JP6625609B2 - Transparent article, method for producing the same, and film forming solution used therefor - Google Patents

Description

  The present invention relates to a transparent article including a transparent substrate typified by a glass plate, and an organic-inorganic composite film containing an ultraviolet absorber formed on the transparent substrate.

  In the sol-gel method, a solution of a metal organic or inorganic compound is used as a starting material, and the solution is converted into a sol in which fine particles of a metal oxide or hydroxide are dissolved by a hydrolysis reaction and a condensation polymerization reaction of the compound in the solution. In this method, the gel is solidified, and the gel is heated as necessary to obtain an oxide solid. There is known a technique of forming a film in which an inorganic component and an organic component are combined on a transparent substrate by a sol-gel method. The sol-gel method is characterized by forming a film at a low temperature, so that an organic-inorganic composite film containing an organic substance can be formed.

  As a vehicle window glass, a glass plate on which an organic-inorganic composite film containing an ultraviolet absorber as an organic substance is formed is used. Vehicle window glass is required to shield ultraviolet light while transmitting visible light. Further, the coating film formed on the window glass for vehicles is required to be excellent in wear resistance and not deteriorate in characteristics even after long-term use. An opaque ceramic shielding layer may be formed on the periphery of the vehicle window glass. The ceramic shielding layer is formed by applying a ceramic paste and firing at a high temperature. In order to avoid decomposition of organic substances when firing at a high temperature, the organic-inorganic composite film is formed by a sol-gel method on the surface of a glass plate on which a ceramic shielding layer has been formed in advance.

  Patent Document 1 discloses that a component (a) derived from an epoxy group-containing organooxysilane compound is obtained by reacting a hydroxyl group-containing benzophenone compound with an epoxy group-containing organooxysilane compound in the presence of a quaternary ammonium salt. A solution for forming a film having an ultraviolet shielding ability, which contains an organooxysilane compound (b) and an organooxysilane compound (c) other than (a) and (b) is disclosed. In Patent Document 1, in order to obtain component (b), 1.0 to 3.0 mol of an epoxy group-containing organooxysilane compound as a silane coupling agent is reacted with 1 mol of a benzophenone-based compound as an ultraviolet absorber. In other words, it is recommended that the entire amount of the ultraviolet absorber be silylated beforehand (paragraph 0031). According to Patent Literature 1, an organic-inorganic composite film formed from a solution containing an ultraviolet absorber that has been silylated by reacting with a silane coupling agent has excellent abrasion resistance, and a decrease in ultraviolet absorption ability due to long-term use is suppressed. Will be something.

International Publication No. WO 2010/131744

  However, in order to carry out the manufacturing method disclosed in Patent Document 1, it is necessary to react the ultraviolet absorber and the silane coupling agent to prepare the component (b) in advance, and thus the organic-inorganic composite film is required. (Film forming solution) must be prepared by mixing and reacting the components of the film in at least two stages.

  In view of the above circumstances, the present invention provides a manufacturing method that is excellent in abrasion resistance and in which deterioration in properties due to long-term use is suppressed, is suitable for manufacturing a transparent article including an organic-inorganic composite film, and does not require complicated steps. The purpose is to provide. Another object of the present invention is to provide a transparent article including an organic-inorganic composite film, which is excellent in abrasion resistance and in which deterioration in properties due to long-term use is suppressed. Still another object of the present invention is to provide a film forming solution suitable for forming the organic-inorganic composite film.

  The decrease in the transparency of the organic-inorganic composite film due to long-term use may be remarkable due to the catalyst remaining in the organic-inorganic composite film, more specifically, the hydrolysis catalyst contained in the film-forming solution remaining in the film. Was found. By suppressing the hydrolysis catalyst from remaining in the film and by including appropriate components in the film-forming solution, it is possible to prevent the ultraviolet absorber from reacting with the silane coupling agent in advance, and to use it for long-term use. Can be reduced.

The present invention
A method for producing a transparent article, comprising a transparent substrate and an organic-inorganic composite film formed on the surface of the transparent substrate,
At least a silicon compound A represented by the following formula (1), a silicon compound B represented by the following formula (2), an ultraviolet absorber which is an organic substance, an organic polymer, and an acid dissociation constant of less than 1 and a boiling point A step of preparing a film-forming solution by supplying an acid having a temperature of 130 ° C. or less and water to a container and mixing in the container.
Applying the film-forming solution to the surface of the transparent substrate,
Drying the transparent substrate coated with the film-forming solution to form an organic-inorganic composite film on the transparent substrate,
As the ultraviolet absorber, supply only the ultraviolet absorber that has not reacted with any of the silicon compound A and the silicon compound B to the container,
A method for producing a transparent article, wherein the transparent substrate coated with the film-forming solution is heated to 130 ° C. or higher and dried to form the organic-inorganic composite film.
SiX ¹ ₄ ⁽¹⁾
[X ¹ is a hydrolyzable functional group or a halogen atom. ]
R ¹ _m R ² _n SiX ² _4-mn (2)
[R ¹ is an organic group having a reactive functional group, R ² is an organic group having no reactive functional group, X ² is a hydrolyzable functional group or a halogen atom, and m is 0 or more and 2 or less. N is an integer of 0 or more and 2 or less, and m + n is 1 or more and 2 or less. ]

Also, the present invention
A transparent substrate, including an organic-inorganic composite film formed on the surface of the transparent substrate,
The organic-inorganic composite film is at least a silicon compound A represented by the above formula (1), a silicon compound B represented by the above formula (2), and an organic substance. Including a reaction product obtained by reacting a constituent component containing an ultraviolet absorber and an organic polymer that have not reacted with any,
A transparent article having a difference in haze ratio of 1.0% or less before and after a test of leaving for 500 hours in an environment at a temperature of 50 ° C. and a relative humidity of 95%.

Also, the present invention
A transparent substrate, including an organic-inorganic composite film formed on the surface of the transparent substrate,
The organic-inorganic composite film is at least a silicon compound A represented by the above formula (1), a silicon compound B represented by the above formula (2), and an organic substance. Including a reaction product obtained by reacting a constituent component containing an ultraviolet absorber and an organic polymer that have not reacted with any,
A transparent article having a haze ratio of 1.0% or less after being left for 500 hours in an environment at a temperature of 50 ° C. and a relative humidity of 95%.

Also, the present invention
At least a silicon compound A represented by the above formula (1), a silicon compound B represented by the above formula (2), an ultraviolet absorber which is an organic substance, an organic polymer, and an acid dissociation constant of less than 1 and a boiling point A film forming solution for forming an organic-inorganic composite film, which is prepared by supplying an acid having a temperature of 130 ° C. or lower and water to a container and mixing the mixture in the container. However, as the ultraviolet absorber, only an ultraviolet absorber that has not reacted with any of the silicon compound A and the silicon compound B is supplied to the container.

