Glass substrate with functional film

Abstract

The present disclosure provides a glass substrate with a functional film comprising a glass substrate 1 and a functional film 2 on the glass substrate 1, wherein the functional film 2 includes: an inorganic substance; an organic substance A for imparting at least one function selected from the group consisting of ultraviolet shielding properties, infrared absorption properties, anti-fogging properties, water repellency, and light control properties to the functional film 2; and an organic substance B that is a light stabilizer for suppressing deterioration due to ultraviolet irradiation of the functional film 2.

Description

Functional film-coated glass substrate

[0001] The present invention relates to a glass substrate with a functional film.

[0002] Various functions are being added to glass substrates, such as glass plates. For example, in applications such as window glass for vehicles, such as automobiles, there is a high demand for glass substrates with ultraviolet shielding properties, due to the need for sun protection. For this reason, glass substrates are known that have formed thereon a functional film containing an organic ultraviolet shielding component to adequately shield UVA, which is ultraviolet light in the long wavelength range. In addition to ultraviolet shielding properties, functions added by the functional film include infrared absorption, anti-fogging properties, water repellency, and dimming properties. Depending on the required functions, the functional film may contain various organic substances.

[0003] Functional films containing organic substances may experience a decline in functionality or film deterioration over time. A typical example of film deterioration is the occurrence of cracks. To address this issue, Patent Document 1 discloses a technology that uses a silylated benzophenone compound as an ultraviolet-blocking component. The silylated ultraviolet-blocking component reacts with other silane compounds and is incorporated into an Si-O network composed of silicon atoms and oxygen atoms in the functional film. In other words, the technology disclosed in Patent Document 1 allows the organic substance to be integrated with the inorganic substance in the functional film, thereby suppressing the occurrence of cracks.

[0004] International Publication No. 2010 / 131744

[0005] The technology disclosed in Patent Document 1 requires silylation of the organic substance, and therefore cannot be applied to organic substances that are unsuitable for silylation, or causes undesirable changes in the properties of the organic substance, making the manufacturing process complicated even when these circumstances are not present. Therefore, an object of the present invention is to provide a new glass substrate with a functional film that can suppress the occurrence of cracks in the film without requiring silylation of the organic substance in the manufacturing process.

[0006] Since cracks do not occur in a film composed solely of an inorganic substance such as silica, increasing the amount of organic substance A that imparts a desired function or adding an organic substance other than organic substance A can basically be a factor that promotes cracking in the functional film. However, according to the inventor's investigations, unexpectedly, the addition of organic substance B, which corresponds to a light stabilizer, suppresses cracking in the functional film.

[0007] That is, the present invention provides a glass substrate with a functional film, comprising: a glass substrate; and a functional film on the glass substrate, wherein the functional film contains an inorganic substance; an organic substance A that imparts to the functional film at least one function selected from the group consisting of ultraviolet shielding, infrared absorbing, anti-fogging, water repellency, and dimming; and an organic substance B that is a light stabilizer that suppresses deterioration of the functional film due to ultraviolet irradiation.

[0008] From another aspect, the present invention provides a dispersion for application to a glass substrate, which dispersion contains at least (i) at least one organic compound selected from the group consisting of benzotriazole-based compounds, benzophenone-based compounds, triazine-based compounds, benzodithiol-based compounds, azomethine-based compounds, and indole-based compounds as an organic compound A1 having an ultraviolet-shielding property, (ii) a dispersion medium, and (iii) a light stabilizer, wherein the organic compound exists as particles.

[0009] According to the present invention, it is possible to provide a novel glass substrate with a functional film that can suppress the occurrence of cracks in the functional film.

[0010] 1 is a cross-sectional view showing one embodiment of a glass substrate according to the present invention.

[0011] Preferred embodiments of the present invention will be described below, but the following description is not intended to limit the present invention to any particular embodiment. In this specification, the term "main component" refers to a component that accounts for 50% or more, and in some cases 55% or more, by mass. The term "particles" is used to include not only solid particles but also liquid particles. Furthermore, "room temperature" refers to 25°C.

[0012] The functional film-coated glass substrate of this embodiment shown in Figure 1 includes a glass substrate 1 and a functional film 2 disposed on the glass substrate 1. The functional film 2 may be formed directly on the surface of the glass substrate 1, or may be formed via an underlayer (not shown). The underlayer may be a single layer film or a multilayer film including two or more layers.

[0013] The functional film 2 may be a film formed by applying a coating liquid (application liquid). The film quality of the functional film 2 may be glassy. Note that glassy means that the main component of the film is amorphous, but does not mean that the film does not contain crystals.

[0014] The functional film 2 contains an inorganic substance, an organic substance A, and an organic substance B corresponding to a light stabilizer. These components will be described below.

