded to the inorganic particles via these polar groups. As additives, for example, polycarboxylic acids and their salts, polymer unsaturated acid esters, modified or unmodified polyurethanes, modified or unmodified polyesters, modified or unmodified polymethacrylates, (meth) acrylic copolymers, polyoxyethylene alkyl phosphates, alkoxysilanes and alkoxysilane condensates cited as component C, and acrylic-urethane resins can be exemplified. The polymer additives are adsorbed on the surface of the inorganic particles and act to prevent reaggregation. Therefore, it is preferred to have an additive with an anchoring site on the particle surface. Terminal modified polymers, grafted polymers, and block polymers can be cited as preferred structures. The surface treatment of the inorganic particles can be performed, for example, by mixing a liquid containing inorganic particles, additives, and a solvent.

[0163] Method for producing inorganic fine particle dispersion

[0164] The inorganic fine particle dispersion can be prepared by combining part or all of the following steps [Step 1] to [Step 10] in any order, but the method is not limited to these methods.

[0165] [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 a metal salt aqueous solution, hydrothermal treatment of the metal salt aqueous solution, and mixing the inorganic fine particles X in a liquid dispersion medium and stirring to disperse the mixture. Commercially available products can also be used as the dispersion of inorganic fine particles X.

[0166] [Step 2] A step of obtaining a dispersion of inorganic particles Y. The dispersion of inorganic 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 a metal salt aqueous solution, hydrothermal treatment of the metal salt aqueous solution, and mixing the inorganic particles Y in a liquid dispersion medium and stirring to disperse the mixture. Commercially available products can also be used as the dispersion of inorganic particles Y.

[0167] [Step 3] A step of obtaining a first dispersion liquid. The first dispersion liquid comprises inorganic particles X and a first liquid dispersion medium. The first dispersion liquid may, as needed, comprise inorganic particles Y, liquid dispersion medium A, liquid dispersion medium B, water, component C, a surfactant, or other components contained in the inorganic particle dispersion liquid. In this case, the weight ratio of these components may be the total amount contained in the inorganic particle dispersion liquid or a portion thereof. The first liquid dispersion medium may be composed of a single liquid dispersion medium or a mixture of multiple liquid dispersion media.

[0168] [Step 4] A step of obtaining a second dispersion liquid. The second dispersion liquid comprises inorganic particles Y and a second liquid dispersion medium. The second dispersion liquid may contain inorganic particles X, liquid dispersion medium A, liquid dispersion medium B, water, component C, a surfactant, or other components contained in the inorganic particle dispersion liquid, as needed. In this case, the weight ratio of these components may be the total amount contained in the inorganic particle dispersion liquid or a portion thereof. The second liquid dispersion medium may be composed of a single liquid dispersion medium or a mixture of multiple liquid dispersion media.

[0169] [Step 5] A step of obtaining a third dispersion liquid. The third dispersion liquid comprises component C and a third liquid dispersion medium. The third dispersion liquid may, as needed, comprise inorganic particles X, inorganic particles Y, liquid dispersion medium A, liquid dispersion medium B, water, a surfactant, or other components contained in the inorganic particle dispersion liquid. In this case, the weight ratio of these components may be the total amount contained in the inorganic particle dispersion liquid or a portion thereof. The third liquid dispersion medium may be composed of a single liquid dispersion medium or a mixture of multiple liquid dispersion media.

[0170] [Step 6] A step of obtaining a fourth dispersion liquid. The fourth dispersion liquid comprises a surfactant and a fourth liquid dispersion medium. The fourth dispersion liquid may, as needed, comprise inorganic particles X, inorganic particles Y, liquid dispersion medium A, liquid dispersion medium B, water, component C, or other components contained in the inorganic particle dispersion liquid. In this case, the weight ratio of these components may be the total amount contained in the inorganic particle dispersion liquid or a portion thereof. The fourth liquid dispersion medium may be composed of a single liquid dispersion medium or a mixture of multiple liquid dispersion media.

[0171] [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, as needed, comprise inorganic particles X, inorganic particles Y, liquid dispersion medium B, water, component C, a surfactant, or other components contained in the inorganic particle dispersion. In this case, the weight ratio of these components may be the total amount contained in the inorganic particle dispersion or a portion thereof. The fifth liquid dispersion medium may be composed of a single liquid dispersion medium or a mixture of multiple liquid dispersion media.

[0172] [Step 8] A step of obtaining a sixth dispersion liquid. The sixth dispersion liquid comprises liquid dispersion medium B and a sixth liquid dispersion medium. The sixth dispersion liquid may, as needed, comprise inorganic particles X, inorganic particles Y, liquid dispersion medium A, water, component C, a surfactant, or other components contained in the inorganic particle dispersion liquid. In this case, the weight ratio of these components may be the total amount contained in the inorganic particle dispersion liquid or a portion thereof. The sixth liquid dispersion medium may be composed of a single liquid dispersion medium or a mixture of multiple liquid dispersion media.

[0173] [Step 9] A step of obtaining a seventh dispersion liquid. The seventh dispersion liquid comprises water and a seventh liquid dispersion medium. The seventh dispersion liquid may, as needed, comprise inorganic particles X, inorganic particles Y, liquid dispersion medium A, liquid dispersion medium B, component C, a surfactant, or other components contained in the inorganic particle dispersion liquid. In this case, the weight ratio of these components may be the total amount contained in the inorganic particle dispersion liquid or a portion thereof. The seventh liquid dispersion medium may be composed of a single liquid dispersion medium or a mixture of multiple liquid dispersion media.

[0174] [Step 10] A step of obtaining an eighth dispersion liquid. The eighth dispersion liquid comprises the other components contained in the inorganic particle dispersion liquid and an eighth liquid dispersion medium. The eighth dispersion liquid may contain inorganic particles X, inorganic particles Y, liquid dispersion medium A, liquid dispersion medium B, water, component C, or a surfactant, as needed. In this case, the weight ratio of these components may be the total amount contained in the inorganic particle dispersion liquid or a portion thereof. The eighth liquid dispersion medium may be composed of a single liquid dispersion medium or a mixture of multiple liquid dispersion media.

[0175] In the above-mentioned steps [1] to

[10] and other optional steps for preparing the inorganic fine particle dispersion, the inorganic fine particles can be dispersed particularly uniformly in the inorganic fine particle dispersion by applying a strong dispersion method such as ultrasonic dispersion or ultrahigh pressure dispersion.

[0176] To achieve more uniform dispersion, the inorganic particles are preferably in a colloidal state in the dispersion of inorganic particles X, the dispersion of inorganic particles Y, and the final inorganic particle dispersion used in the preparation of the inorganic particle dispersion. Water or a volatile organic solvent can be used as the dispersion medium.

[0177] In addition, in the above-mentioned steps [1] to

[10] and other optional steps for preparing the inorganic fine particle dispersion, when the dispersion of inorganic fine particles X, the dispersion of inorganic fine particles Y, or both the dispersion of inorganic fine particles X and the dispersion of inorganic fine particles Y are colloidal alumina, in order to stabilize the positively charged alumina particles, it is preferable to add anions such as chloride ions, sulfate ions, and acetate ions as counter anions to the colloidal alumina. The pH of the colloidal alumina is not particularly limited, but from the perspective of the stability of the inorganic fine particle dispersion, the pH is preferably 2 to 6.

[0178] In addition, in the above-mentioned steps [Step 1] to [Step 10] and other optional steps for preparing the 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 of the inorganic fine particles X or the inorganic fine particles Y or the inorganic fine particle dispersion is in a colloidal state, it is preferred to add anions such as chloride ions, sulfate ions, and acetate ions to the dispersion.

[0179] In addition, in the above-mentioned steps [1] to

[10] and other optional steps for preparing the inorganic fine particle dispersion, when the dispersion of inorganic fine particles X, the dispersion of inorganic fine particles Y, or both the dispersion of inorganic fine particles X and the dispersion of inorganic fine particles Y are dispersions of colloidal silica, cations such as ammonium ions may be added to the colloidal silica as counter cations to stabilize the negatively charged silica particles. The pH of the colloidal silica is not particularly limited.

[0180] In addition, in the above-mentioned steps [Step 1] to [Step 10] and other optional steps for preparing the 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, cations such as ammonium ions can be added to the dispersion.

[0181] As a preferred method when the inorganic fine particle dispersion contains component C, from the perspective of long-term stable storage and management of the coating agent, the following method can be cited: the inorganic fine particle dispersion is prepared by dividing the inorganic fine particle dispersion into the following agent A and agent B, and mixing the agent A and agent B immediately before coating to prepare the inorganic fine particle dispersion.

[0182] [Agent A]: Contains inorganic fine particles and water, and may appropriately contain liquid dispersion medium A, liquid dispersion medium B, a surfactant, and other components.

[0183] [Agent B]: Contains component C, and may appropriately contain liquid dispersion medium A, liquid dispersion medium B, water, a surfactant, and other components.

[0184] The agent A contains inorganic fine particles and water, and may appropriately contain a liquid dispersion medium A, a liquid dispersion medium B, a surfactant, and other components.

[0185] When the total weight of Agent A is 100 mass %, the weight ratio of the inorganic fine particles contained in Agent A is preferably 0.05 mass % to 30 mass %, more preferably 0.1 mass % to 20 mass %, and even more preferably 0.5 mass % to 15 mass %.

[0186] When the total weight of Agent A is set to 100% by mass, the lower limit of the weight ratio of water contained in Agent A is preferably 1% by mass or more of water, more preferably 5% by mass or more of water, more preferably 10% by mass or more of water, and more preferably 15% by mass or more of water.

[0187] In addition, as the upper limit of the weight ratio of water contained in Agent A, it is preferred that it contains 90% by mass or less of water, more preferably 80% by mass or less of water, more preferably 60% by mass or less of water, more preferably 50% by mass or less of water, more preferably 40% by mass or less of water, and more preferably 30% by mass or less of water.