  According to the production method of the present invention, there is no need to prepare a film forming solution for an organic-inorganic composite film by multi-stage mixing and reaction. Further, in this manufacturing method, a silicon compound B and an organic polymer are added to the film forming solution together with the silicon compound A, and an acid that can be easily removed as a hydrolysis catalyst is used to form a film at a temperature suitable for removing the acid. The solution has been dried. This production method is suitable for producing a transparent article containing an organic-inorganic composite film, which has excellent abrasion resistance and suppresses a decrease in properties due to long-term use, in particular, a decrease in transparency. Further, according to the present invention, it is possible to provide a transparent article which can be provided by this manufacturing method and a film forming solution suitable for carrying out this manufacturing method.

FIG. 1 is a plan view showing a vehicle window glass on which a ceramic shielding layer is formed as an embodiment of the transparent article according to the present invention. It is sectional drawing of the window glass for vehicles shown in FIG.

  Hereinafter, embodiments of the present invention will be described, but the following description is not intended to limit the present invention to a specific embodiment.

  First, each component constituting a film forming solution for forming an organic-inorganic composite film and a method for preparing the film forming solution will be described below.

[Silicon compound A]
The silicon compound A is a compound represented by the formula (1).
SiX ¹ ₄ ⁽¹⁾
In the formula (1), X ¹ is a hydrolyzable functional group or a halogen atom. The hydrolyzable functional group is a functional group that is hydrolyzed by a hydrolysis catalyst, and is, for example, at least one selected from an alkoxyl group, an acetoxy group, and an alkenyloxy group. All of the exemplified hydrolyzable functional groups are converted to hydroxyl groups by hydrolysis. Preferred hydrolyzable functional groups are alkoxyl groups. Examples of the alkoxyl group include an alkoxyl group having 1 to 4 carbon atoms (a methoxy group, an ethoxy group, a propoxy group and a butoxy group). Halogen is, for example, chlorine and bromine, preferably chlorine.

  Preferred examples of the silicon compound A include tetraalkoxysilanes, specifically, tetramethoxysilane, tetraethoxysilane, and tetraisopropoxysilane. Instead of or together with the silicon compound A, a compound obtained by at least partially hydrolyzing the silicon compound A in advance, or a compound obtained by at least partially hydrolyzing the silicon compound and further polycondensing it can be used. Hydrolysates of the silicon compound A are available as commercial products.

[Silicon compound B]
Silicon compound B is a compound represented by the formula (2).
R ¹ _m R ² _n SiX ² _4-mn (2)
In the formula (2), R ¹ is an organic group having a reactive functional group, R ² is an organic group having no reactive functional group, X ² is a hydrolyzable functional group or a halogen atom, and m Is an integer of 0 or more and 2 or less, n is an integer of 0 or more and 2 or less, and m + n is 1 or more and 2 or less.

  The reactive functional group is, for example, at least one selected from a vinyl group, an acryloyl group, a methacryloyl group, an isocyanurate group, an ureido group, a mercapto group, a sulfide group, an isocyanate group, an epoxy group, and an amino group. The epoxy group may be part of a glycidyl group, especially an oxyglycidyl group. The amino group may be any of a primary amino group, a secondary amino group, and a tertiary amino group. Preferred reactive functional groups are epoxy groups and amino groups, especially epoxy groups. The organic group having a reactive functional group may be, for example, the organic group itself may be a reactive functional group (for example, a vinyl group), or may be, for example, an aliphatic hydrocarbon in which at least one hydrogen atom is substituted by the reactive functional group. Or an aromatic hydrocarbon group. Examples of the aliphatic hydrocarbon group include a linear alkyl group having 1 to 10 carbon atoms and a branched alkyl group having 3 to 10 carbon atoms. Examples of the aromatic hydrocarbon group include a phenyl group.

  The organic group having no reactive functional group is, for example, an aliphatic or aromatic hydrocarbon group. Examples of the aliphatic hydrocarbon group include a linear alkyl group having 1 to 10 carbon atoms and a branched alkyl group having 3 to 10 carbon atoms. Examples of the aromatic hydrocarbon group include a phenyl group.

X ² is a hydrolyzable functional group or a halogen atom, and specific examples of X ² are the same as the specific examples of X ¹ .

  m may be 1 or 2, preferable n may be 0 or 1, and m + n may be 1 or 2.

The silicon compound B may include a silicon compound B1 in which m in the formula (2) is 1 or 2 and n is 0 or 1. Examples of the silicon compound B1 include vinyltriethoxysilane, p-styryltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-methacryloxypropyltrimethoxysilane, Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, tris- (trimethoxysilylpropyl) isocyanurate, 3-ureidopropyltrimethoxysilane, 3-mercaptopropyltri Methoxysilane can be exemplified. The silicon compound B1 is a so-called silane coupling agent. Silicon Compound B1 as a reactive functional group contained in R ^1, preferably has an epoxy group.

The silicon compound B may include a silicon compound B2 in which m in the formula (2) is 0 (not including the organic group R ¹ having a reactive functional group) and n is 1 or 2. Preferred silicon compound B2 is a silicon alkoxide having a phenyl group, specifically, phenyltriethoxysilane.

[UV absorber]
As the ultraviolet absorber, for example, a benzotriazole compound [2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) Benzotriazole and the like], benzophenone compounds [2,2 ', 4,4'-tetrahydroxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 5, 5′-methylenebis (2-hydroxy-4-methoxybenzophenone)], a hydroxyphenyltriazine compound [2- (2-hydroxy-4-octoxyphenyl) -4,6-bis (2,4-di-t-) (Butylphenyl) -s-triazine, 2- (2-hydroxy-4-methoxyphenyl) -4 6-diphenyl-s-triazine, 2- (2-hydroxy-4-propoxy-5-methylphenyl) -4,6-bis (2,4-di-t-butylphenyl) -s-triazine, etc.] and cyano Acrylate compounds [ethyl-α-cyano-β, β-diphenyl acrylate, methyl-2-cyano-3-methyl-3- (p-methoxyphenyl) acrylate, etc.] can be used. In addition, ultraviolet absorbers, polymethine compounds, imidazoline compounds, coumarin compounds, naphthalimide compounds, perylene compounds, azo compounds, isoindolinone compounds, quinophthalone compounds and quinoline compounds, thiophene compounds, stilbenzene compounds, naphthalene compounds and benzimidazole compounds And at least one organic dye selected from the group consisting of: Preferred among the ultraviolet absorbers are at least one selected from benzotriazole compounds, benzophenone compounds, hydroxyphenyltriazine compounds, and cyanoacrylate compounds, and more preferred are benzophenone compounds. Only one UV absorber may be used, or two or more UV absorbers may be used in combination.

  The ultraviolet absorber preferably has at least one kind selected from an amino group and a hydroxyl group, particularly a hydroxyl group, in the molecule, and particularly preferably has two or more hydroxyl groups in one molecule. Here, the amino group may be any of a primary amino group, a secondary amino group, and a tertiary amino group. The ultraviolet absorber may have a benzene skeleton in which two or more hydroxyl groups are bonded.