[0015] <Components of Functional Film> (Inorganic Substance) The inorganic substance may contain silicon oxide. The inorganic substance may be the main component of the functional film. The inorganic substance may have silicon oxide as its main component. Silicon oxide may also be the main component of the functional film. The inorganic substance may contain components other than silicon oxide, such as aluminum oxide, titanium oxide, or zirconium oxide. However, the inorganic substance is not limited to oxides. The inorganic substance may contain nitrides or other substances, such as polysilazane. The inorganic substance may contain a functional inorganic substance to complement the function of organic substance A or to impart a function different from that of organic substance A. An example of a functional inorganic substance is indium tin oxide (ITO) fine particles. ITO fine particles are suitable for imparting infrared absorption properties to the functional film.

[0016] (Organic Substance A) The organic substance A is a substance that can impart to the film at least one function selected from the group consisting of ultraviolet shielding, infrared absorbing, anti-fogging, water repellency, and photochromic properties. The functional film may be imparted with two or more of these functions.

[0017] An example of the organic substance A is an organic compound A1 having ultraviolet blocking properties. The organic compound A1 may include at least one selected from the group consisting of a benzotriazole-based compound, a benzophenone-based compound, a triazine-based compound, a benzodithiol-based compound, an azomethine-based compound, and an indole-based compound. The organic compound A1 may be a benzotriazole-based compound and / or a benzophenone-based compound, or may be a benzotriazole-based compound.

[0018] As the organic compound A1, an organic compound that is solid at room temperature is suitable. Polymers obtained by polymerizing a polymerizable ultraviolet absorber are also known as ultraviolet-shielding components that are solid at room temperature. However, because ultraviolet-shielding polymers are produced by polymerizing an ultraviolet absorber into which a polymerizable functional group such as a (meth)acrylic group has been introduced, their ultraviolet-shielding effect is inferior to that of low-molecular-weight ultraviolet absorbers when compared per unit mass. It is preferable that the organic compound A1 be a material other than a polymer.

[0019] The molecular weight of organic compound A1 may be 5,000 or less, 3,000 or less, 2,000 or less, 1,500 or less, 1,300 or less, even 1,200 or less, particularly 900 or less, and especially 800 or less. The molecular weight of organic compound A1 may be 200 or more, or 300 or more. Organic compound A1 may not contain silicon atoms. Not limited to organic compound A1, organic substance A may not contain silicon atoms.

[0020] The organic substance A may be an infrared-absorbing organic compound A2, which may include at least one selected from the group consisting of a cyanine dye, a phthalocyanine dye, a naphthalocyanine compound, a nickel dithiolene complex, a squarylium dye, a quinone compound, a diimmonium compound, and an azo compound.

[0021] The organic substance A may be an organic compound A3 having antifogging properties. The organic compound A3 may be a water-absorbing organic compound. Examples of the water-absorbing organic compound include polyvinyl acetal, polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene vinyl acetate copolymer resin, urethane resin, and acrylic resin.

[0022] The organic substance A may be an organic compound A4 having water repellency. The organic compound A4 may be a water-repellent group-containing organic compound. An example of the water-repellent group contained in the water-repellent group-containing organic compound is a hydrocarbon group in which a hydrogen atom may be substituted with a fluorine atom. The hydrocarbon group is not particularly limited, but examples include an alkyl group and an aryl group. The alkyl group may be linear or branched, and the number of carbon atoms is, for example, 1 to 10.

[0023] The organic substance A may be a photochromic organic compound A5. The organic compound A5 may be at least one selected from the group consisting of a photochromic compound, a thermochromic compound, an electrochromic compound, a piezochromic compound, and a liquid crystal compound. Examples of the photochromic compound include an azobenzene-based compound, a spiropyran-based compound, a furylfulgide-based compound, and a diarylethene-based compound. Known materials can also be used for other chromic compounds and liquid crystal compounds.

[0024] The organic substance A may be added as particles. Addition of the organic substance A as particles can improve the durability of its function. From the viewpoint of suppressing the haze ratio of the film, the average particle size of the particles is preferably 150 nm or less, particularly 10 nm to 150 nm. Of the organic substances A, it is particularly preferable that the organic compound A1 exists as particles. Examples of organic compounds A1 suitable for being refined to an average particle size of 150 nm or less include benzotriazole-based compounds, particularly compounds having the structural formula described below. However, the organic substance A can also be introduced into the film as a solute dissolved in an organic solvent that can dissolve it.

[0025] The particles may be solid or liquid. In other words, organic substance A may be present in the film as solid particles or as liquid particles (particulate droplets). Solid or liquid particles can be introduced into the film from the coating liquid in their respective states. A coating liquid containing solid particles is a dispersion, and a coating liquid containing liquid particles is an emulsion.