[0188] The above-mentioned agent B contains component C and may contain liquid dispersion medium A, liquid dispersion medium B, water, a surfactant, and other components as appropriate. Regarding agent B, only component C may be used as agent B.

[0189] The weight ratio of water contained in Agent B is preferably small. When the total weight of Agent B is 100 mass %, it is preferably 5 mass % or less, more preferably 3 mass % or less, more preferably 1 mass % or less, and particularly preferably 0.8 mass % or less.

[0190] <Method for producing laminate>

[0191] The method for manufacturing a laminate of the present invention is a method for manufacturing a laminate having a substrate and a coating applied to the main surface of at least one side of the substrate, and the method for manufacturing the laminate includes the following steps: a step of coating the above-mentioned inorganic fine particle dispersion on the substrate (coating step); and a step of performing a heat treatment at a temperature of greater than 200°C and less than 1000°C for more than 10 minutes (heat treatment step).

[0192] In addition, the present invention is preferably a method for manufacturing a laminate having a substrate and a coating applied to the main surface of at least one side of the substrate, the method for manufacturing the laminate comprising the following steps: a step of coating the above-mentioned inorganic particle dispersion on the substrate (coating step); a step of removing the liquid dispersion medium from the inorganic particle dispersion coated on the substrate by an appropriate method to form a coating before heat treatment on the substrate (dispersion medium removal step); and a step of performing heat treatment at a temperature of above 200°C and below 1000°C for more than 10 minutes (heat treatment step).

[0193] [Coating process]

[0194] The method for coating the inorganic fine particle dispersion on the substrate is not particularly limited, and examples thereof include gravure coating, reverse coating, brush roller coating, spray coating, kiss roller coating, die coating, dipping, and bar coating.

[0195] The shape of the substrate is not particularly limited, and examples thereof include films, sheets, plates, and tubes.

[0196] The material of the substrate is not particularly limited, and examples thereof include plastics 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. Furthermore, optical components such as polarizing plates, diffusers, light guide plates, brightness enhancement films, and reflective polarizing plates may also be used as substrates. The substrate may have a hard coat layer comprising a UV-curable resin or an antistatic layer containing conductive fine particles as a surface layer.

[0197] From the viewpoint of high heat resistance and transmittance, a glass substrate is preferred.

[0198] When glass is used as the substrate, there are no particular restrictions on the composition and manufacturing method of the glass. Soda glass, crystal glass, borosilicate glass, quartz glass, sapphire glass, aluminosilicate glass, borate glass, phosphate glass, alkali-free glass, or composite glass with ceramics can be used.

[0199] Quartz glass or sapphire glass is preferred due to its high transmittance over a wide wavelength range. Quartz glass or sapphire glass is preferred due to its high ultraviolet transmittance. Quartz glass is particularly preferred. Examples of quartz glass include fused silica glass and synthetic silica glass. Synthetic silica glass is more preferably used as the substrate.

[0200] Before coating the inorganic fine particle dispersion on 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.

[0201] [Dispersion medium removal step] and [heat treatment step]

[0202] The coating film before heat treatment can be formed on the substrate surface by removing the liquid dispersion medium from the inorganic fine particle dispersion liquid applied on the substrate surface (dispersion medium removal process). The removal of the liquid dispersion medium can be carried out by natural drying at room temperature in one embodiment, or by heating at normal pressure or under reduced pressure in one embodiment. In one embodiment, the removal of the liquid dispersion medium can be carried out by natural drying at room temperature and then heating at normal pressure or under reduced pressure.

[0203] When drying naturally at room temperature, the drying time is not particularly limited, but in one embodiment, it is preferably less than 24 hours, and in another embodiment, it is preferably 60 minutes or less. Alternatively, in another embodiment, it can be 24 hours or more.

[0204] When heating is performed at normal pressure or under reduced pressure, the pressure and heating temperature when the liquid dispersion medium is removed by heating can be appropriately selected according to the material used (i.e., inorganic particles X, inorganic particles Y and liquid dispersion medium). For example, it is usually possible to dry at a temperature of greater than or equal to 50°C and less than 200°C, preferably greater than or equal to 50°C and less than 120°C, more preferably greater than or equal to 60°C and less than 110°C. In one embodiment, it can be dried at a temperature of greater than or equal to 50°C and less than 80°C, and in one embodiment, it can be dried at a temperature of greater than or equal to 20°C and less than 50°C. The heating time is not particularly limited, and in one embodiment, it is preferably less than 24 hours, and in one embodiment, it is preferably less than 60 minutes. Alternatively, in one embodiment, it can be more than 24 hours.

[0205] After removing the liquid dispersion medium in the above-mentioned dispersion medium removal process, the substrate formed with the coating before heat treatment on the surface can be heat-treated to improve the adhesion of the substrate and the coating before heat treatment (heat treatment process). In this specification, the coating before heat treatment after heat treatment is recorded as "coating". The heat treatment method in the heat treatment process is not particularly limited, and for example, local heating of the coating before heat treatment using a heat treatment furnace, electromagnetic wave radiation, etc. can be mentioned. As heat treatment furnaces, muffle furnaces, bell furnaces, mesh belt furnaces, etc. can be mentioned.

[0206] During the heat treatment step, the substrate is preferably maintained within a temperature range of 200°C to 1000°C for a period of more than 10 minutes, and more preferably maintained within a temperature range of 200°C to 1000°C for a period of more than 60 minutes. This heat treatment step is preferred from the perspective of improving the wear resistance of the coating film. The reason for the improved wear resistance of the coating film is not yet clear, but it is speculated that this heat treatment step stabilizes the agglomerated structure of the inorganic fine particles, resulting in high wear resistance.

[0207] In one embodiment, the substrate is maintained at a temperature in the range of 200° C. to 1000° C. for a period of more than 720 minutes.

[0208] 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, 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 further preferably 500°C or higher and 720°C or lower.

[0209] In the heat treatment step, the substrate is preferably maintained in a temperature range of 200°C to 1000°C for more than 10 minutes, more preferably, the substrate is maintained in a temperature range of 200°C to 1000°C for more than 60 minutes, more preferably, the substrate is maintained in a temperature range of 200°C to 1000°C for more than 180 minutes, more preferably, the substrate is maintained in a temperature range of 200°C to 1000°C for more than 360 minutes, and more preferably, the substrate is maintained in a temperature range of 200°C to 1000°C for more than 720 minutes.

[0210] In the heat treatment step, the substrate is preferably maintained in a temperature range of 300°C to 900°C for more than 10 minutes, more preferably, the substrate is maintained in a temperature range of 300°C to 900°C for more than 60 minutes, more preferably, the substrate is maintained in a temperature range of 300°C to 900°C for more than 180 minutes, more preferably, the substrate is maintained in a temperature range of 300°C to 900°C for more than 360 minutes, and more preferably, the substrate is maintained in a temperature range of 300°C to 900°C for more than 720 minutes.

[0211] In the heat treatment step, the substrate is preferably maintained in a temperature range of 300°C to 800°C for more than 10 minutes, more preferably, the substrate is maintained in a temperature range of 300°C to 800°C for more than 60 minutes, more preferably, the substrate is maintained in a temperature range of 300°C to 800°C for more than 180 minutes, more preferably, the substrate is maintained in a temperature range of 300°C to 800°C for more than 360 minutes, and more preferably, the substrate is maintained in a temperature range of 300°C to 800°C for more than 720 minutes.

[0212] In the heat treatment step, the substrate is preferably maintained in a temperature range of 400°C to 800°C for more than 10 minutes, more preferably, the substrate is maintained in a temperature range of 400°C to 800°C for more than 60 minutes, more preferably, the substrate is maintained in a temperature range of 400°C to 800°C for more than 180 minutes, more preferably, the substrate is maintained in a temperature range of 400°C to 800°C for more than 360 minutes, and more preferably, the substrate is maintained in a temperature range of 400°C to 800°C for more than 720 minutes.

[0213] In the heat treatment step, the substrate is preferably maintained in a temperature range of 500°C to 800°C for more than 10 minutes, more preferably, the substrate is maintained in a temperature range of 500°C to 800°C for more than 60 minutes, more preferably, the substrate is maintained in a temperature range of 500°C to 800°C for more than 180 minutes, more preferably, the substrate is maintained in a temperature range of 500°C to 800°C for more than 360 minutes, and more preferably, the substrate is maintained in a temperature range of 500°C to 800°C for more than 720 minutes.

[0214] In the heat treatment step, the substrate is preferably maintained in a temperature range of 500°C to 720°C for more than 10 minutes, more preferably maintained in a temperature range of 500°C to 720°C for more than 60 minutes, more preferably maintained in a temperature range of 500°C to 720°C for more than 180 minutes, more preferably maintained in a temperature range of 500°C to 720°C for more than 360 minutes, and more preferably maintained in a temperature range of 500°C to 720°C for more than 720 minutes.

[0215] When heating is performed in a heat treatment furnace, the temperature of the substrate maintained during the heat treatment process can also be regarded as the temperature of the heat treatment furnace. When local heating is performed by electromagnetic wave radiation, etc., the temperature of the substrate maintained during the heat treatment process is the temperature of the substrate.

[0216] The heating 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 is preferably air.

[0217] In one embodiment, the heat treatment process includes a process of raising the temperature to a target temperature (heating process), a process of maintaining the target temperature (temperature holding process), and a process of lowering the temperature (cooling process). In the heating process, the temperature before raising the temperature is not particularly limited, and in one embodiment is above 0°C and below 40°C. The heating rate in the heating process is preferably below 10°C / minute, and more preferably below 5°C / minute. The target temperature is above 200°C and below 1000°C, preferably above 300°C and below 900°C, more preferably above 300°C and below 800°C, more preferably above 400°C and below 800°C, more preferably above 500°C and below 800°C, more preferably above 500°C and below 720°C. The holding time in the temperature holding process is greater than 10 minutes, preferably greater than 15 minutes, and more preferably greater than 20 minutes. The cooling method in the cooling process is not particularly limited, and cooling can be performed by stopping heating and allowing natural cooling.