  The ultraviolet absorber does not need to be reacted with a silicon compound such as the silicon compound B1 to be silylated in advance, and a commercially available product may be used as it is. For this reason, in the present embodiment, an ultraviolet absorber containing no silicon atom in the molecule can be used as it is for preparing the film forming solution. The silylation of the ultraviolet absorber is effective in suppressing the bleed out of the ultraviolet absorber, but requires a preliminary step only for that purpose. In the present embodiment, the ultraviolet absorber is usually a component capable of reacting with or interacting with the ultraviolet absorber in the film-forming solution, specifically, a silicon compound A, a silicon compound B, an organic polymer, or the like. React with or interact with molecules. This reaction or intermolecular interaction occurs competitively. Here, examples of the reaction include a reaction in which a covalent bond or an ionic bond is formed. Examples of the intermolecular interaction include a hydrogen bond and a π-π interaction. Therefore, even if the film-forming solution contains the silicon compound B1 (silane coupling agent), the UV absorber does not react with the silicon compound B1 nor interact with molecules, and usually at least the ultraviolet absorber does not. Some of them react with at least one selected from the silicon compound A, the silicon compound B (excluding the silicon compound B1), and the organic polymer or have an intermolecular interaction. This reaction or intermolecular interaction contributes to the suppression of bleed-out by fixing the ultraviolet absorber in the film, similarly to the reaction with the silicon compound B1.

[Organic polymer]
Examples of the organic polymer include polyethylene glycol, polyether resin, polyurethane resin, starch resin, cellulose resin, acrylic resin, polyester polyol, hydroxyalkyl cellulose, polyvinyl alcohol, polyvinylpyrrolidone, polycaprolactone polyol, and polyvinyl acetal resin. , Polyvinyl acetate, polyalkylene glycol resins and the like are known. A preferred organic polymer in the present embodiment is an organic polymer having an epoxy group in the molecule. However, this organic polymer can exist as an organic polymer formed by ring-opening of at least a part, and in some cases, all of the epoxy groups in the film-forming solution or the organic-inorganic composite film. As another preferable organic polymer, an organic polymer containing a polar group capable of hydrogen bonding with a silanol group or a phenolic hydroxyl group (a carbonyl group, a hydroxyl group, a phenolic hydroxyl group, etc.) can be exemplified. Among these, a particularly preferred organic polymer is a polyalkylene glycol-based resin. Examples of the polyalkylene glycol-based resin include polyethers that are glycols and derivatives of polyethers. Examples of these polymers include polypropylene glycol and polyethylene glycol dimethacrylate. The use of a polyalkylene glycol-based resin can effectively suppress the generation of foreign matter in the organic-inorganic composite film, and has a high abrasion resistance even when the drying temperature after application of the film forming solution is low. Can be obtained. Still another preferred organic polymer is an organic polymer containing an organic group (such as a phenyl group or an alkenyl group having a conjugated double bond) capable of π-π interaction with the aromatic ring of the ultraviolet absorber. As an example, bisphenol polyol can be mentioned. The organic polymer is preferably an organic polymer soluble in ethanol and / or water. Whether or not the organic polymer is dissolved in ethanol (water) is determined based on whether or not 1 g or more of the organic polymer is dissolved in 100 g of ethanol (water) at 25 ° C. Since the organic polymer does not require ultraviolet absorbing ability, the organic polymer does not correspond to the compounds not corresponding to the ultraviolet absorber, specifically, the compounds and organic dyes from the benzotriazole compounds to the cyanoacrylate compounds listed above. It is better to use one. The average number of epoxy groups in the molecule of the organic polymer having an epoxy group may be 2 to 10.

  Examples of the organic polymer having an epoxy group include polyglycidyl compounds such as polyglycidyl ether compounds, polyglycidyl ester compounds, and polyglycidylamine compounds. The organic polymer having an epoxy group may be either an aliphatic polyepoxide or an aromatic polyepoxide, but is preferably an aliphatic polyepoxide. Preferred organic polymers having epoxy groups are polyglycidyl ether compounds, especially aliphatic polyglycidyl ether compounds. The polyglycidyl ether compound is preferably an glycidyl ether of an alcohol having two or more hydroxyl groups. The alcohol is preferably an aliphatic alcohol, an alicyclic alcohol or a sugar alcohol.

  As the glycidyl ether of an alcohol having two or more hydroxyl groups, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, glycerol polyglycidyl ether, Examples thereof include diglycerol polyglycidyl ether, polyglycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, sorbitol polyglycidyl ether, and pentaerythritol polyglycidyl ether. These may be used alone or in combination of two or more.

  Among these, from the point of abrasion resistance of the organic-inorganic composite film, aliphatic having three or more hydroxyl groups such as glycerol polyglycidyl ether, diglycerol polyglycidyl ether, polyglycerol polyglycidyl ether, and sorbitol polyglycidyl ether. Polyglycidyl ethers of polyols (having an average number of glycidyl groups (epoxy groups) per molecule of more than 2 per molecule) are preferred.

  The organic polymer is a component that contributes to improving the dispersibility of the ultraviolet absorber through high affinity with the ultraviolet absorber, which is also an organic substance, and suppresses bleed out. Even in such a case, it is a component that hardly causes cracks in the film and also contributes to improvement of the abrasion resistance of the film. In particular, an organic polymer having an epoxy group is a component that also contributes to improving the adhesion of a film formed on the surface of the transparent substrate having low reactivity.

[acid]
The acid has an acid dissociation constant of less than 1 and a boiling point of 130 ° C. or less, and may be an inorganic acid or an organic acid. Examples of the inorganic acid include at least one selected from hydrochloric acid, nitric acid, hydrobromic acid and hydroiodic acid, preferably hydrochloric acid and nitric acid. These volatile acids are easier to remove by heating than non-volatile inorganic acids represented by sulfuric acid and phosphoric acid.

  Examples of the organic acid include trifluoroacetic acid (pKa: 0.23, boiling point: 72.4 ° C.). Organic acids having a low boiling point can be easily removed by heating, similarly to volatile inorganic acids. In this embodiment, an acid which is easily removed in the drying step is used as a hydrolysis catalyst regardless of whether it is an inorganic acid or an organic acid. The component derived from the hydrolysis catalyst remaining in the membrane may be a factor that impairs the transparency of the membrane after long-term use.

As is well known, when the chemical formula of an acid is [HA], the pKa of the acid is calculated from the following formula.
_{pKa = -log {[H 3 O} +] [A -] / [HA]}
In the formula, [H ₃ O ⁺ ] is the hydrogen ion concentration (mol / L) in the aqueous acid solution, [A ⁻ ] is the base concentration (mol / L) in the aqueous acid solution, and [HA] is the aqueous HA solution. Represents the concentration (mol / L). When the acid dissociates from the acidic group of HA in multiple stages, pKa means the first stage acid dissociation constant.

  When an acid having a pKa of less than 1 is used, a denser organic-inorganic composite membrane can be easily obtained than when an acid having a relatively high pKa is used as a hydrolysis catalyst. The wear resistance of the film is improved by improving the denseness of the film.

  The boiling point of the acid is preferably 100 ° C. or lower, and may be 80 ° C. or lower.

  The acid is preferably at least one selected from hydrochloric acid, nitric acid and trifluoroacetic acid.