[0026] Among these, it is particularly preferred that the organic compound A1 is a benzotriazole-based compound, particularly a compound having the structural formula described below, present as solid particles. The solid particles have an average particle size of 10 nm or more and 150 nm or less, and particularly preferably 15 nm or more and 35 nm or less.

[0027] The "average particle size" can be defined as a measurement value obtained by dynamic light scattering, a type of photon correlation spectroscopy; specifically, as the particle size at which the cumulative frequency is 50% in a volume-based distribution of equivalent sphere diameters. The average particle size before dispersion in a film can be measured, for example, using a Nikkiso Microtrac Ultrafine Particle Size Distribution Meter 9340-UPA150. The average particle size of particles dispersed in a film can be measured using a scanning electron microscope (SEM) or a transmission electron microscope (TEM). The average value a of the top 10% of the maximum lengths of each particle present in the film cross section observed by SEM or TEM does not fall below the value of the "average particle size" defined above. Therefore, if the average value a is 150 nm or less, the "average particle size" can be considered to be 150 nm or less. Furthermore, the average value b of the bottom 10% of the lengths in the direction perpendicular to the direction defining the maximum length of each particle present in the film cross section does not exceed the value of the "average particle size" defined above. Therefore, for example, if the average value b is 50 nm or more, the "average particle size" may be considered to be 50 nm or more.

[0028] (Organic Substance B / Light Stabilizer) The light stabilizer may function as a radical scavenger. Unlike a silane coupling agent, the light stabilizer does not need to contain a silicon atom.

[0029] The light stabilizer may be a hindered amine light stabilizer (hereinafter, sometimes referred to as "HALS"). HALS generates a nitroxy radical (-NO.) when oxidized, and this radical functions as an active species to neutralize degradation factors. The mechanism of detoxification is generally presumed to be as follows: When a nitroxy radical captures, for example, an alkyl radical (R.), it transforms into an amino ether (RON). The amino ether captures a peroxide radical (ROO.) generated by the reaction of an alkyl radical with oxygen in the air, generating a ketone (R=O) and an alcohol (ROH) that do not contribute to the decomposition of organic substances, while also returning to a nitroxy radical. In this way, HALS functions as a radical scavenger and can contribute to the suppression of cracking in functional films.

[0030] Specifically, HALS are secondary or tertiary amines in which the carbon atom adjacent to the amino group is substituted with an alkyl group to sterically protect the amino group. HALS may be a compound containing a heterocyclic structure, particularly a piperidine structure, and more specifically, a compound having a 2,2,6,6-tetraalkylpiperidine structure, particularly a 2,2,6,6-tetramethylpiperidine structure. HALS may be a compound represented by formula (1):

[0031]

[0032] In formula (1), R 1 is an oxy radical, a hydrogen atom, a hydroxy group, or an alkyl group, hydroxyalkyl group, hydroxyalkoxy group, or alkoxy group having 1 to 30 carbon atoms; R 2 From R 5 are independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, such as a methyl group, and R x is any organic group, and n is 0 or 1. More specifically, the HALS may be a compound represented by the following formulas (2) to (5).

[0033]

[0034] In formulas (2) to (5), R 1~R 5 and n are the same as above, and R 6 is a hydrogen atom, or an alkyl group, acyl group, or aryl group having 1 to 10 carbon atoms; R 7 and R 8 are independently a hydrogen atom, or an alkyl group, acyl group, or aryl group having 1 to 10 carbon atoms; R 9 From R 11 are independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an acyl group, an amino group, an alkoxy group, a hydroxy group, or an aryl group, and R 12 is a hydrogen atom, or an alkyl group having 1 to 10 carbon atoms, an amino group, an alkoxy group, a hydroxy group, or an aryl group.