[0218] The coating film is formed on at least one main surface of the substrate by the heat treatment step. Alternatively, the coating film may be formed on both main surfaces of the substrate, or may be formed on all surfaces of the substrate.

[0219] 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. In another embodiment, the method for producing a laminate may include two or more coating steps. A laminate obtained by a production method including two or more coating steps has a higher transmittance than a laminate obtained by a production method including only a single coating step.

[0220] In one embodiment, after the coating process, the dispersion medium removal process or the heat treatment process, the process (coating process) of applying the inorganic particle dispersion or the coating liquid described later to the substrate can be implemented again. For example, after the coating process and the dispersion medium removal process, the coating process and the dispersion medium removal process are passed through again, and a heat treatment process is implemented, thereby forming a two-layer coating film on the substrate. In addition, for example, after the coating process and the dispersion medium removal process, the coating process and the dispersion medium removal process are passed through again, and the coating process and the dispersion medium removal process are further passed through again, and a heat treatment process is implemented, thereby forming a three-layer coating film on the substrate.

[0221] <Laminated body>

[0222] The thickness of the film in the laminate with base material and film obtained by said method is not particularly limited.In one mode, the thickness of film is more than 20nm and below 200nm, in another mode, the thickness of film is more than 20nm and below 100nm, in addition, in another mode, the thickness of film is more than 20nm and below 75nm, in addition, in another mode, the thickness of film is more than 25nm and below 60nm.From the viewpoint of the transmittance improving the ultraviolet region (wavelength range of more than 185nm and below 300nm) of laminate, the thickness of film is preferably more than or equal to 20nm and less than 75nm, more preferably more than 25nm and below 60nm.

[0223] The thickness of the coating film can be measured using an image of a coating film cross section obtained by observation using a scanning electron microscope (SEM).

[0224] Furthermore, the present invention also relates to a laminated body obtainable by a method for producing a laminated body according to the various embodiments described above.

[0225] Furthermore, the present invention also provides the following laminate:

[0226] A laminate comprising a substrate and a coating film applied to at least one main surface of the substrate, wherein:

[0227] The coating film has a thickness of greater than or equal to 20 nm and less than 75 nm,

[0228] The average transmittance of the laminate in the wavelength range of 185 nm to 300 nm is higher by 0.5 percentage points or more than the average transmittance of a substrate having no coating film in the wavelength range of 185 nm to 300 nm.

[0229] The coating film may be formed on both main surfaces of the substrate or on all surfaces of the substrate. The coating film has a thickness of 20 nm or more and less than 75 nm. In another embodiment, the coating film has a thickness of 25 nm or more and less than 75 nm. In another embodiment, the coating film has a thickness of 25 nm or more and less than 60 nm.

[0230] The average transmittance of the laminate in a wavelength range of more than 185 nm and less than 300 nm relative to the average transmittance in a wavelength range of more than 185 nm and less than 300 nm of the substrate without the coating is 0.5 percentage points or more, preferably 1.0 percentage points or more, more preferably 1.5 percentage points or more. The increase in transmittance is achieved by the coating not absorbing light in a wavelength range of more than 185 nm and less than 300 nm and having an anti-reflection effect. The anti-reflection effect is an effect produced by the reflected light from the coating surface and the reflected light from the substrate surface offsetting each other, and the size of the effect depends on the refractive index and film thickness of the coating. In addition, in the case of two or more coatings, the size of the anti-reflection effect depends on the refractive index and thickness of each layer.

[0231] The increase relative to the above-mentioned average transmittance can be achieved by adjusting the refractive index and film thickness of the coating formed on the substrate. It should be noted that the increase in the above-mentioned average transmittance is calculated by the method described in the Examples. The increase in the average transmittance within a specific wavelength range can be calculated as follows: for the laminate and the uncoated substrate, the transmittance of each wavelength within the specific wavelength range is measured and the average value is calculated, and then the average transmittance of the uncoated substrate is subtracted from the average transmittance of the laminate.

[0232] This laminate can be obtained by the method for producing a laminate according to the various embodiments described above.

[0233] 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 and the coating amount of the inorganic fine particle dispersion.

[0234] Furthermore, the present invention also provides the following laminated body.

[0235] A laminate comprising a substrate and a coating film applied to at least one main surface of the laminate, characterized in that:

[0236] The coating film has a porous structure and a thickness greater than or equal to 20 nm and less than 100 nm.

[0237] The transmittance of the laminated body at any wavelength of 150 nm or more and less than 300 nm is 80.0% or more.

[0238] The same substrate as the above-mentioned substrate can be used as the substrate, and the preferred substrate is also as described above.

[0239] The coating film may be the same coating film as the aforementioned coating film and the coating film described below.

[0240] A porous structure refers to a structure in which a large number of nanometer-sized fine pores and voids are present inside. When a surface or cross-section of a coating having this structure is observed using a scanning electron microscope (SEM), fine pores can be confirmed. On the other hand, a coating formed on a substrate by dry coating (sputtering, vapor deposition, etc.) is a dense film without fine pores or voids and does not have a porous structure.

[0241] The transmittance of the laminate at any wavelength of 150 nm or more and less than 300 nm is preferably 80.0% or more, more preferably 85.0% or more, further preferably 90.0% or more, and even more preferably 92.0% or more.

[0242] The transmittance of the laminate at any wavelength of 160 nm or greater and less than 300 nm is preferably 80.0% or greater, more preferably 85.0% or greater, further preferably 90.0% or greater, and even more preferably 92.0% or greater.

[0243] The transmittance of the laminate at any wavelength of 185 nm or greater and less than 300 nm is preferably 80.0% or greater, more preferably 85.0% or greater, further preferably 90.0% or greater, and even more preferably 92.0% or greater.

[0244] The transmittance of the laminate at any wavelength of 150 nm or more and less than 280 nm is preferably 80.0% or more, more preferably 85.0% or more, further preferably 90.0% or more, and even more preferably 92.0% or more.

[0245] The transmittance of the laminate at any wavelength of 160 nm or greater and less than 280 nm is preferably 80.0% or greater, more preferably 85.0% or greater, further preferably 90.0% or greater, and even more preferably 92.0% or greater.

[0246] The transmittance of the laminate at any wavelength of 185 nm to 280 nm is preferably 80.0% or more, more preferably 85.0% or more, further preferably 90.0% or more, and even more preferably 92.0% or more.

[0247] In one embodiment, the transmittance of the laminate at a wavelength of 254 nm is preferably 80.0% or higher, more preferably 85.0% or higher, even more preferably 90.0% or higher, even more preferably 92.0% or higher, and even more preferably 94.0% or higher.

[0248] In one embodiment, the transmittance of the laminate at a wavelength of 222 nm is preferably 80.0% or higher, more preferably 85.0% or higher, even more preferably 90.0% or higher, even more preferably 92.0% or higher, and even more preferably 94.0% or higher.

[0249] In one embodiment, the transmittance of the laminate at a wavelength of 185 nm is preferably 80.0% or higher, more preferably 85.0% or higher, even more preferably 90.0% or higher, even more preferably 91.0% or higher, and even more preferably 91.5% or higher.

[0250] In one embodiment, the average transmittance of the laminate in a wavelength range of 185 nm to 300 nm is preferably 80.0% or more, more preferably 85.0% or more, further preferably 90.0% or more, further preferably 92.0% or more, and further preferably 93.0% or more.

[0251] In one embodiment, the average transmittance of the laminate in a wavelength range of 185 nm to 280 nm is preferably 80.0% or more, more preferably 85.0% or more, further preferably 90.0% or more, further preferably 92.0% or more, and further preferably 93.0% or more.

[0252] In one embodiment, the laminate preferably satisfies any one of “a transmittance of 94.0% or more at a wavelength of 254 nm,” “a transmittance of 94.0% or more at a wavelength of 222 nm,” and “a transmittance of 91.5% or more at a wavelength of 185 nm.”

[0253] The laminate having the above transmittance means that the substrate and coating film constituting the laminate have high deep UV transmittance. The reasons for the high deep UV transmittance are speculated to be: (1) low silanol content, resulting in silanol group condensation; (2) low metal impurity content; (3) low residual organic components; or (4) low coating surface roughness. It is speculated that the laminate achieves excellent alkali resistance and / or abrasion resistance due to at least one of the above reasons (1) to (4).

[0254] The laminate comprises a substrate and a coating film applied to at least one main surface of the substrate. The coating film may be formed on both main surfaces of the substrate, or may be formed on all surfaces of the substrate. The coating film has a thickness of 20 nm or greater and less than 100 nm. In another embodiment, the coating film has a thickness of 20 nm or greater and less than 75 nm. In another embodiment, the coating film has a thickness of 25 nm or greater and less than 75 nm. In another embodiment, the coating film has a thickness of 25 nm or greater and less than 60 nm.

[0255] This laminate can be obtained by a method for producing a laminate according to various embodiments described above and below (a method using a coating agent such as an inorganic fine particle dispersion or a coating liquid).

[0256] When the aforementioned inorganic fine particle dispersion 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 and the coating amount of the inorganic fine particle dispersion.

[0257] When a coating liquid described later is used, the thickness of the coating film can be adjusted by changing the weight ratio of the alkoxysilane in the coating liquid and the coating amount of the coating liquid.

[0258] The ratio of the number of carbon atoms in the surface of the coating film to the total number of atoms of sodium, potassium, magnesium, calcium, aluminum and silicon (number of carbon atoms / sum of the number of atoms of silicon, etc.) is preferably 1.00 or less, more preferably 0.60 or less, further preferably 0.50 or less, further preferably 0.40 or less, further preferably 0.30 or less, and further preferably 0.25 or less.

[0259] In one embodiment, the ratio of the number of carbon atoms in the surface of the coating film to the total number of sodium, potassium, magnesium, calcium, aluminum, and silicon atoms is preferably 0.20 or less, more preferably 0.15 or less, and even more preferably 0.10 or less.