  The film forming solution may contain an infrared absorbent. As the infrared absorber, for example, polymethine compounds, cyanine compounds, phthalocyanine compounds, naphthalocyanine compounds, naphthoquinone compounds, anthraquinone compounds, dithiol compounds, immonium compounds, diimonium compounds, aminium compounds, pyrylium compounds, cerium compounds, squarylium compounds, benzene Organic infrared absorbers such as a counter ion conjugate of a dithiol metal complex anion and a cyanine dye cation; tungsten oxide, tin oxide, indium oxide, magnesium oxide, titanium oxide, chromium oxide, zirconium oxide, nickel oxide, aluminum oxide, oxide Zinc, iron oxide, antimony oxide, lead oxide, bismuth oxide, lanthanum oxide, tungsten oxide, indium tin oxide, antimony tin oxide, fluorine-doped tin oxide, etc. Inorganic infrared absorbing agent; and the like. The infrared absorbers may be used alone or in combination of two or more. The infrared absorber is preferably at least one selected from indium tin oxide, antimony tin oxide and fluorine-doped tin oxide.

  The film forming solution may contain inorganic oxide fine particles. The inorganic oxide constituting the inorganic oxide fine particles is, for example, an oxide of at least one element selected from Si, Ti, Zr, Ta, Nb, Nd, La, Ce and Sn, and preferably silica fine particles. is there. Silica fine particles can be introduced into a film forming solution by adding, for example, colloidal silica. The inorganic oxide fine particles are excellent in transmitting the stress applied to the organic-inorganic composite film to a substrate supporting the organic-inorganic composite film, and have high hardness. Therefore, the addition of the inorganic oxide fine particles is advantageous from the viewpoint of improving the wear resistance of the organic-inorganic composite film.

  It is preferable to add an organic solvent to the film-forming solution in order to increase the solubility of organic substances in the constituent components. As the organic solvent, a solvent mixed with water at an arbitrary ratio is preferable, and a lower alcohol having 1 to 3 carbon atoms (methanol, ethanol, propanol) is particularly preferable.

  Other additives may be added to the film forming solution. Examples of the additive include a surfactant having a function of improving the appearance of the organic-inorganic composite film and the dispersibility of the ultraviolet absorbent. As an additive, a leveling agent, an antifoaming agent, a preservative and the like may be added.

The component CA generated by the condensation polymerization of the hydrolyzate of the silicon compound A represented by the formula (1) is SiO ₂ . The component CB produced by condensation polymerization of the hydrolyzate of the silicon compound B represented by the formula (2) can be represented by [R ¹ _m R ² _n SiO _{(4-mn) / 2} ]. The component CB includes a component CB1 generated by polycondensation of a hydrolyzate of the silicon compound B1 and a component CB2 generated by polycondensation of a hydrolyzate of the silicon compound B2. Here, R ¹ , R ² , m and n are as described above.

  The ratio (p / r) of the total mass p of the component CA to the total mass r of the component CA and the component CB is preferably 0.1 or more and less than 0.8, more preferably 0.35 or more and 0.48 or less. It may be .40 or more and 0.48 or less. The ratio (q / r) of the total mass q of the component CB to the total mass r of the component CA and the component CB is preferably more than 0.2 and 0.9 or less, more preferably 0.52 or more and 0.65 or less, It may be 0.52 or more and 0.60 or less. The ratio (c / r) of the mass c of the component CB1 to the total mass r of the component CA and the component CB may be 0 or more and 0.9 or less. The ratio (d / r) of the mass d of the component CB2 to the total mass r of the component CA and the component CB may be 0 or more and 0.4 or less.

  Further, the ratio (s / r) of the mass s of the organic polymer to the total mass r of the component CA and the component CB is preferably 0.001 or more and 1 or less, more preferably 0.001 or more and 0.8 or less. It may be 001 or more and 0.6 or less.

  It is preferable to prepare a film-forming solution so that the above ratios (p / r), (q / r), (c / r), (d / r) and (s / r) are all within desirable ranges. . The ultraviolet absorber is preferably contained in the film-forming solution so that the content in the formed organic-inorganic composite film is 0.5 to 40% by mass, and more preferably 10 to 40% by mass. It is. The ratio (e / r) of the mass e of the ultraviolet absorbent to the total mass r of the component CA and the component CB may be 0.005 or more and 0.7 or less.

  The preferred content of the acid in the film-forming solution is 0.001 to 1% by mass, more preferably 0.001 to 0.6% by mass, based on the mass of the film-forming solution.

  The number of moles of water in the film forming solution is preferably 15 times or less, more preferably 4 to 12 times, for example, 4 to 10 times, relative to the total number of moles of silicon atoms contained in the film forming solution. If the number of moles of water is suppressed to the above level without being excessive, it becomes easy to obtain a transparent film. Also, when the number of moles of water is at least as high as the above, and it is easy to obtain a denser film having high wear resistance.

  The method for preparing the film-forming solution is not particularly limited, but may be carried out by sequentially supplying each of the above-described components to a single vessel, for example, a mixing tank equipped with a stirrer without any limitation, and stirring. . In the container, only an ultraviolet absorber that has not reacted with any of the silicon compound A and the silicon compound B is supplied as an ultraviolet absorber. In other words, the entire amount of the ultraviolet absorber is supplied to the container without undergoing a silylation treatment using the silicon compound A and the silicon compound B. In the present embodiment, preferably, only an acid having an acid dissociation constant of less than 1 and a boiling point of 130 ° C. or less is supplied as a hydrolysis catalyst into the container.

  Next, the transparent substrate to which the film forming solution is applied will be described below.

[Transparent substrate]
Regardless of the type and shape of the transparent substrate, a glass plate, a resin plate, or the like can be used. The transparent substrate is, for example, a glass plate (a glass plate with a ceramic shielding layer) having a ceramic shielding layer formed on the peripheral edge of the surface for use as a vehicle window glass. However, the transparent substrate may be a glass plate having no ceramic shielding layer. A glass plate having no ceramic shielding layer is also used as a window glass for a vehicle as a door glass or the like. Note that the glass plate with a ceramic shielding layer is also a transparent substrate as long as all regions on the surface of the glass plate are not covered with the ceramic shielding layer. As is clear from this, in the present specification, the “transparent substrate” means a substrate having a transparent region on at least a part of its surface (the “transparent article” has the same meaning).

  Although the size of the transparent substrate is not particularly limited, the maximum length measured along the two directions may be more than 30 cm, and may be 40 cm or more, in any case, regardless of how two directions perpendicular to each other are set. It may have a certain size.

(Glass plate)
The glass sheet may be, for example, a float sheet glass most commonly used in the vehicular, architectural and industrial fields. The glass plate may be colored green, bronze, or the like, or may be processed or processed into tempered glass, laminated glass, double-glazed glass, or the like. The shape of the main surface of the glass plate may be either flat or curved. The thickness of the glass plate is, for example, 1 to 12 mm, preferably 3 to 10 mm for architectural use, and 1 to 5 mm for vehicle use.

(Resin plate)
As the resin plate, an acrylic resin plate represented by a polymethyl methacrylate plate, a polycarbonate resin plate, or the like is suitable. The thickness of the resin plate is suitably from 2 to 8 mm, and preferably from 3 to 6 mm. The surface of the resin plate may be subjected to a surface treatment for improving adhesion to the organic-inorganic composite film. The surface treatment of the resin plate includes corona discharge treatment, plasma treatment, chromic acid treatment (wet type), flame treatment, hot air treatment, oxidation treatment such as ozone / ultraviolet irradiation treatment, and unevenness treatment such as sandblasting and solvent treatment. Can be mentioned. Among these treatments, a corona discharge treatment is preferable from the viewpoint of effects and operability.