[0035] The HALS may be any of the following exemplary compounds: 2,2,6,6-tetramethyl-4-piperidone; 2,2,6,6-tetramethyl-4-piperidinol; bis-(1,2,2,6,6-pentamethylpiperidyl)-(3',5'-di-t-butyl-4'-hydroxybenzyl)butylmalonate; di-(2,2,6,6-tetramethyl-4-piperidyl)sebacate (Tinuvin® 770, MW 481); oligomer of N-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-piperidinol and succinic acid (T Tinuvin® 622); oligomer of cyanuric acid and N,N-di(2,2,6,6-tetramethyl-4-piperidyl)-hexamethylenediamine; bis-(2,2,6,6-tetramethyl-4-piperidinyl)succinate; bis-(1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl)sebacate (Tinuvin® 123); bis-(1,2,2,6,6-pentamethyl-4-piperidinyl)sebacate (Tinuvin® 765); Tinuvin® 144; Tinuvin® tetrakis-(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate; N,N'-bis-(2,2,6,6-tetramethyl-4-piperidyl)-hexane-1,6-diamine (Chimasorb® T5); N-butyl-2,2,6,6-tetramethyl-4-piperidinamine; 2,2'-[(2,2,6,6-tetramethyl-piperidinyl)-imino]-bis-[ethanol]; poly((6-morpholine-triazine-2,4-diyl)(2,2,6,6-tetramethyl) 5-(2,2,6,6-tetramethyl-4-piperidinyl)-iminohexamethylene-(2,2,6,6-tetramethyl-4-piperidinyl)-imino) (Cyasorb® UV3346); 5-(2,2,6,6-tetramethyl-4-piperidinyl)-2-cyclo-undecyl-oxazole) (Hostavin® N20); 1,1'-(1,2-ethane-di-yl)-bis-(3,3',5,5'-tetramethyl-piperazinone); 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro(4,5)decane-2,4-dione;Polymethylpropyl-3-oxy-[4(2,2,6,6-tetramethyl)-piperidinyl]siloxane (Uvasil® 299); 1,2,3,4-butanetetracarboxylic acid-1,2,3-tris(1,2,2,6,6-pentamethyl-4-piperidinyl)-4-tridecyl ester; copolymer of α-methylstyrene-N-(2,2,6,6-tetramethyl-4-piperidinyl)maleimide and N-stearylmaleimide; 1,2,3,4-butanetetracarboxylic acid, β,β,β',β'-tetramethyl-2,4,8 ,10-tetraoxaspiro[5.5]undecane-3,9-diethanol, 1,2,2,6,6-pentamethyl-4-piperidinyl ester polymer (Mark® LA63); 2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-diethanol, 1,2,3,4-butanetetracarboxylic acid, 2,2,6,6-tetramethyl-4-piperidinyl ester, β,β,β',β'-tetramethyl-polymer (Mark® LA68); D-glucitol, 1,3:2,4-bis-O-(2,2 ,6,6-tetramethyl-4-piperidinylidene)-(HALS7); oligomer of 7-oxa-3,20-diazadispiro[5.1.11.2]-heneicosan-21-one-2,2,4,4-tetramethyl-20-(oxiranylmethyl) (Hostavin® N30); propanedioic acid, [(4-methoxyphenyl)methylene]-, bis(1,2,2,6,6-pentamethyl-4-piperidinyl) ester (Sanduvor® PR31); formamide, N,N'-1,6-hexanediylbis[N-( 2,2,6,6-tetramethyl-4-piperidinyl)] (Uvinul® 4050H); 1,3,5-triazine-2,4,6-triamine, N,N′″-[1,2-ethanediylbis[[4,6-bis[butyl(1,2,2,6,6-pentamethyl-4-piperidinyl)amino]-1,3,5-triazin-2-yl]imino]-3,1-propanediyl]-bis[N′,N″-dibutyl-N′,N″-bis(1,2,2,6,6-pentamethyl-4-piperidinyl)] (Chimassorb® 119 MW 2286);Poly[[6-[(1,1,3,3-tetramethylbutyl)amino]-1,3,5-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidinyl)-imino]-1,6-hexanediyl[(2,2,6,6-tetramethyl-4-piperidinyl)imino]] (Chimassorb® 944 MW 2000-3000); 1,5-dioxaspiro(5,5)undecane-3,3-dicarboxylic acid, bis(2,2,6,6-tetramethyl-4-peridinyl) ester (Cyasorb® UV-500); 1,5-dioxaspiro(5,5)undecane-3,3-dicarboxylic acid, bis(1,2,2,6,6-pentamethyl-4-peridinyl) ester (Cyasorb® UV-516); N-2, 2,6,6-tetramethyl-4-piperidinyl-N-amino-oxamide; 4-acryloyloxy-1,2,2,6,6-pentamethyl-4-piperidine; 1,5,8,12-tetrakis[2',4'-bis(1'',2'',2'',6'',6''-pentamethyl-4''-piperidinyl(butyl)amino)-1',3',5'-triazin-6'-yl]-1,5,8,12-tetraazadodecane; HALS PB-41 (Clariant Huningue S.A.); Nylostab® S-EED (Clariant Huningue S.A.); 3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidyl)-pyrrolidine-2,5-dione; Uvasorb® HA88; 1,1'-(1,2-ethane-di-yl)-bis-(3,3',5,5'-tetra-methyl-piperazinone) (Good-rite® 3034); 1,1'1''-(1,3,5-triazine-2,4,6-triyltris((cyclohexyl) 1,1',1''-(1,3,5-triazine-2,4,6-triyltris((cyclohexylimino)-2,1-ethanediyl)tris(3,3,4,5,5-tetramethylpiperazinone)) (Good-rite® 3159);

[0036] HALS can be detected by electron spin resonance (ESR) using the generation of nitroxy radicals (-NO.), and the content in the film can be estimated. When forming a functional film, it is possible and preferable to incorporate a light stabilizer such as HALS into a coating liquid such as a dispersion of an organic substance in advance.