[0260] The ratio of the number of carbon atoms to the total number of sodium, potassium, magnesium, calcium, aluminum, and silicon atoms in the surface of the coating film can be determined by a method using a photoelectron spectrometer as described later.

[0261] In one embodiment, the coating film preferably contains inorganic fine particles. As the inorganic fine particles, the same inorganic fine particles as those described above can be used.

[0262] The inorganic fine particles are preferably inorganic fine particles containing silicon dioxide.

[0263] The primary particle size of the inorganic fine particles is preferably greater than or equal to 1 nm and less than 50 nm, more preferably greater than or equal to 1 nm and less than 40 nm, more preferably greater than or equal to 1 nm and less than 30 nm, further preferably greater than or equal to 1 nm and less than 20 nm, and particularly preferably greater than or equal to 3 nm and less than 10 nm.

[0264] 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.

[0265] In the above-mentioned laminate, the coating film has a kurtosis of brightness distribution in a cross-sectional image of the coating film under a scanning electron microscope of preferably 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.

[0266] The coating (film with porous structure) has the gaps derived from the gaps between particles etc. in the cross-sectional image obtained by the method for observing using a scanning electron microscope (SEM) described later, and therefore, the coating has a concavo-convex structure in its cross section. Thus, the cross-sectional image obtained by the method for observing using a scanning electron microscope (SEM) described later has both bright and dark parts, and has a brightness distribution. The kurtosis in the brightness distribution in the cross-sectional image of the scanning electron microscope of the coating is less than 0.320. The kurtosis in the brightness distribution in the cross-sectional image of the scanning electron microscope can be obtained by the method described later. The kurtosis in the brightness distribution is preferably less than 0.300, more preferably less than 0.250, more preferably less than 0.200, more preferably less than 0.150, more preferably less than 0.130, more preferably less than 0.120, more preferably less than 0.110, more preferably less than 0.100, more preferably less than 0.090. When it is the kurtosis in such a brightness distribution, it is a good porous structure with excellent transmittance.

[0267] In the above-mentioned laminate, the arithmetic mean roughness of the coating is preferably 0.1 nm or more and 10.0 nm or less, more preferably 0.2 nm or more and 7.0 nm or less, further preferably 0.2 nm or more and 5.0 nm or less, and particularly preferably 0.2 nm or more and 1.5 nm or less. When the arithmetic mean roughness of the coating is within the above range, a laminate with excellent deep ultraviolet transmittance and wear resistance can be obtained. The arithmetic mean roughness of the coating can be determined by the measurement using a scanning probe microscope (SPM) described later.

[0268] In the above-mentioned laminate, the substrate is preferably quartz glass or sapphire glass, and more preferably quartz glass. Examples of quartz glass include fused quartz glass and synthetic quartz glass, and synthetic quartz glass is more preferably used as the substrate.

[0269] In the above-mentioned laminate, the thickness of the substrate is preferably 0.1 mm to 100 mm, more preferably 0.1 mm to 50 mm, and even more preferably 0.3 mm to 30 mm.

[0270] The laminate is preferably obtained by a production method comprising the steps of applying a coating agent to a substrate and performing a heat treatment at a temperature of 200° C. to 1000° C. for more than 10 minutes.

[0271] The coating agent may be the same as the aforementioned inorganic fine particle dispersion, or may be the same as the coating liquid described later.

[0272] The substrate, coating step, and heat treatment step may be the same as those described above or below.

[0273] In one embodiment, the laminate can be obtained by a production method comprising: applying a coating solution comprising an alkoxysilane, water, an acid catalyst, and a pore-forming agent onto a substrate; and performing a heat treatment at a temperature of 200° C. to 1000° C. for more than 10 minutes.

[0274] In the above-mentioned laminate, the alkoxysilane, acid catalyst and pore former described below can be used. In the above-mentioned laminate, the coating step and the heat treatment step can be the same as those described above or below.

[0275] Furthermore, the present invention also provides the following laminated body.

[0276] A laminated body, wherein the laminated body can be obtained by a method for manufacturing a laminated body, wherein the laminated body has a substrate and a coating film applied to the main surface of at least one side of the substrate, the method for manufacturing the laminated body comprising the steps of: applying a coating agent on the substrate; and performing a heat treatment at a temperature of 200°C or higher and 1000°C or lower for more than 10 minutes.

[0277] The coating agent may be the same as the aforementioned inorganic fine particle dispersion, or may be the same as the coating liquid described later.

[0278] The substrate, coating step, heat treatment step, and coating film may be the same as those described above or below.

[0279] Furthermore, the present invention also provides the following coating liquid.

[0280] A coating liquid comprising an alkoxysilane, water, an acid catalyst, a pore-forming agent, 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 greater than or equal to 0.5% by mass and less than 15% by mass when the total amount of the coating liquid is set to 100% by mass.

[0281] In the coating solution of the present invention, the weight ratio of water, liquid dispersion medium A, and liquid dispersion medium A may be the same as described above.

[0282] In the coating solution of the present invention, the alkoxysilane may be the same as described above.

[0283] In the coating liquid of the present invention, the alkoxysilane is preferably the following alkoxysilane.

[0284] An alkoxysilane containing the following alkoxysilane C01 and alkoxysilane C02 as alkoxysilanes, wherein the ratio of the weight of SiO2 contained in the alkoxysilane C02 to the total weight of SiO2 contained in the alkoxysilane ([the weight of SiO2 contained in the alkoxysilane C02] / [the total weight of SiO2 contained in the alkoxysilane]) is greater than 0.00 and less than 0.50.

[0285] Alkoxysilane C01: at least one alkoxysilane selected from the group consisting of tetraalkoxysilane and a condensate of an alkoxysilane represented by the following general formula (01).

[0286] General formula (01)

[0287]

[0288] (In formula (01), each R independently represents an alkyl group having 1 to 6 carbon atoms, and n is an integer of 2 to 1000.)

[0289] Examples of R in the alkyl group having 1 to 6 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, and tert-amyl (1,1-dimethylpropyl). Preferred examples include methyl, ethyl, and butyl, and more preferred examples include methyl and ethyl.

[0290] In the general formula (01), n represents an integer of 2 to 1000, preferably 2 to 100, more preferably 3 to 50, and even more preferably 3 to 30.

[0291] The weight average molecular weight of the silicon compound having a structure represented by the above-mentioned 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.

[0292] The silicon compound having the structure represented by the general formula (01) may be partially hydrolyzed at the alkoxy portion, or may be further condensed at the hydrolyzed portion.

[0293] Examples of commercially available products of the alkoxysilane condensate include Methyl Silicate 51, Methyl Silicate 53A, Ethyl Silicate 40, Ethyl Silicate 48, and EMS-485 (all manufactured by Colcoat Corporation).

[0294] Moreover, as a commercial item of the hydrolysis condensate of methyl silicate among alkoxysilane condensates, MS51, MS56, MS57, and MS56S (all manufactured by Mitsubishi Chemical Corporation) are mentioned, for example.

[0295] Moreover, as a commercial item of the hydrolysis condensate of ethyl silicate among alkoxysilane condensates, HAS-1, HAS-6, and HAS-10 (all manufactured by Colcoat Co., Ltd.) are mentioned, for example.

[0296] Alkoxysilane C02: at least one alkoxysilane selected from the group consisting of alkoxysilanes represented by the following general formula (02) and condensates thereof.

[0297] Si(R a ) q (R b ) 4-q (02)

[0298] In formula (02), R a represents a hydrogen atom or a non-hydrolyzable organic group, R b represents a hydrolyzable group. q represents an integer of 1 to 2.

[0299] As 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-pentyl (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.

[0300] As R b Examples of the hydrolyzable group include alkoxy groups having 1 to 5 carbon atoms, such as methoxy, ethoxy, and propoxy, and methoxy and ethoxy are preferred.

[0301] The silicon compound represented by the formula (02) may undergo hydrolysis of the hydrolyzable group, or may further undergo condensation at the hydrolyzed portion.

[0302] Examples of the silicon compound represented by formula (02) include silicon compounds wherein q is 1, such as methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltriisopropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, phenyltrimethoxysilane, and phenyltriethoxysilane; and silicon compounds wherein q is 2, such as dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, and methylphenyldimethoxysilane. Particularly preferred are methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, and diethyldiethoxysilane.

[0303] The ratio of the weight of SiO2 contained in the alkoxysilane C02 to the total weight of SiO2 contained in the alkoxysilane ([the weight of SiO2 contained in the alkoxysilane C02] / [the total weight of SiO2 contained in the alkoxysilane]) is preferably greater than 0.00 and less than 0.50, more preferably greater than 0.10 and less than 0.50, further preferably greater than 0.20 and less than 0.50, and further preferably greater than 0.25 and less than 0.40.

[0304] When the total amount of the coating liquid is set to 100 mass%, the total weight of SiO2 contained in alkoxysilane C01 and alkoxysilane C02 is preferably 0.05 mass% or more and 10 mass% or less, more preferably 0.1 mass% or more and 7.5 mass% or less, further preferably 0.2 mass% or more and 5.0 mass% or less, and particularly preferably 0.5 mass% or more and 2.0 mass% or less.

[0305] 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 may be the same as described above.

[0306] [Pore-forming agent]

[0307] The coating liquid of the present invention contains a pore-forming agent. As described later, in the present invention, for example, a coating step using the coating liquid and a dispersion medium removal step form a substrate having a pre-heat-treated coating film formed on its surface. This pre-heat-treated coating film contains a pore-forming agent, and in the subsequent heat treatment step, the pore-forming agent in the pre-heat-treated coating film is thermally decomposed and removed, thereby imparting pores to the coating film. The presence of voids derived from the pore-forming agent in this coating film creates a low-refractive-index layer, thereby contributing to improved light transmittance.