(Glass plate with ceramic shielding layer)
In order to improve the design of a vehicle, a ceramic shielding layer may be formed on a peripheral portion of a vehicle window glass. The ceramic shielding layer also plays a role in preventing a resin material such as an adhesive or a foam material for joining the window glass to the vehicle body from being deteriorated by ultraviolet rays. The ceramic shielding layer is formed by applying a ceramic paste and firing at a high temperature. As shown in FIG. 1, on the surface of a transparent article 1 manufactured using a glass plate with a ceramic shielding layer, there are a shielding region 12 on which a ceramic shielding layer is formed and a transparent region 11 surrounded by the shielding region. I do.

  The surface of the ceramic shielding layer has fewer hydroxyl groups per unit area than the surface of the glass plate. Therefore, when the organic-inorganic composite film is formed up to the surface of the ceramic shielding layer together with the transparent region where the surface of the glass plate is exposed, the organic-inorganic composite film may be peeled off from the surface of the ceramic shielding layer. Unlike the transparent region, the light shielding region and the field of view are shielded in the shielding region where the ceramic shielding layer is formed. For this reason, the loss or deterioration of the function due to the peeling of the organic-inorganic composite film does not cause a problem in the shielding region. However, partial peeling of the organic-inorganic composite film causes appearance problems on the window glass.

  From the above circumstances, when the ceramic shielding layer is present on the surface of the glass plate on which the organic-inorganic composite film is to be formed, the coating liquid is applied only to the transparent region after masking the ceramic shielding layer using a masking tape. . The necessity of attaching a masking tape greatly impairs mass productivity in forming an organic-inorganic composite film. In order to form an organic-inorganic composite film without masking the ceramic shielding layer using a masking tape, it is desired to suppress peeling of the organic-inorganic composite film from the ceramic shielding layer.

  It has been found that the organic-inorganic composite film formed from the film-forming solution according to the present invention is also effective in suppressing film peeling from the surface of the ceramic shielding layer. Therefore, in the present embodiment, a glass plate on which a ceramic shielding layer is formed is used as a transparent substrate, and a film forming solution is applied to a shielding region where the ceramic shielding layer is formed and a transparent region where the ceramic shielding layer is not formed. Applied. As shown in FIG. 2, the transparent article 1 thus obtained has a surface of the ceramic shielding layer 22 formed in advance on the periphery of the glass plate 21 and the glass plate 21 without the ceramic shielding layer 22 formed thereon. The organic-inorganic composite film 23 is formed on both of the surfaces.

[Coating step and drying step]
Application of the film-forming solution may be performed using a conventionally known method, for example, a flow coating method, a dip coating method, a spin coating method, a spray coating method, a roll coating method, a meniscus coating method, a die coating method, or the like. Can be.

  In the step of applying the film forming solution, it is preferable to maintain the relative humidity (RH) of the atmosphere at less than 40%, and more preferably at 30% or less. By keeping the relative humidity low, it is possible to prevent the applied film from excessively absorbing moisture from the atmosphere. If a large amount of moisture is absorbed from the atmosphere, water remaining in the matrix of the film may reduce the strength of the film.

  The temperature at which the transparent substrate is dried after applying the film forming solution is 130 ° C. or higher, preferably 160 ° C. or higher, more preferably 170 ° C. or higher, and may be 180 ° C. or higher in some cases. Further, the drying temperature is preferably 300 ° C. or less, particularly 250 ° C. or less, and in some cases, 200 ° C. or less, from the viewpoint of avoiding decomposition of the ultraviolet absorber, the organic polymer, and the like.

  The drying step preferably includes an air drying step and a heating drying step involving heating. The air drying step may be performed by exposing the film-forming solution to an atmosphere in which the relative humidity is kept at less than 40%, and more preferably at 30% or less. The air drying step can be performed at room temperature as a non-heating step. In the heating and drying step, a dehydration reaction involving the silanol groups contained in the hydrolyzate of the silicon compound A and the silicon compound B and the hydroxyl groups present on the transparent substrate proceeds, and a matrix composed of silicon atoms and oxygen atoms The organic-inorganic composite film is fixed on the transparent substrate by the development of the structure (Si-O bond network).

[Transparent article]
The transparent article obtained according to the present embodiment includes a transparent substrate and an organic-inorganic composite film formed on the surface of the transparent substrate. The organic-inorganic composite film is a single-layer film. The thickness of the organic-inorganic composite film may be appropriately adjusted according to the required performance, and is, for example, 1 to 15 μm, preferably 2 to 12 μm, and more preferably 3 to 10 μm.

  The organic-inorganic composite film is made of a silicon compound A represented by the formula (1), a silicon compound B represented by the formula (2), an organic substance, and an ultraviolet ray which does not react with any of the silicon compound A and the silicon compound B. It includes a reaction product obtained by reacting a constituent component containing an absorbent and an organic polymer. The constituent components may further include other components. In the present embodiment, the silylation reaction of the ultraviolet absorber proceeds competitively with other reactions, for example, the reaction between the ultraviolet absorber and the organic polymer. Therefore, even if the silicon compound B1 (silane coupling agent) is contained in the constituent components, the UV absorber does not completely react with the silicon compound B1 in the reaction product, and usually at least a part thereof. Reacts with at least one selected from silicon compound A, silicon compound B (excluding silicon compound B1) and organic polymer.

  The transparent article according to the present embodiment has high transparency immediately after film formation, and has a haze ratio of preferably 1.0% or less, more preferably 0.8% or less, particularly preferably 0.6% or less, Most preferably, it has a characteristic of 0.3% or less. The transparent article according to the present embodiment has a reduced transparency even after long-term use, and the difference in the haze ratio before and after the test is left for 500 hours in an environment of a temperature of 50 ° C. and a relative humidity of 95% is 1. 0% or less, preferably 0.7% or less, more preferably 0.5% or less, particularly preferably 0.2% or less. Further, the haze ratio after being left for 500 hours in an environment of a temperature of 50 ° C. and a relative humidity of 95% is preferably 1.0% or less, more preferably 0.8% or less, particularly preferably 0.6% or less, most preferably. Preferably, it has a characteristic of 0.3% or less.

  In addition, the transparent article according to the present embodiment not only has high transparency immediately after film formation, but also suppresses a decrease in ultraviolet absorbing ability even after long-term use. The transparent article according to the present embodiment has a UV transmittance Tuv380 calculated according to ISO 9050 (2003 edition) of preferably 2.0% or less, more preferably 1.0% or less, and in some cases 0.5% or less. May be provided. In the transparent article according to the present embodiment, the UV transmittance Tuv400 calculated according to ISO 13837 (convention A) is preferably 5.0% or less, more preferably 2.0% or less, still more preferably 1.0% or less, and particularly preferably. May have properties of 0.7% or less, and in some cases 0.5% or less. The transparent article according to the present embodiment can also be excellent in the ability to shield light rays in the ultraviolet long wavelength region. The UV transmittance Tuv 380 and the UV transmittance Tuv 400 of the transparent article according to the present embodiment are maintained in the above ranges even after the transparent article according to the present embodiment is left under an environment of a temperature of 50 ° C. and a relative humidity of 95% for 500 hours. I have.