[0037] The content of the light stabilizer (organic substance B) is suitably, for example, 1.0 part by mass or more and 50 parts by mass or less relative to 100 parts by mass of organic substance A. The content of the light stabilizer may be 1.5 parts by mass or more, 2.0 parts by mass or more, or even 3.0 parts by mass or more, and in some cases 5.0 parts by mass or more relative to 100 parts by mass of organic substance A.

[0038] (Other Components) The functional film may contain other components, such as components derived from a silane coupling agent.

[0039] Other components can be added by selecting them appropriately depending on the function of the functional film, in other words, the type of organic substance A. For example, a functional film containing an organic substance A that is not a polymer may contain a polymer P as another compound. The polymer P contributes to improving the dispersibility of the organic substance A and can also suppress deterioration of the organic substance A. Furthermore, when forming a relatively thick functional film (for example, a thickness of more than 300 nm, and in some cases 500 nm or more) by a liquid phase film formation method such as a sol-gel method, the polymer P is also a component that facilitates the formation of a thick film while suppressing the occurrence of cracks.

[0040] The polymer P may be hydrophilic or hydrophobic. The polymer P may be at least one selected from the group consisting of polyether compounds, polyol compounds, polyvinylpyrrolidones, polyvinylcaprolactams, and acrylic copolymers. The polyether compounds are compounds containing two or more ether bonds. The polyol compounds are compounds containing two or more hydroxy groups. The polyvinylpyrrolidones are polymers containing vinylpyrrolidone and its derivatives as monomers. The polyvinylcaprolactams are polymers containing vinylcaprolactam and its derivatives as monomers. Specifically, the polymer P may be a polyether surfactant or a polyol compound produced by reaction of the epoxy group of a polyepoxy compound. Examples of the polymer P include polycaprolactone polyol, bisphenol A polyol, polyethylene glycol, polypropylene glycol, polyoxyalkylene derivatives, and controlled polymerization acrylic copolymers.

[0041] The functional film may contain a component derived from a silane coupling agent. The solution for forming the functional film, i.e., the film-forming solution, may contain a silane coupling agent. The silane coupling agent may be represented by the formula LSiM3. Here, L is an organic group containing at least one selected from the group consisting of a vinyl group, a glycidoxy group, a methacryl group, an amino group, and a mercapto group. M is a halogen element or an alkoxy group. In the silane coupling agent, the L group reacts with organic substances in the film, and the M group hydrolyzes and reacts with inorganic substances in the film. Through these reactions, the silane coupling agent can contribute to improving the dispersibility of organic substances in the film.

[0042] The portion represented by -SiM3 in the silane coupling agent is present in the film after changing to a -Si(-O-)3 structure. 1.5 and constitutes part of the inorganic substance. On the other hand, the part represented by L- usually constitutes part of the organic substance after reacting with an organic substance depending on its type. In the functional film, part of the inorganic substance and organic substance may be derived from the silane coupling agent.

[0043] <Characteristics of functional film> (Functional film as ultraviolet shielding film / ultraviolet shielding properties) When the functional film is an ultraviolet shielding film, the glass substrate with the functional film has an ultraviolet transmittance T UV The glass substrate with a functional film can have an ultraviolet transmittance T of 2% or less, preferably 1% or less, and more preferably 0.5% or less, as specified in ISO 9050:2003. UV (Hereinafter referred to as “T UV The glass substrate with a functional film may have an ultraviolet transmittance of 2.5% or less, preferably 1.3% or less, and more preferably 0.7% or less, as measured by the YA method (hereinafter referred to as "CIE Standard A illuminant"). The glass substrate with a functional film may have a visible light transmittance of 70% or more, as measured by the YA method (hereinafter referred to as "YA"), as measured using the CIE Standard A illuminant.

[0044] When the functional film is an ultraviolet-shielding film, the glass substrate with the functional film has a low ΔT UV ΔT UV is the above T specified in ISO9050:1990 UV When the functional film is an ultraviolet ray blocking film, the glass substrate with the functional film has a low ΔT UV (2003). UV is the above T specified in ISO9050:2003 UV (2003) is the change amount.

[0045] In an accelerated weathering tester, simulated sunlight from a carbon arc lamp was irradiated at a black panel temperature of 83±2°C, a relative humidity of 55±5%, and an illuminance of 78.5 W / m with a wavelength of 300 to 400 nm. 2 After irradiating the surface of the glass substrate opposite to the functional film for 2000 hours under the conditions of UV can be 0.45% or less, 0.40% or less, 0.35% or less, or even 0.30% or less, and in some cases 0.25% or less. After irradiation under similar conditions, ΔT UV (2003) can be 0.60% or less, 0.45% or less, 0.30% or less, or even 0.25% or less.