[0308] As one form of the pore-forming agent, organic ammonium salts and pyridine are mentioned. The salt is preferably an organic ammonium salt. Preferred examples include organic ammonium salts having a structure represented by the following general formula (4).

[0309] General formula (4)

[0310]

[0311] (In formula (4), each of L1 to L4 independently represents 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 in L1 to L4 is 1 to 40. E1 represents a monovalent anion.)

[0312] In the general formula (4), each of L1 to L4 independently represents a hydrogen atom and 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.

[0313] In the 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. Chloride ions, bromide ions, and hydrogen sulfate ions are preferred, chloride ions and bromide ions are more preferred, and chloride ions are even more preferred.

[0314] Examples of the organic ammonium salt having a structure represented by the general formula (4) include preferably secondary ammonium salts, tertiary ammonium salts, and quaternary ammonium salts, more preferably tertiary ammonium salts and quaternary ammonium salts, and even more preferably quaternary ammonium salts. Specific examples of the quaternary ammonium salts include the following.

[0315] 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)trimethylammonium chloride, trimethylpropyl ammonium 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, tetradecylammonium bromide, tetraheptylammonium bromide, tetra-n-octylammonium bromide, didecyldimethylammonium bromide, and didodecyldimethylammonium bromide.

[0316] In general formula (4), each of L1 to L4 independently represents a hydrogen atom or an organic group having 1 to 15 carbon atoms. The organic groups in L1 to L4 preferably have 1 to 12 carbon atoms, more preferably 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and even more preferably 1 to 7 carbon atoms. These organic groups can exhibit good coating properties.

[0317] In the general formula (4), the total number of carbon atoms of the organic groups contained in L1 to L4 is 1 to 40.

[0318] 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 substance can exhibit good coating properties.

[0319] <Ratio of the weight of the pore former to the total weight of SiO2 contained in the alkoxysilane>

[0320] In the coating solution (coating liquid) of the present invention, the ratio of the weight of the pore-forming agent to the total weight of SiO2 contained in the alkoxysilane ([weight of the pore-forming agent] / [total weight of SiO2 contained in the alkoxysilane]) is 0.10 or more. As a lower limit, it 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, more preferably 2.60 or more. As an upper limit, it is preferably 8.00 or less, more preferably 5.00 or less, more preferably 4.50 or less, more preferably 4.00 or less, more preferably 3.00 or less.

[0321] <Ratio of the amount of the pore former to the amount of the alkyl group contained in the alkoxysilane C02>

[0322] In the coating liquid of the present invention (coating liquid), the ratio of the amount of the pore-forming agent to the amount of the alkyl groups contained in the alkoxysilane C02 ([amount of alkoxysilane C02] × q (number of alkyl groups in alkoxysilane C02)) is 0.1 or greater. The lower limit is preferably 0.1 or greater, more preferably 0.3 or greater, and even more preferably 0.5 or greater.

[0323] [Acid catalyst]

[0324] The coating liquid of the present invention contains an acid catalyst.

[0325] Examples of the acid catalyst include organic acids and inorganic acids. Examples of organic acids include formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, maleic acid, phthalic acid, and fumaric acid. Examples of inorganic acids include hydrochloric acid, nitric acid, sulfuric acid, and phosphoric acid.

[0326] Preferred are formic acid, acetic acid, oxalic acid, hydrochloric acid, nitric acid, sulfuric acid and phosphoric acid, more preferred are formic acid, acetic acid, hydrochloric acid, nitric acid, sulfuric acid and phosphoric acid, more preferred are hydrochloric acid, nitric acid, sulfuric acid and phosphoric acid, more preferred are hydrochloric acid, nitric acid and sulfuric acid, and more preferred are hydrochloric acid and nitric acid.

[0327] [Other ingredients]

[0328] 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. Furthermore, depending on the application and method of use, the coating liquid may contain a thickener, a thixotropic agent, a defoaming agent, a light stabilizer, a pigment, a mildewproofing agent, a dustproofing agent, an antifreeze performance improving agent, a weathering agent, a UV stabilizer, a surfactant, and the like.

[0329] [Surfactant]

[0330] The coating liquid of the present invention may contain a surfactant.

[0331] When the coating liquid of the present invention contains a surfactant, the same surfactant as described above in [Surfactant] may be contained.

[0332] As the surfactant that may be contained in the coating liquid of the present invention, a cationic surfactant or a nonionic surfactant is preferable.

[0333] Examples of the cationic surfactant include hexadecyltrimethylammonium chloride, dioctadecyldimethylammonium chloride, and N-octadecylpyridinium bromide. and hexadecyltriethyl bromide wait.

[0334] Examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene steryl ether, and polyoxyethylene polyoxypropylene alkyl ether.

[0335] <Method for preparing coating solution>

[0336] The coating liquid of the present invention can be prepared by the same method as described in the above-mentioned <Method for producing an inorganic fine particle dispersion> except that the inorganic fine particles are not contained.

[0337] One preferred embodiment of the method for preparing the coating liquid of the present invention includes a method in which the following agent A01 or agent B01 is prepared and the coating liquid is prepared using the agent A01 or B01.

[0338] [A01 dose]

[0339] Agent A01 contains component C (alkoxysilane), water, and an acid catalyst, and may contain a liquid dispersion medium B as appropriate. When containing liquid dispersion medium B, Agent A01 can be prepared by adding liquid dispersion medium B to component C, followed by adding water and an 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.

[0340] Component C: When the total weight of the A01 agent is 100 mass %, the weight ratio of SiO2 contained in the alkoxysilane is 5 mass % or more and 25 mass % or less.

[0341] Water: The amount of water added is 2 to 20 times the amount of silicon atoms contained in the alkoxysilane.

[0342] Acid catalyst: An added amount of 0.001 to 0.1 times the amount of silicon atoms contained in the alkoxysilane.

[0343] Liquid dispersion medium B: When the total weight of agent A01 is 100% by mass, the weight ratio of the liquid dispersion medium B is 20% by mass or more and 80% by mass or less.

[0344] In addition, it is preferable that the agent A01 contains alkoxysilane C01.

[0345] [B01 dose]

[0346] Agent B01 can be prepared by further adding component C to agent A01, adding liquid dispersion medium B as needed, and mixing at room temperature or a temperature of 10° C. to 40° C. The amounts of each component added in this preparation method are as follows.

[0347] Component C: An amount in which the weight ratio of SiO 2 contained in the alkoxysilane is 7% by mass or more and 30% by mass or less, based on 100% by mass of the total weight of the B01 agent.

[0348] Water: The amount of water added is 2 to 15 times the amount of silicon atoms contained in the alkoxysilane.

[0349] Acid catalyst: 0.001 to 0.1 times the amount of silicon atoms contained in the alkoxysilane

[0350] Liquid dispersion medium B: When the total weight of agent B01 is 100% by mass, the weight ratio of the liquid dispersion medium B is 20% by mass or more and 80% by mass or less.

[0351] [Coating liquid]

[0352] The coating solution can be prepared by mixing the aforementioned Agent A01 or Agent B01, liquid dispersion medium A, a pore-forming agent, and, if necessary, liquid dispersion medium B, water, an acid catalyst, and the other components described above. The mixing temperature is not limited, but can be room temperature or a temperature between 10°C and 40°C. The content of each component can be exemplified in the coating solution described above.

[0353] <Method for producing a laminate having a coating film formed using a coating liquid>

[0354] The method for producing a laminate having a coating film formed using the coating liquid of the present invention may be the same as the method described in the aforementioned <Method for Producing Laminated Body>, using the coating liquid instead of or in addition to the inorganic fine particle dispersion.

[0355] <Laminated body>

[0356] 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 and can be the same as the aforementioned thickness, for example, greater than or equal to 20 nm and less than 100 nm. In another embodiment, the thickness of the coating film is greater than or equal to 20 nm and less than 75 nm. In another embodiment, the thickness of the coating film is greater than or equal to 25 nm and less than 75 nm. In another embodiment, the thickness of the coating film is greater than or equal to 25 nm and less than 60 nm. The thickness of the coating film can be adjusted by changing the weight ratio of the alkoxysilane in the coating solution and the coating amount of the coating solution.

[0357] The thickness of the coating film can be measured using an image of a coating film cross section obtained by observation using a scanning electron microscope (SEM).

[0358] Example

[0359] Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.

[0360] The main materials used are described below.

[0361] [Base material]

[0362] Quartz glass plate (manufactured by Kenis Co., Ltd.; synthetic quartz glass; average transmittance (wavelength range: 185 nm to 300 nm): 91.0%; width: 26 mm, length: 76 mm, thickness: 1.0 mm). The quartz glass plate having an average transmittance of 91.0% is referred to as substrate-1.

[0363] Quartz glass plate (manufactured by Tokyo Glass Instruments Co., Ltd.; fused silica; average transmittance (wavelength range: 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.

[0364] Soda lime glass plate (manufactured by AS ONE Co., Ltd.; soda lime glass; width 26 mm, length 76 mm, thickness 1.3 mm) The soda lime glass plate is referred to as substrate-3.

[0365] The average transmittance of the quartz glass plate was measured using the following method. Transmittance was measured using a UV-3600 UV / Vis / Near-Infrared spectrophotometer (Shimadzu Corporation). The transmittance values within the wavelength range of 185 nm to 300 nm were read from the resulting transmittance spectrum, and the average transmittance was calculated.

[0366] [Inorganic particles]

[0367] As the inorganic fine particles, the following dispersion was used.

[0368] Microparticles-1 (inorganic microparticles X): SNOWTEX (registered trademark) ST-OXS (manufactured by Nissan Chemical Industries, Ltd.; aqueous dispersion of colloidal silica; average particle size of 4 nm to 6 nm; solid content concentration of 10% by mass)

[0369] The numerical values of the weight ratio of the inorganic fine particles in Tables 1-1 and 1-2 are weight ratios calculated based on the solid content concentration of the inorganic fine particles when the total amount of the composition (total amount of the inorganic fine particle dispersion) is set to 100% by mass.