  The transparent article according to the present embodiment may have excellent infrared shielding properties because the organic-inorganic composite film further includes an infrared shielding agent. The transparent article according to the present embodiment can have excellent infrared shielding properties such that the light transmittance at a wavelength of 1500 nm is 30% or less, and in some cases 25% or less.

  The transparent article according to the present embodiment may have a property that the visible light transmittance Tvis calculated according to ISO 9050 (2003 version) is preferably 70.0% or more, more preferably 71.0% or more.

  In the transparent article according to the present embodiment, regarding the chromaticity of the transmitted color, the dominant wavelength (λd) of the C light source calculated according to JIS Z 8701 (1995 version) is preferably 565 nm or less, more preferably 562 nm or less, and still more preferably. It may have a characteristic of 560 nm or less, particularly preferably 558 nm or less, and in some cases, 555 nm or less. When λd is in the above range, the transparent article hardly feels yellowish, or has a chromaticity that gives a favorable impression even when yellowish is felt. In the transparent article according to the present embodiment, λd is in the above range, and the visible light transmittance Tvis calculated according to ISO 9050 (2003 version) is preferably 70.0% or more, more preferably 71.0%. It can have the above characteristics.

  In the transparent article according to the present embodiment, the stimulus purity (Pe) of the C light source calculated according to JIS Z 8701 (1995 version) is preferably 13% or less, more preferably 11% or less, with respect to the chromaticity of the transmitted color. It may have a property of preferably 10% or less, particularly preferably 9% or less, and in some cases preferably 6% or less. When Pe is in the above range, the transparent article hardly feels yellowish, or has a chromaticity that gives a favorable impression even when yellowish is felt. In the transparent article according to the present embodiment, Pe is within the above range, and the visible light transmittance Tvis calculated according to ISO 9050 (2003 version) is preferably 70.0% or more, more preferably 71.0%. It can have the above characteristics.

  The transparent article according to the present embodiment has excellent abrasion resistance. After performing the Taber abrasion test specified in Japanese Industrial Standards (JIS) R 3212 on the surface of the organic-inorganic composite film, no peeling was observed in the portion where the test was applied, and the haze ratio was 5%. It may have the following excellent properties. The haze ratio in the portion where the test is applied is preferably 4% or less, particularly preferably 3% or less, and most preferably 2% or less.

  The transparent article according to the present embodiment can exhibit excellent abrasion resistance with respect to the organic-inorganic composite film formed on the surface of the ceramic shielding layer even when a glass plate with a ceramic shielding layer is used as a transparent substrate. Specifically, even after performing the above-mentioned Taber abrasion test on the organic-inorganic composite film formed on the surface of the ceramic shielding layer, in the portion where the test was applied, excellent abrasion resistance to such an extent that no peeling was observed was realized. It is possible to do.

  Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited by the following Examples.

<Examples 1 to 23 and Comparative Examples 1 to 5>
Each component shown in Table 1 was put into a mixing tank equipped with a stirrer and a temperature control function, and stirred at 20 ° C. to prepare a film forming solution for forming an organic-inorganic composite film. Next, a UV-cut green glass [thickness: 3.1 mm, manufactured by Nippon Sheet Glass] is cut into dimensions shown in Table 1 and washed, and the film-forming solution is flowed through the glass plate at 20 ° C. and 30% RH. It was applied by a coating method. After drying under the same environment for 5 minutes, the drying was carried out such that the temperature of the glass plate to which the film forming solution was applied was as shown in Table 1 to produce a transparent article.

Details of each component shown in Table 1 are as follows.
-UV absorber: 2,2 ', 4,4'-tetrahydroxybenzophenone "UVINUL 3050" [manufactured by BASF]
-Organic polymer A: sorbitol polyglycidyl ether "SR-SEP" [Sakamoto Yakuhin Kogyo]
-Organic polymer B: polypropylene glycol "PPG700" [manufactured by Kishida Chemical]
-Silicon compound A: tetraethoxysilane [manufactured by Tama Chemical Industry]
-Silicon compound B1: 3-glycidoxypropyltrimethoxysilane "KBM-403" [Shin-Etsu Chemical Co., Ltd.]
-Silicon compound B2: phenyltriethoxysilane "KBE-103" [Shin-Etsu Chemical Co., Ltd.]
Trifluoroacetic acid: pKa; 0.23, boiling point: 72.4 ° C., concentration: 100% by mass [manufactured by Kishida Chemical]
-Hydrochloric acid: pKa; -8, boiling point: 48 ° C, concentration: 35% by mass [manufactured by Futaba Chemical]
Nitric acid: pKa; -1.4, boiling point: 82.6 ° C, concentration: 60% by mass [manufactured by Futaba Chemical]
-Paratoluenesulfonic acid monohydrate: pKa; -2.8, boiling point: 140 ° C (20 mmHg), concentration: 100% by mass [Kanto Chemical]
-Phosphoric acid: pKa: 2.12, boiling point: 213 ° C, concentration: 85% by mass [Sigma-Aldrich Japan]
・ Sulfuric acid: pKa; −3, boiling point: 290 ° C., concentration: 95% by mass [manufactured by Futaba Chemical]
-Surfactant A: Silicone surfactant "SH28 paint additive" [manufactured by Dow Corning Toray]
-Surfactant B: Silicone surfactant "BYK-345" [manufactured by BYK]
Infrared absorber: Indium tin oxide fine particle dispersion [Ethyl alcohol solution containing 40% by mass of indium tin oxide fine particle dispersion, manufactured by Mitsubishi Materials Electronic Chemicals]
The organic polymer “SR-SEP” is a polymer that dissolves in an amount of 1 g or more in 100 g of water or 100 g of ethanol at 25 ° C.

  The performance of the transparent articles produced in Examples 1 to 23 and Comparative Examples 1 to 5 was evaluated by the following method. Table 2 shows the results.

<Optical characteristics>
According to ISO 9050 (2003 version), the visible light transmittance (Tvis) and the ultraviolet light transmittance (Tuv380) were measured. According to ISO 13837 (convention A), the ultraviolet transmittance (Tuv400) was measured. The transmittance (T1500) at a wavelength of 1500 nm was measured. All of the above optical characteristics were measured using a spectrophotometer “UV-3100PC” (manufactured by Shimadzu Corporation).

<Primary wavelength (λd), stimulus purity (Pe)>
The chromaticity was measured using a spectrophotometer “UV-3100PC” (manufactured by Shimadzu Corporation), and the dominant wavelength (λd) and stimulus purity (Pe) of the C light source were calculated according to JIS Z 8701 (1995 version).

<Wear resistance>
The wear test was performed according to JIS R 3212. Specifically, using a Taber abrasion tester "5150 ABRASER" (manufactured by TABER INDUSTRIES), the transparent article was abraded 1000 times with a load of 500 g, and the haze ratio of the transparent article before and after the abrasion test was measured. The smaller the difference in the haze ratio of the transparent article before and after the abrasion test, the better the abrasion resistance. The haze ratio of the transparent article was measured using "HZ-1S" manufactured by Suga Test Instruments.