[0046] In an accelerated weathering tester, light from a xenon arc lamp was irradiated at a black panel temperature of 83±2°C, a relative humidity of 50%, and an illuminance of 150 W / m with a wavelength of 300 to 400 nm. 2 After irradiating the functional film side for 300 hours under the conditions of UV can be 4.0% or less, 3.0% or less, 2.0% or less, in some cases 1.5% or less, particularly 1.0% or less. After irradiation under similar conditions, ΔT UV (2003) can be 6.0% or less, 3.0% or less, 2.0% or less, or even 1.5% or less.

[0047] (Crack prevention properties) In an accelerated weathering tester, light from a xenon arc lamp was irradiated at a black panel temperature of 83±2°C, a relative humidity of 50%, and an illuminance of 150 W / m at a wavelength of 300 to 400 nm. 2 Under the conditions above, after 300 hours of irradiation from the side on which the functional film is formed, no cracks can be observed in the functional film. Here, the presence or absence of cracks is confirmed by irradiating the functional film with a high-intensity lamp as described in the Examples section and visually observing it.

[0048] <Glass Substrate> The glass substrate is not particularly limited, and for example, soda-lime silicate glass can be used. From the viewpoint of further improving the ultraviolet shielding property, a glass substrate containing 0.2% or more, 0.4% or more, or in some cases 0.6% or more of T-Fe2O3 by mass may be used. As is well known, T-Fe2O3 is total iron oxide converted to Fe2O3. The glass substrate is typically a glass plate, but is not limited thereto and may have a shape other than a plate.

[0049] <Formation of Functional Film> A functional film can be formed on a glass substrate by a known liquid-phase film formation method, specifically a sol-gel method. The coating liquid for forming the film may contain, in addition to organic substance A and organic substance B, a metal alkoxide such as silicon alkoxide as a component for generating an inorganic substance (inorganic substance precursor). As described above, the inorganic substance may contain silicon oxide, and the inorganic substance precursor may be a silicon oxide precursor, typified by silicon alkoxide. The coating liquid may further contain a silane coupling agent. As described in the next paragraph, the coating liquid may further contain a dispersion medium and a dispersant. The functional film can be obtained by a manufacturing method including applying the coating liquid to a glass substrate and drying the applied coating liquid.

[0050] When adding organic substance A as particles, the following method can be used. First, a dispersion containing organic substance A as a dispersoid is prepared, and this is mixed with the inorganic substance and silane coupling agent described above to form a coating liquid (application liquid), which is then applied to a glass substrate to produce a glass substrate having a functional film. However, an inorganic substance precursor may be used together with or instead of the inorganic substance. To prepare such a dispersion of organic substance A, it is preferable to mix at least organic substance A, a dispersion medium containing lower alcohol and water as main components (which may be 100% lower alcohol and water), and a dispersant, and wet-pulverize the organic compound A to the above-mentioned average particle size using a media mill or the like. As the lower alcohol, an alcohol having 1 to 3 carbon atoms is suitable. In this case, the presence of a dispersant is preferable in order to prepare a stable coating liquid dispersed to a preferred particle size. As the dispersant, one or more surfactants or polymer dispersants such as those described in JP 2022-115764 can be selected and used, and it is preferred. The surfactant is not particularly limited, but a polyoxyalkylene derivative is preferred. The HLB of the surfactant may be 9 to 16, preferably 11 to 15, and particularly 13.2. The surfactant may have 1 to 3 benzyl groups, or 1 to 3 benzyl groups may be bonded to any portion of the phenyl ether group. The polymer dispersant is not particularly limited, but the aforementioned polymer P can also be used, and an acrylic copolymer obtained by controlled polymerization is particularly preferred. Furthermore, a dispersion containing a light stabilizer in addition to the organic substance A, dispersion medium, and dispersant can be prepared, and the liquid properties of the coating liquid and the performance of the resulting film are particularly high, which is preferred. The blending ratio of these components is such that the content of the organic substance such as organic substance A in the dispersion is 5 to 20% by mass, particularly 8 to 12% by mass, and of these 10% by mass is preferred; the content of the polymer dispersant is 1 to 100 parts by mass, particularly 50 to 90 parts by mass, and even more preferably 75 to 85 parts by mass, and of these 80 parts by mass, per 100 parts by mass of the organic substance such as organic substance A; and the content of the surfactant is 1 to 100 parts by mass, particularly 5 to 40 parts by mass, and even more preferably 10 to 30 parts by mass, and of these 20 parts by mass, per 100 parts by mass of the organic substance such as organic substance A.By using such a dispersion of an organic substance, particularly a dispersion of organic substance A containing organic substance A and a light stabilizer and dispersed with an average particle size of 150 nm or less, it is possible to obtain a glass substrate in which organic substance A and light stabilizer are relatively uniformly present in the functional film and which exhibits excellent performance. The particle size of organic substance A in the dispersion can be measured using the dynamic light scattering method described above.