[0370] [Liquid dispersion medium A]

[0371] The following liquid dispersion medium A was used.

[0372] A-1: 3-methoxy-3-methylbutanol (boiling point 174°C)

[0373] A-2: 2-methoxyethyl acetate (boiling point 143°C)

[0374] [Liquid dispersion medium B]

[0375] B-1: Ethanol (boiling point 78°C)

[0376] [Other liquid dispersion media]

[0377] S-1: n-Butanol (boiling point 118°C)

[0378] [Alkoxysilane]

[0379] C-1: MKC Silicate (registered trademark) MS56S (manufactured by Mitsubishi Chemical Corporation; polymethoxysiloxane)

[0380] C-2: Dimethoxydimethylsilane

[0381] C-3: Tetraethyl orthosilicate

[0382] C-4: Triethoxymethylsilane

[0383] [Pore-forming agent]

[0384] P-1: Benzyltriethylammonium chloride

[0385] P-2: Dodecyltrimethylammonium chloride

[0386] [Acid catalyst]

[0387] AC-1: Nitric Acid

[0388] [Other ingredients, etc.]

[0389] Component-1: BYK (registered trademark)-349 (manufactured by BYK Chemicals Japan Ltd.; polyether-modified silicone)

[0390] The laminates including the substrate and the coating film in Examples and Comparative Examples were produced by the following method.

[0391] Examples 1 to 4 and Comparative Example 1

[0392] Alkoxysilane was added to a mixture of inorganic fine particles, liquid dispersion medium A, liquid dispersion medium B, water, and other components at the weight ratios listed in Tables 1-1 and 1-2, and stirred to prepare an inorganic fine particle dispersion. Next, a substrate was prepared by masking one side of the substrate listed in Table 1-1 with masking tape. Substrate-1, Substrate-2, or Substrate-3 was used as the substrate.

[0393] Using an ultra-low-speed dip coater MD-0408-01 (manufactured by SDI Co., Ltd.), the prepared inorganic fine particle dispersion was applied to the unmasked side of the masked substrate at a pull-up rate of 1.666 mm / s. After coating, the masking tape was removed from the substrate, and the substrate was allowed to air dry at room temperature.

[0394] The resulting substrate was heated in an oven at 100°C for 3 minutes in an air atmosphere to remove the solvent. The substrate was then subjected to the heat treatment step 1 or heat treatment step 2 of the present invention described below in a muffle furnace to form a coating film on the substrate, thereby obtaining a laminate comprising the substrate and the coating film. In the heat treatment step 1, the time spent in the temperature range of 200°C to 1000°C was 271 minutes, the time spent in the temperature range of 300°C to 900°C was 186 minutes, the time spent in the temperature range of 300°C to 800°C was 186 minutes, the time spent in the temperature range of 400°C to 800°C was 122 minutes, the time spent in the temperature range of 500°C to 800°C was 70 minutes, and the time spent in the temperature range of 500°C to 720°C was 70 minutes. In the heat treatment process-2, the time for maintaining in the temperature range of 200°C to 1000°C is 2 minutes, the time for maintaining in the temperature range of 300°C to 900°C, the time for maintaining in the temperature range of 300°C to 800°C, the time for maintaining in the temperature range of 400°C to 800°C, the time for maintaining in the temperature range of 500°C to 800°C, and the time for maintaining in the temperature range of 500°C to 720°C are all 2 minutes.

[0395] After the heat treatment step, the laminate including the substrate and the coating film was taken out from the muffle furnace and naturally cooled at room temperature.

[0396] Heat treatment process-1:

[0397] In air atmosphere, the temperature was raised from room temperature to 600°C at a rate of 4°C / min.

[0398] In air atmosphere / maintain at 600℃ for 30 minutes

[0399] In air atmosphere, stop heating and cool from 600°C to 200°C by natural cooling

[0400] Heat treatment process-2:

[0401] In air atmosphere / maintained within the range of 650°C to 710°C for 2 minutes

[0402] Example 5

[0403] The same procedures as in Example 1 were carried out except that a coating liquid was prepared using the components as follows so as to have the weight ratios described in Table 1-2, and this coating liquid was used instead of the inorganic fine particle dispersion to produce a laminate.

[0404] (Preparation of A01 dose-1)

[0405] When B-1 (49.4 g) and C-1 (25.0 g) were mixed, an aqueous solution (17.7 g) containing 0.1 mol / L AC-1 was added, mixed at room temperature for 1 hour, and then allowed to stand for 1 day to prepare A01 agent-1.

[0406] (Preparation of B01 agent-1)

[0407] C-2 (3.0 g) was added to the weighed A01 formulation-1 (27.8 g), mixed at room temperature for 1 hour, and then allowed to stand for 1 day to prepare B01 formulation-1.

[0408] (Preparation of coating solution)

[0409] Water (19.3 g), B-1 (109.0 g), A-1 (8.3 g), a solution containing P-1 / B-1 / water in a weight ratio of 50 / 40 / 10 (9.5 g), an aqueous solution containing 1 mol / L AC-1 (4.2 g), and B01 agent-1 (9.7 g) were mixed at room temperature for 1 hour to prepare a coating solution in a manner to achieve the weight ratio described in Table 1-1.

[0410] Example 6

[0411] Alkoxysilane was added to a mixture of inorganic fine particles, liquid dispersion medium A, liquid dispersion medium B, water, and other components at the weight ratios listed in Table 1-2 and stirred to prepare an inorganic fine particle dispersion. Next, a substrate was prepared, one side of which had been masked with masking tape. Substrate-1 was used as the substrate.

[0412] Using an ultra-low speed dip coater MD-0408-01 (manufactured by SDI Co., Ltd.), the prepared inorganic fine particle dispersion was applied to the unmasked side of the masked substrate at a pull-up rate of 1.666 mm / s. After coating, the coating was allowed to dry naturally at room temperature.

[0413] The resulting substrate was heated in an oven at 100°C for 3 minutes in an air atmosphere to remove the solvent. The prepared inorganic fine particle dispersion was then applied again to the unmasked side of the substrate using an ultra-low-speed dip coater, MD-0408-01 (manufactured by SDI Co., Ltd.), at a pull rate of 1.666 mm / s. After the second application, the masking tape was removed from the substrate, and the substrate was allowed to air dry at room temperature.

[0414] The obtained substrate was heated at 100°C for 3 minutes in an air atmosphere using an oven to remove the solvent, and then the heat treatment step-1 of the present invention was applied to the substrate in a muffle furnace in the same manner as in Example 1, thereby forming a coating film on the substrate, thereby obtaining a laminate including the substrate and the coating film.

[0415] After the heat treatment step, the laminate including the substrate and the coating film was taken out from the muffle furnace and allowed to cool naturally at room temperature.

[0416] Example 7

[0417] Alkoxysilane was added to a mixture of inorganic fine particles, liquid dispersion medium A, liquid dispersion medium B, water, and other components at the weight ratios listed in Table 1-2 and stirred to prepare an inorganic fine particle dispersion. Next, a substrate was prepared, one side of which had been masked with masking tape. Substrate-1 was used as the substrate.

[0418] Using an ultra-low-speed dip coater MD-0408-01 (manufactured by SDI Co., Ltd.), the prepared inorganic fine particle dispersion was applied to the unmasked side of the masked substrate at a pull-up rate of 1.666 mm / s. After coating, the masking tape was removed from the substrate, and the substrate was allowed to air dry at room temperature.

[0419] The resulting substrate was heated in an oven at 100°C for 3 minutes in an air atmosphere to remove the solvent. The substrate was then subjected to the heat treatment step 3 of the present invention described below in a muffle furnace to form a coating film on the substrate, thereby obtaining a laminate comprising the substrate and the coating film. In the heat treatment step 3, the time spent in the temperature range of 200°C to 1000°C was 335 minutes, the time spent in the temperature range of 300°C to 900°C was 247 minutes, the time spent in the temperature range of 300°C to 800°C was 247 minutes, the time spent in the temperature range of 400°C to 800°C was 180 minutes, the time spent in the temperature range of 500°C to 800°C was 124 minutes, and the time spent in the temperature range of 500°C to 720°C was 124 minutes.

[0420] After the heat treatment step, the laminate including the substrate and the coating film was taken out from the muffle furnace and allowed to cool naturally at room temperature.

[0421] Heat treatment process-3:

[0422] In air atmosphere, the temperature was raised from room temperature to 650°C at a rate of 4°C / min.

[0423] In air atmosphere / maintained at 650℃ for 60 minutes

[0424] In air atmosphere, stop heating and cool from 650°C to 200°C by natural cooling

[0425] Comparative Example 2

[0426] Alkoxysilane was added to a mixture of other liquid dispersion media, water, and other components at the weight ratios listed in Table 1-2 and allowed to react for two days. Next, a substrate was prepared, one side of which was masked with masking tape. Substrate-3 was used as the substrate.

[0427] Using an ultra-low-speed dip coater MD-0408-01 (manufactured by SDI Co., Ltd.), the prepared coating solution was applied to the unmasked side of the masked substrate at a pull-up rate of 1.666 mm / s. After coating, the masking tape was removed from the substrate, and the coating was allowed to dry naturally at room temperature.

[0428] The resulting substrate was heated in an oven at 80°C for 2 minutes in an air atmosphere, and then further heated in an oven at 150°C for 2 minutes in an air atmosphere. After removing the solvent, the substrate was subjected to the following heat treatment step-4, which is not based on the present invention, in a muffle furnace to attempt to form a coating film on the substrate. However, the substrate repelled the coating liquid, and thus a uniform coating film was not formed. In heat treatment step-4, the time within the temperature range of 200°C to 1000°C, the time within the temperature range of 300°C to 900°C, and the time within the temperature range of 300°C to 800°C were all 2 minutes. The time within the temperature range of 400°C to 800°C, the time within the temperature range of 500°C to 800°C, and the time within the temperature range of 500°C to 720°C were all 0 minutes.