<High temperature and high humidity resistance>
In a high-temperature and high-humidity test apparatus “IG420” (manufactured by Yamato Kagaku) at 50 ° C. and a relative humidity of 95% RH, the transparent articles not subjected to the abrasion resistance test were left for 300 hours and 500 hours, respectively. A high-temperature and high-humidity resistance test was performed, and the optical properties and haze ratio of the transparent article before and after the test were measured. The haze ratio was measured using "HZ-1S" manufactured by Suga Test Instruments. Further, the transparent article after the high-temperature and high-humidity resistance test was visually observed using a high-intensity halogen lamp and observed with a dark-field optical microscope to confirm the presence or absence of bleed-out of the ultraviolet absorbent.

<Peeling test>
A flat soda lime silicate glass plate “UV cut green glass” [a square having a side of 600 mm, a thickness of 3.1 mm, manufactured by Nippon Sheet Glass] was prepared. On one main surface of the glass plate, a black ceramic shielding layer having a width of 120 mm is formed along a peripheral end thereof, and a shielding region which cannot be seen through by this layer surrounds a central transparent region. This glass plate was washed and held so that the main surface was vertical.

  Subsequently, the solution for forming the organic-inorganic composite film prepared in Examples 3, 8, 10 and 11 was sprayed on the main surface of the glass plate using a nozzle. This forming solution was supplied while moving the nozzle along the long side located above the glass plate. The coating liquid supplied to the upper end of the main surface of the glass plate flowed downward, and flowed down from the lower end of the glass plate. The glass plate was dried in that state for 5 minutes, and heated so that the temperature of the glass plate to which the film-forming solution was applied was as shown in Table 1. Thus, a window glass having the ceramic shielding layer and the organic-inorganic composite film formed on the glass surface was obtained.

  The film forming solutions of Examples 3 and 10 have an ultraviolet shielding ability but do not have a special infrared shielding property. The film forming solutions of Examples 8 and 11 have an infrared shielding ability in addition to the ultraviolet shielding ability. It is an example to have. Further, the organic-inorganic composite films of Examples 3 and 8 are examples in which the film thickness is relatively thin, and the organic-inorganic composite films of Examples 10 and 11 are examples in which the film thickness is relatively large.

In the obtained four examples of window glasses, the organic-inorganic composite film immediately after film formation did not show cracks or peeling on both the ceramic shielding layer and the glass surface. With respect to these window glasses, an organic-inorganic test was performed in a cloth friction test (the surface state of the test object was visually observed after reciprocating 1000 times while applying a pressure of 4.9 N / 400 mm ^{2 to} the flannel cloth). In the composite film, no cracks or peeling were observed on both the ceramic shielding layer and the glass surface. In addition, these windows did not change in appearance even after being left for 1000 hours in an environment of a temperature of 50 ° C. and a relative humidity of 95%.

  Comparing the transparent articles of Examples 1 to 23 with the transparent articles of Comparative Examples 1 to 5, the transparent articles of Comparative Examples 1 to 5 had the same level of abrasion resistance as the transparent articles of Examples 1 to 23. . However, the transparent articles of Comparative Examples 1 to 5 after the high-temperature and high-humidity resistance test have significantly reduced transparency. In particular, in the transparent article of Comparative Example 5, the film became cloudy immediately after the drying of the film forming solution applied to the glass plate was completed.

  As apparent from the above disclosure, the present invention also provides the following transparent article manufacturing method, transparent article, and film-forming solution from another aspect.

A method for producing a transparent article, comprising a transparent substrate and an organic-inorganic composite film formed on the surface of the transparent substrate,
At least a silicon compound A represented by the above formula (1), a silicon compound B represented by the above formula (2), an ultraviolet absorber which is an organic substance, an organic polymer, and an acid dissociation constant of less than 1 and a boiling point A step of preparing a film-forming solution by supplying an acid having a temperature of 130 ° C. or less and water to a container and mixing in the container.
Applying the film-forming solution to the surface of the transparent substrate,
Drying the transparent substrate coated with the film-forming solution to form an organic-inorganic composite film on the transparent substrate,
As the ultraviolet absorber, only an ultraviolet absorber that has not reacted with the silicon compound B1 represented by the same formula as the above formula (2) except that m is 1 or 2 and n is 0 or 1. To the container,
A method for producing a transparent article, wherein the transparent substrate coated with the film-forming solution is heated to 130 ° C. or higher and dried to form the organic-inorganic composite film.

A transparent substrate, including an organic-inorganic composite film formed on the surface of the transparent substrate,
The organic-inorganic composite film is at least a silicon compound A represented by the above formula (1), a silicon compound B represented by the above formula (2), and an organic substance, and m is 1 or 2 and n is Except that it is 0 or 1, it is obtained by reacting a component containing an organic polymer with an ultraviolet absorber not reacted with the silicon compound B1 represented by the same formula as the above formula (2). Including reaction products,
A transparent article having a haze ratio of 1.0% or less after being left in an environment at a temperature of 50 ° C. and a relative humidity of 95% for 500 hours.

At least a silicon compound A represented by the above formula (1), a silicon compound B represented by the above formula (2), an ultraviolet absorber which is an organic substance, an organic polymer, and an acid dissociation constant of less than 1 and a boiling point A film-forming solution for forming an organic-inorganic composite film, prepared by supplying an acid having a temperature of 130 ° C. or less and water to a container and mixing in the container.
However, as the ultraviolet absorber, ultraviolet rays which have not reacted with the silicon compound B1 represented by the same formula as the above formula (2) except that m is 1 or 2 and n is 0 or 1 Only the absorbent is supplied to the container.

  INDUSTRIAL APPLICABILITY The transparent article according to the present invention has excellent abrasion resistance and suppresses a decrease in transparency due to long-term use.

Claims (29)