[0051] <Thickness of Functional Film> The thickness of the functional film may be adjusted appropriately depending on the function to be imparted. When the functional film is an ultraviolet ray blocking film, the thickness may be more than 300 nm and not more than 15 μm, further 500 nm or more and not more than 10 μm, particularly 1000 nm or more and not more than 5000 nm.

[0052] <Examples of Organic Compound A1> Examples of organic compound A1 that is particularly suitable for addition as solid particles include benzotriazole compounds. The benzotriazole-based compound may have the structure shown below.

[0053]

[0054] In the formula, R1 and R1' may be the same or different and are a hydrogen atom, a halogen atom, a nitro group, a cyano group, a perfluoroalkyl group having 1 to 12 carbon atoms, an RSO- group, or an R0- group. R2 and R2' may be the same or different and are an alkyl group having 1 to 12 carbon atoms, an alkyl group having 1 to 12 carbon atoms in which a hydrogen atom is substituted with a COH group, a phenyl group, a phenylalkyl group containing 1 to 4 carbon atoms in the alkyl group moiety, or a cycloalkyl group having 5 to 8 carbon atoms. R2 and R2' are preferably alkyl groups having 1 to 12 carbon atoms. A tert-octyl group is most preferred. R3 is an alkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 2 to 20 carbon atoms, an alkyl group having 2 to 9 carbon atoms in which a hydrogen atom is substituted with an alkoxycarbonyl group having 2 to 9 carbon atoms, an alkenyl group having 3 to 18 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, a phenylalkyl group having 7 to 15 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aryl group in which a hydrogen atom is substituted with one or two alkyl groups having 1 to 4 carbon atoms, or a 1,1,2,2-tetrahydroxyperfluoroalkyl group (the perfluoroalkyl portion of this group contains 6 to 16 carbon atoms). In particular, from the viewpoint of ultraviolet absorption performance, R1 and R1' are preferably hydrogen atoms or halogen atoms. More preferably, they are halogen atoms. Most preferably, they are chlorine atoms. Among these compounds, the compound in which R1 and R1' are chlorine atoms and R2 and R2' are tert-octyl groups, i.e., 2,2'-methylenebis[6-(5-chloro-benzotriazol-2-yl)-4-tert-octylphenol], is most preferred.

[0055] (Example) A glass substrate with a functional film was produced and evaluated. An ultraviolet-shielding film was formed as the functional film. The evaluation items were as follows.

[0056] <Optical Properties> Optical properties were measured using a spectrophotometer (Shimadzu Corporation, UV-3100PC). The measured properties were ultraviolet transmittance T UV is.

[0057] <Light resistance (ultraviolet light resistance characteristics)> The following two types of tests were carried out. (First test / irradiation from glass surface) The first test was a test in which light was irradiated from the surface of a glass substrate on which no functional film was formed. In this test, an accelerated weathering tester, specifically a Sunshine Weather Meter S80B manufactured by Suga Test Instruments Co., Ltd., was used. The light source used was a carbon arc lamp. The measurement conditions were an illuminance of 78.5 W / m2 at a wavelength of 300 to 400 nm. 2 The black panel temperature was 83±2°C, and the relative humidity was 55±5%. Each sample was irradiated with simulated sunlight from a carbon arc lamp from the front side of the glass substrate for a predetermined time, and the ultraviolet transmittance T defined in ISO 9050:1990 was measured. UV Regarding T after irradiation UV From T before irradiation UV Subtracting ΔT UV The ultraviolet transmittance T stipulated in ISO 9050:2003 was calculated. UV For 2003, T after irradiation UV T before irradiation from 2003 UV Subtract 2003, ΔT UV 2003 was calculated.

[0058] (Second Test / Irradiation from the Film Surface) The second test is a test in which light is irradiated from the side where the functional film is formed. In this test, an accelerated weathering tester, specifically, a Super Xenon Weather Meter SX75 manufactured by Suga Test Instruments Co., Ltd., was used. The light source used was a xenon lamp. The measurement conditions were an illuminance of 150 W / m at a wavelength of 300 to 400 nm. 2 The black panel temperature was 83±2°C and the relative humidity was 50%. Light from a xenon lamp was irradiated for a predetermined time, and the ultraviolet transmittance T stipulated in ISO 9050:1990 was measured. UV Regarding T after irradiation UV From T before irradiation UV Subtracting ΔT UV The ultraviolet transmittance T stipulated in ISO 9050:2003 was calculated. UV For 2003, T after irradiation UV T before irradiation from 2003 UV Subtract 2003, ΔT UV 2003 was calculated.