[0429] Heat treatment process-4:

[0430] Muffle furnace / air atmosphere / maintain at 300℃ for 2 minutes

[0431] Evaluations of Examples and Comparative Examples were performed by the following methods.

[0432] [Thickness of coating film]

[0433] Evaluation was performed using an image of a coating film cross section observed using a scanning electron microscope (SEM) as described below.

[0434] Scanning electron microscopy (SEM) observation

[0435] Scanning electron microscope (SEM) observation was performed according to the following procedure.

[0436] The laminate consisting of the substrate and the coating film was cut to create a sample with a cross section exposed. The resulting sample was secured to a sample stand with carbon tape, with the cross section facing upward. Carbon paste was then applied to the sides, and approximately 0.5 nm of Pt-Pd was vapor-deposited for conductive treatment using an E1030 ion sputtering system manufactured by Hitachi High-Technologies Corporation.

[0437] The SEM used was a Hitachi High-Technologies Corporation (HITACHI SU8020) with an accelerating voltage of 2 kV and an SE (U)-based secondary electron imaging mode. The measurement magnification was 100,000x, and 10 fields of view were measured.

[0438] The thickness of the coating film was evaluated using an image of the obtained coating film cross section, and the average value of the thickness in 10 fields of view was used.

[0439] [Kurtosis of Brightness Distribution in Cross-Sectional Images of Scanning Electron Microscopes]

[0440] The kurtosis (sometimes referred to as the kurtosis of the brightness distribution) in a scanning electron microscope cross-sectional image was evaluated using the following method. From the grayscale image (10 fields of view) of the laminate cross-section observed using the scanning electron microscope (SEM), only the coating film portion was cropped to an image size of 25 pixels x 1280 pixels. The kurtosis K of the brightness was calculated for this cropped portion using the Fisher-defined formula (X100).

[0441]

[0442] In formula (X100), h and w are the vertical and horizontal dimensions of the cropped image, i and j are the vertical and horizontal coordinates of the image, respectively. ij is the brightness at the coordinate (i, j), μ and σ are the average value and standard deviation of the brightness, respectively, and are calculated using the following formulas (Y100) and (Z100).

[0443]

[0444]

[0445] The kurtosis K of the brightness in each field of view was calculated, and the average value in 10 fields of view was taken as the kurtosis of the brightness distribution in the scanning electron microscope image of the cross section.

[0446] [Spectral transmittance]

[0447] The transmittance of the laminate comprising a substrate and a coating film was measured using an ultraviolet / visible / near-infrared spectrophotometer UV-3600 (manufactured by Shimadzu Corporation). The transmittance values within the range of a wavelength of 185 nm or more and 300 nm or less were then read from the resulting transmittance spectrum, and the average transmittance (wavelength 185 nm to 300 nm) was calculated. Additionally, the transmittance values at wavelengths of 185 nm, 222 nm, and 254 nm were also read. Additionally, the transmittance values within the range of a wavelength of 185 nm or more and 280 nm or less were read, and the average transmittance (wavelength 185 nm to 280 nm) was calculated.

[0448] The average transmittance of the obtained laminate relative to the uncoated substrate (substrate without a coating film) and the increase in transmittance at wavelengths of 185 nm, 222 nm, and 254 nm were observed. The average transmittance and the increase in transmittance at wavelengths of 185 nm, 222 nm, and 254 nm are defined by the following formulae, respectively.

[0449] [Increase in average transmittance (percentage points) (wavelength range of 185 nm to 300 nm)]

[0450] = [Average transmittance (%) of the laminate (average value of transmittance at each wavelength within the wavelength range of 185 nm to 300 nm)] - [Average transmittance (%) of the uncoated substrate (average value of transmittance at each wavelength within the wavelength range of 185 nm to 300 nm)]

[0451] [Increase in transmittance at a wavelength of 185 nm (percentage points)]

[0452] = [Transmittance of the laminate at a wavelength of 185 nm (%)] - [Transmittance of the uncoated substrate at a wavelength of 185 nm (%)]

[0453] [Increase in transmittance at a wavelength of 222 nm (percentage points)]

[0454] = [Transmittance of the laminate at a wavelength of 222 nm (%)] - [Transmittance of the uncoated substrate at a wavelength of 222 nm (%)]

[0455] [Increase in transmittance at a wavelength of 254 nm (percentage points)]

[0456] = [Transmittance of the laminate at a wavelength of 254 nm (%)] - [Transmittance of the uncoated substrate at a wavelength of 254 nm (%)]

[0457] [Increase in average transmittance (percentage points) (wavelength range of 185 nm to 280 nm)]

[0458] = [Average transmittance (%) of the laminate (average transmittance at each wavelength within the range of 185 nm to 280 nm)] - [Average transmittance (%) of the uncoated substrate (average transmittance at each wavelength within the range of 185 nm to 280 nm)]

[0459] [Number of carbon atoms / Sum of the number of silicon atoms]

[0460] The ratio of the number of carbon atoms in the surface of the coating film to the total number of atoms of sodium, potassium, magnesium, calcium, aluminum, and silicon (number of carbon atoms / sum of the number of atoms of silicon, etc.) is measured as follows.

[0461] A photoelectron spectrometer (trade name "AXIS-ULTRA", manufactured by KRATOS) was used with an X-ray source of AlKα (monochromatic) at 15 kV and 10 mA, wide scan, energy level of 160 eV, step size of 1 eV, accumulation times of 3, and vacuum degree of approximately 5 × 10 -8 Torr, temperature: The measurement was carried out under room temperature conditions.

[0462] Among the peaks attributed to sodium, potassium, magnesium, calcium, aluminum, silicon, oxygen, and carbon, those confirmed by wide scan were measured by narrow scan. Peaks confirmed by wide scan were C1s, O1s, Si2p, and Na1s. Na1s was confirmed only in Comparative Example 1.

[0463] In the narrow scan, a photoelectron spectrometer (trade name "AXIS-ULTRA", manufactured by KRATOS) was used, with an X-ray source of AlKα (monochromatic) 15 kV 10 mA, narrow scan, energy level of 20 eV, step size of 0.1 eV, accumulation times of 15 for C1s, 3 for O1s, 10 for Si2p, and 15 for Na1s, and a vacuum degree of approximately 5 × 10 -8 Torr, temperature: The measurement was carried out under room temperature conditions, and the intensity of the emitted photoelectrons on the film surface was measured, thereby obtaining the ratio of the number of each atom.

[0464] When charging occurs during measurement, an electron gun for charge correction is used.

[0465] Furthermore, when performing charge correction of the chemical shift of the measured energy spectrum, a standard sample can be used as appropriate. In this case, the energy spectrum due to C of the CC structure in the C1s spectrum was corrected to an energy reference of 284.8 eV.

[0466] [Arithmetic mean roughness of coating film]

[0467] The arithmetic mean roughness Sa of the coating film was evaluated using a scanning probe microscope (SPM) as follows.

[0468] [SPM measurement conditions]

[0469] Apparatus: Scanning probe microscope (SPM-9600) (manufactured by Shimadzu Corporation)

[0470] Cantilever: NCHR-20 manufactured by NanoWorld

[0471] T (thickness): 4 μm

[0472] L (length): 125 μm

[0473] W (width): 30 μm

[0474] f0 (resonance frequency): 320kHz

[0475] k (spring constant): 42N / m

[0476] Test conditions: dynamic mode

[0477] Setting parameters

[0478] Observation condition setting

[0479]

[0480] (Tilt Correction)

[0481] Average value in the X direction

[0482] Average value in the Y direction

[0483] ·Central value in the X direction

[0484] Center value in the Y direction

[0485] Scanning probe microscopy (SPM) measurements were performed according to the following procedures.

[0486] A sample of a laminate composed of a glass substrate and a coating film was fixed on a sample stage of an SPM with the coating film facing upward. The fixation was performed using carbon tape.

[0487] SPM was performed using a scanning probe microscope (SPM-9600) manufactured by Shimadzu Corporation and a cantilever using NCHR-20 manufactured by NanoWorld. Measurement was performed under the conditions of a scanning range of 1 μm×1 μm and a scanning speed of 0.501 Hz.

[0488] The obtained image was set to 256 pixels×256 pixels, and the feedback was measured with the I gain set to 0.001 and the P gain set to 500.

[0489] The obtained height image is tilt-corrected based on the average value in the X direction, the average value in the Y direction, the central value in the X direction, and the central value in the Y direction, and the arithmetic mean height Sa of the contour surface is calculated based on the definitions of ISO 25178-2:2012 and JIS B 0681-2:2018.

[0490] [Abrasion resistance test 1]

[0491] In a state where a probe having a nonwoven surface of a sponge cut into 1 cm × 1 cm (manufactured by 3M, Scotch-Brite Sponge AceS yellow) was in contact with the laminate at the front end, a medium-sized vibrator R-10 (manufactured by TAITEC Co., Ltd.) was used to reciprocate the laminate in one direction at a speed of (41 ± 1) round trips / minute for 20 seconds under a load of 1 kg to evaluate the wear resistance of the coating. At this point, in the case where the coating could not be confirmed to fall off, it was judged that the wear resistance of the coating was sufficiently high, and the evaluation in this case was recorded as "0". In the case where the coating could be confirmed to fall off, it can be said that the wear resistance of the coating was low, and the evaluation in this case was recorded as "×".

[0492] [Abrasion resistance test 2]

[0493] In a state where a non-woven fabric surface having a sponge cut into 1 cm × 1 cm (manufactured by 3M, Scotch-Brite SpongeAce S yellow) cut into 1 cm × 1 cm is installed at the front end and a probe having a Kimwipe pasted thereon is in contact with the laminate, a medium-sized vibrator R-10 (manufactured by TAITEC Co., Ltd.) is used to move the laminate back and forth for a distance of 35 mm in one direction at a speed of (41 ± 1) round trips / minute for 60 seconds under a load of 1 kg, and the wear resistance of the coating is evaluated. When damage cannot be confirmed on the surface of the coating, it is judged that the wear resistance of the coating is extremely high, and the evaluation in this case is recorded as “◎”. When damage is confirmed only in a part of the contact portion of the probe, it is judged that the wear resistance of the coating is higher, and the evaluation in this case is recorded as “○”. When damage is confirmed as a whole in the contact portion of the probe or when the coating is confirmed to fall off, it is judged that the wear resistance of the coating is extremely low, and the evaluation in this case is recorded as “×”.