A method for producing a transparent article, comprising a transparent substrate and an organic-inorganic composite film formed on the surface of the transparent substrate,
At least a silicon compound A represented by the following formula (1), a silicon compound B represented by the following formula (2), an ultraviolet absorber which is an organic substance, an organic polymer, and an acid dissociation constant of less than 1 and a boiling point A step of preparing a film-forming solution by supplying an acid having a temperature of 130 ° C. or less and water to a container and mixing in the container.
Applying the film-forming solution to the surface of the transparent substrate,
Drying the transparent substrate coated with the film-forming solution to form an organic-inorganic composite film on the transparent substrate,
As the ultraviolet absorber, supply only the ultraviolet absorber that has not reacted with any of the silicon compound A and the silicon compound B to the container,
A method for producing a transparent article, wherein the transparent substrate coated with the film-forming solution is heated to 130 ° C. or higher and dried to form the organic-inorganic composite film.
SiX ¹ ₄ ⁽¹⁾
[X ¹ is a hydrolyzable functional group or a halogen atom. ]
R ¹ _m R ² _n SiX ² _4-mn (2)
[R ¹ is an organic group having a reactive functional group, R ² is an organic group having no reactive functional group, X ² is a hydrolyzable functional group or a halogen atom, and m is 0 or more and 2 or less. N is an integer of 0 or more and 2 or less, and m + n is 1 or more and 2 or less. ]   The method for producing a transparent article according to claim 1, wherein the acid is at least one selected from hydrochloric acid, nitric acid, and trifluoroacetic acid.   The method for producing a transparent article according to claim 1, wherein the ultraviolet absorber has a hydroxyl group in a molecule.   The method for producing a transparent article according to claim 1, wherein the ultraviolet absorber is at least one selected from a benzotriazole compound, a benzophenone compound, a hydroxyphenyltriazine compound, and a cyanoacrylate compound.   The method for producing a transparent article according to claim 1, wherein the organic polymer is dissolved in ethanol and / or water.   The method according to claim 1, wherein the organic polymer has an epoxy group in a molecule.   The method for manufacturing a transparent article according to claim 1, wherein the silicon compound B includes a silicon compound B1 in which m is 1 or 2 and n is 1 or 2 in the formula (2). It said silicon compound B1 has an epoxy group as the reactive functional group contained in R ^1, method for producing a transparent article according to claim 7.   The method for producing a transparent article according to claim 1, wherein the silicon compound B includes a silicon compound B2 in which m in the formula (2) is 0 and n is 1 or 2.   2. The production of the transparent article according to claim 1, wherein the film forming solution contains the ultraviolet absorber such that the content of the ultraviolet absorber in the organic-inorganic composite film is 0.5 to 40% by mass. Method.   The method for producing a transparent article according to claim 1, wherein the film forming solution further includes an infrared absorber. A transparent substrate, including an organic-inorganic composite film formed on the surface of the transparent substrate,
The organic-inorganic composite film is at least a silicon compound A represented by the following formula (1), a silicon compound B represented by the following formula (2), and an organic substance. Including a reaction product obtained by reacting a constituent component containing an ultraviolet absorber and an organic polymer that have not reacted with any,
A transparent article having a difference in haze ratio of 1.0% or less before and after a test left for 500 hours in an environment of a temperature of 50 ° C and a relative humidity of 95%.
SiX ¹ ₄ ⁽¹⁾
[X ¹ is a hydrolyzable functional group or a halogen atom. ]
R ¹ _m R ² _n SiX ² _4-mn (2)
[R ¹ is an organic group having a reactive functional group, R ² is an organic group having no reactive functional group, X ² is a hydrolyzable functional group or a halogen atom, and m is 0 or more and 2 or less. N is an integer of 0 or more and 2 or less, and m + n is 1 or more and 2 or less. ]   13. The transparent article according to claim 12, wherein the difference in haze ratio before and after the test is left for 500 hours in an environment of a temperature of 50 ° C and a relative humidity of 95% is 0.7% or less.   The transparent article according to claim 12, wherein a haze ratio after the test is 1.0% or less. A transparent substrate, including an organic-inorganic composite film formed on the surface of the transparent substrate,
The organic-inorganic composite film is at least a silicon compound A represented by the following formula (1), a silicon compound B represented by the following formula (2), and an organic substance. Including a reaction product obtained by reacting a constituent component containing an ultraviolet absorber and an organic polymer that have not reacted with any,
A transparent article having a haze ratio of 1.0% or less after being left in an environment at a temperature of 50 ° C. and a relative humidity of 95% for 500 hours.
SiX ¹ ₄ ⁽¹⁾
[X ¹ is a hydrolyzable functional group or a halogen atom. ]
R ¹ _m R ² _n SiX ² _4-mn (2)
[R ¹ is an organic group having a reactive functional group, R ² is an organic group having no reactive functional group, X ² is a hydrolyzable functional group or a halogen atom, and m is 0 or more and 2 or less. N is an integer of 0 or more and 2 or less, and m + n is 1 or more and 2 or less. ]   The transparent article according to claim 12, wherein the ultraviolet absorber includes at least one selected from a benzophenone compound, a hydroxyphenyltriazine compound, and a cyanoacrylate compound.   The transparent article according to claim 12, wherein the content of the ultraviolet absorber in the organic-inorganic composite film is 0.5 to 40% by mass.   The transparent article according to claim 12 or 15, wherein an ultraviolet transmittance Tuv380 calculated according to ISO 9050 (2003 version) is 2.0% or less.   The transparency according to claim 12 or 15, wherein an ultraviolet transmittance Tuv 380 calculated according to ISO 9050 (2003 version) after being left for 500 hours in an environment of a temperature of 50 ° C and a relative humidity of 95% is 2.0% or less. Goods.   The transparent article according to claim 12 or 15, wherein an ultraviolet transmittance Tuv400 calculated according to ISO 13837 (convention A) is 5.0% or less. Temperature 50 ° C., UV transmittance Tuv400 calculated according to the relative humidity of 95% after 500 hours under environment ISO 13837 (conve nt ion A) is not more than 5.0%, according to claim 12 or 15 Transparent goods.   21. The transparent article according to claim 20, wherein the UV transmittance Tuv400 calculated according to ISO 13837 (convention A) is 2.0% or less.   22. The transparent article according to claim 21, wherein an ultraviolet transmittance Tuv400 calculated according to ISO 13837 (convention A) after being left for 500 hours in an environment of a temperature of 50 ° C and a relative humidity of 95% is 2.0% or less. ISO 13837 (conve nt ion A) ultraviolet transmittance Tuv400 calculated according is 1.0% or less, the transparent article of claim 20.   16. The method according to claim 12, wherein the dominant wavelength λd calculated according to JIS Z8701 (1995 version) is 565 nm or less, and the visible light transmittance Tvis calculated according to ISO 9050 (2003 version) is 70% or more. 17. Transparent goods.   The transparent article according to claim 25, wherein the dominant wavelength λd calculated according to JIS Z8701 (1995 version) is 560 nm or less, and the visible light transmittance Tvis calculated according to ISO 9050 (2003 version) is 70% or more. .   The transparent article according to claim 12, wherein the organic-inorganic composite film further includes an infrared absorber.   The transparent article according to claim 27, wherein the light transmittance at a wavelength of 1500 nm is 30% or less. At least a silicon compound A represented by the following formula (1), a silicon compound B represented by the following formula (2), an ultraviolet absorber which is an organic substance, an organic polymer, and an acid dissociation constant of less than 1 and a boiling point A film-forming solution for forming an organic-inorganic composite film, prepared by supplying an acid having a temperature of 130 ° C. or less and water to a container and mixing in the container.
However, as the ultraviolet absorber, the silicon compound A and the silicon compound B
Only the ultraviolet absorber which has not reacted with any of the above is supplied to the container.
SiX ¹ ₄ ⁽¹⁾
[X ¹ is a hydrolyzable functional group or a halogen atom. ]
R ¹ _m R ² _n SiX ² _4-mn (2)
[R ¹ is an organic group having a reactive functional group, R ² is an organic group having no reactive functional group, X ² is a hydrolyzable functional group or a halogen atom, and m is 0 or more and 2 or less. N is an integer of 0 or more and 2 or less, and m + n is 1 or more and 2 or less. ]

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