[0494] [Alkali resistance test]

[0495] 80g of 1M NaOH aqueous solution was taken and the laminate was immersed in the aqueous solution. Then, the sodium hydroxide aqueous solution on the surface of the laminate was rinsed with distilled water and dried in an oven at 100°C for more than 8 hours to remove moisture. Finally, the transmittance of the impregnated surface of the laminate was measured in the range of 185nm to 700nm using an ultraviolet / visible / near-infrared spectrophotometer UV-3600 (manufactured by Shimadzu Corporation) and the spectrum obtained at this time was compared with the transmittance spectrum obtained before immersion. The transmittance change of each wavelength in the range of 185nm to 700nm was calculated. When the average value of the absolute value of the transmittance change (hereinafter referred to as the transmittance change average value) was more than 0.5 percentage points, it was judged that the coating was fully destroyed by the alkali and no longer obtained an anti-reflection effect. The evaluation of the case where the transmittance change average value was less than 0.5 percentage points was recorded as "0", and the evaluation of the case where the transmittance change average value was more than 0.5 percentage points was recorded as "×".

[0496] [Table 1-1]

[0497]

[0498] [Table 1-2]

[0499]

[0500] [Table 1-3]

[0501]

[0502] As can be seen from the results shown in Table 1-1, in Example 1, the average transmittance of the laminate in the wavelength range of greater than 185 nm and less than 300 nm was 2.1 percentage points higher than the average transmittance of the substrate without the coating in the wavelength range of greater than 185 nm and less than 300 nm, and a laminate with high ultraviolet transmittance (energy efficiency) was obtained, and a coating with high wear resistance was obtained.

[0503] Furthermore, as shown in the results in Table 1-2, in Examples 2 to 7, the average transmittance of the laminates in the wavelength range of 185 nm to 300 nm was higher by 2.4 percentage points or more compared to the average transmittance of the substrate without a coating film in the wavelength range of 185 nm to 300 nm. Furthermore, in Examples 2 to 7, laminates having high ultraviolet transmittance (energy efficiency) were obtained, with average transmittances in the wavelength range of 185 nm to 300 nm and average transmittances in the wavelength range of 185 nm to 280 nm being 90.0% or more, and transmittances at a wavelength of 185 nm being 91.0% or more.

[0504] Furthermore, the results shown in Tables 1-3 show that the laminates of Examples 1 to 7 have higher abrasion resistance than the laminate of Comparative Example 1. In contrast, in Comparative Example 1, where the transmittance of the laminate does not meet 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.

[0505] [Table 2]

[0506]

[0507] As can be seen from Tables 1-2, the transmittance of the laminated bodies meets the requirements of Examples 1 to 3, 6, and 7 of the present invention, which are laminated bodies with high ultraviolet transmittance (energy efficiency) of 90.0% or more in the wavelength range of 185 nm or more and 91.0% or more in the wavelength range of 185 nm or more and 91.0% or more at a wavelength of 185 nm. As can be seen from Table 2, the average value of the change in transmittance after the alkali resistance test of these laminated bodies is 0.5 percentage points or less, and the coating film is not easily damaged by alkali and has high alkali resistance. In contrast, it can be seen that in Comparative Example 1, in which the transmittance of the laminated body does not meet the requirements of the present invention, the average value of the change in transmittance after the alkali resistance test is greater than 0.5 percentage points, and the coating film is damaged by alkali and has low alkali resistance.

[0508] Therefore, when the laminate is used in an environment where alkaline substances may adhere, it is expected that the coating film of the laminate of the present invention will not deteriorate and the anti-reflection effect based on the coating film can be continuously obtained. In contrast, the coating film of the laminate that does not meet the requirements of the present invention will be destroyed and the anti-reflection effect based on the coating film will no longer be obtained.

[0509] Industrial Applicability

[0510] According to the present invention, a method for producing a laminate having both high UV transmittance and high environmental resistance (moisture resistance and abrasion resistance) / alkali resistance, a laminate, and a coating solution for use in producing the laminate can be provided. These laminates are suitable for use in various applications, including window materials for optical sensors, mirrors, focusing lenses, illumination windows for light sources (lamps / lasers, etc.), protective glass for solar cells, displays, and various residential equipment and machine parts, various industrial parts, various building material parts, various parts for household appliances, and various automotive interior and exterior parts. These laminates have high practicality in various fields, including the construction industry, the transportation machinery industry, the electrical and electronics industry, and household goods.

[0511] These laminates are particularly suitable for use in components that process ultraviolet light, such as window materials for ultraviolet sensors, ultraviolet focusing lenses, irradiation windows for mercury lamps, and irradiation windows for excimer lasers. They are highly practical in ultraviolet exposure devices for lithography, ultraviolet irradiation devices for curing resins, UV lamps for sterilization, air purifiers, and UV lamps for water treatment.

Claims

1. A method for producing a laminate, wherein: The laminate comprises a substrate and a coating film applied to at least one main surface of the substrate, and the method for producing the laminate comprises the following steps: The process of coating a substrate with an inorganic fine particle dispersion, wherein the inorganic fine particle dispersion comprises inorganic fine 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 greater than or equal to 0.5% by mass and less than 15% by mass when the total amount of the inorganic fine particle dispersion is set to 100% by mass; and A step of performing heat treatment at a temperature of 200°C to 1000°C for more than 10 minutes.

2. The method for producing a laminate according to claim 1, wherein: The substrate is 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. The method for producing a laminate according to claim 1 or 2, 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 claim 1 or 2, wherein: The inorganic fine particle dispersion contains water.

7. The method for manufacturing a laminate according to claim 6, wherein: The inorganic fine particle dispersion contains alkoxysilane.

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

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

005.

10. The method for producing a laminate according to claim 1 or 2, wherein: The primary particle size of the inorganic fine particles is greater than or equal to 1 nm and less than 50 nm.

11. A laminated body, wherein: The laminate can be obtained by a method for producing a laminate comprising a substrate and a coating film applied to at least one main surface of the substrate, the method comprising the following steps: The process of coating a substrate with an inorganic fine particle dispersion, wherein the inorganic fine particle dispersion comprises inorganic fine 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 greater than or equal to 0.5% by mass and less than 15% by mass when the total amount of the inorganic fine particle dispersion is set to 100% by mass; and A step of performing heat treatment at a temperature of 200°C to 1000°C for more than 10 minutes.

12. A laminate comprising a substrate and a coating film applied to at least one main surface of the substrate, characterized in that: The coating film has a thickness of greater than or equal to 20 nm and less than 75 nm, The average transmittance of the laminate in the wavelength range of 185 nm to 300 nm is higher by 0.5 percentage points or more than the average transmittance of a substrate having no coating film in the wavelength range of 185 nm to 300 nm.

13. A laminate comprising a substrate and a coating film applied to at least one main surface of the substrate, wherein: The coating film has a porous structure and a thickness greater than or equal to 20 nm and less than 100 nm. The transmittance of the laminated body at any wavelength of 150 nm or more and less than 300 nm is 80.0% or more.

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

15. The laminate according to claim 13, wherein The ratio of the number of carbon atoms in the surface of the coating film to the total number of atoms of sodium, potassium, magnesium, calcium, aluminum, and silicon 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 silicon dioxide.

18. The laminate according to claim 16, wherein The primary particle size of the inorganic fine particles is greater than or equal to 1 nm and less than 50 nm.

19. The laminate according to claim 13, wherein The laminate can be obtained by the following manufacturing method, which includes the following steps: A step of applying a coating solution comprising alkoxysilane, water, an acid catalyst and a pore-forming agent onto a substrate; and A step of performing heat treatment at a temperature of 200°C to 1000°C for more than 10 minutes.

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

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

22. The laminate according to claim 13 or 14, wherein The substrate is quartz glass or sapphire glass.

23. The laminate according to claim 13 or 14, 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, wherein The laminate can be obtained by the following manufacturing method, which includes the following steps: The process of applying a coating agent to a substrate; and A step of performing heat treatment at a temperature of 200°C to 1000°C for more than 10 minutes.

25. A laminated body, wherein: The laminate can be obtained by a method for producing a laminate comprising a substrate and a coating film applied to at least one main surface of the substrate, the method comprising the following steps: The process of applying a coating agent to a substrate; and A step of performing heat treatment at a temperature of 200°C to 1000°C for more than 10 minutes.

26. A coating liquid, wherein The coating liquid comprises an alkoxysilane, water, an acid catalyst, a pore-forming agent, and a liquid dispersion medium A having a boiling point greater than 121° C. and less than 190° C., and when the total amount of the coating liquid is set to 100% by mass, the weight ratio of the liquid dispersion medium A is greater than or equal to 0.5% by mass and less than 15% by mass.

27. The coating solution according to claim 26, wherein The coating liquid contains the following alkoxysilane C01 and alkoxysilane C02 as alkoxysilanes, and the ratio of the weight of SiO2 contained in the alkoxysilane C02 to the total weight of SiO2 contained in the alkoxysilane ([the weight of SiO2 contained in the alkoxysilane C02] / [the total weight of SiO2 contained in the alkoxysilane]) is 0.00 or more and 0.50 or less, Alkoxysilane C01: at least one alkoxysilane selected from the group consisting of tetraalkoxysilane and a condensate of an alkoxysilane represented by the following general formula (01), General formula (01) In formula (01), 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 the group consisting of 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 to 2.

28. The coating solution 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 solution according to claim 26, wherein The pore-forming agent is an organic ammonium salt.

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

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

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