[0059] In the second test, the functional film was visually observed after the irradiation test to determine which of the following conditions it fell into. The high-intensity lamp used was an ultra-high-intensity inspection lighting device (ULTRA INTENSITY HALOGEN-LIGHT) "UIH-1H" manufactured by Intex Co., Ltd. ◎: No film peeling. No cracks were observed in the film even when irradiated with a high-intensity lamp. ○: No film peeling. Cracks could be observed in the film when irradiated with a high-intensity lamp. △: No film peeling. Many cracks could be observed in the film under fluorescent light. ×: Film peeling could be observed.

[0060] <Preparation of Glass Substrates with Functional Films> The glass substrates with ultraviolet-shielding films to be evaluated (Samples 1 to 5) were prepared as follows. A benzotriazole-based ultraviolet absorber (2,2'-methylenebis[6-(5-chloro-benzotriazol-2-yl)-4-tert-octylphenol]) was used as the ultraviolet (UV)-shielding agent, organic compound A1. Specifically, a dispersion containing organic compound A1 and water as the dispersion medium (UV-shielding component content: 10 wt %, average particle size: 100 nm) was prepared. Organic compound A1 was prepared by mixing and pulverizing a control-polymerized acrylic copolymer, a polyoxyalkylene derivative, and water with zirconia beads using a paint conditioner to achieve the above-mentioned average particle size. Specifically, a dispersion containing organic compound A1 and water as the dispersion medium (UV-shielding component content: 10 wt %, average particle size: 100 nm) was prepared. The organic compound A1 was previously mixed with zirconia beads and pulverized using a paint conditioner to obtain the above average particle size. Furthermore, for preparing the film-forming solutions of each sample other than Sample 1, a dispersion to which a hindered amine light stabilizer (HALS) was further added as a radical scavenger was used. Furthermore, for preparing the film-forming solutions of each sample other than Sample 1, a dispersion to which a hindered amine light stabilizer (HALS) was further added as a radical scavenger was used. These dispersions were mixed and stirred with pure water, ethyl alcohol, tetraethoxysilane (TEOS), glycidoxypropyltrimethoxysilane (GPTMS; 3-glycidyloxypropyltrimethoxysilane), a polyol compound, triethylene glycol (TEG), a polyether compound, a polyether phosphate ester polymer (SOL), an ITO fine particle dispersion (average particle size of 100 nm or less), and concentrated hydrochloric acid (35% by mass) to obtain a coating solution.

[0061] In the coating solutions of Samples 1 to 5, only the parts by mass of the light stabilizer relative to 100 parts by mass of the UV screening agent was changed as shown in Table 1.

[0062] Next, the coating solution was applied to a cleaned soda-lime silicate glass substrate (UV-cut green glass manufactured by Nippon Sheet Glass, 100 x 100 mm, thickness 2.8 mm) using a flow coating method at 30% humidity and room temperature. After drying, the substrate was placed in a heated oven and heated, then cooled to form a functional film. The above measurements were carried out on the film-coated glass substrate thus obtained. The results are shown in Tables 2 to 4.

[0063]

[0064]

[0065]

[0066]

[0067] The UV screening agent was dispersed in the film in a manner that could be considered to have an average particle size of 150 nm or less. The film thickness of each sample was in the range of 1 to 5 μm. Each sample had a T of 2% or less before light exposure (irradiation time 0). UV , 2.5% or less T UV 2003. For Samples 2 to 5 containing a light stabilizer, no cracks were observed in the film even after 300 hours of rigorous testing in which the film surface was irradiated with ultraviolet light. In particular, for Samples 3 to 5, i.e., samples containing a sufficient amount of light stabilizer (organic substance B), no cracks were observed in the film even after 400 hours of irradiating the film surface with ultraviolet light.

[0068] As explained above, the present disclosure provides the following technologies: (Technology A1) A glass substrate with a functional film, comprising: a glass substrate; and a functional film on the glass substrate, wherein the functional film contains: an inorganic substance, an organic substance A that imparts at least one function selected from the group consisting of ultraviolet shielding, infrared absorption, anti-fogging, water repellency, and dimming properties to the functional film, and an organic substance B that is a light stabilizer that suppresses deterioration of the functional film due to ultraviolet irradiation.

[0069] (Technology A2) The glass substrate with a functional film according to Technology A1, wherein the at least one function includes an ultraviolet ray shielding property.

[0070] (Technology A3) T at a wavelength of 380 nm specified in ISO 9050:1990 UV The functional film-coated glass substrate according to Technology A2, wherein 380 is 2% or less.

[0071] (Technology A4) In an accelerated weathering tester, simulated sunlight from a carbon arc lamp was irradiated at a black panel temperature of 83±2°C, a relative humidity of 55±5%, and an illuminance of 78.5 W / m at a wavelength of 300 to 400 nm. 2 After irradiating the glass substrate from the surface side opposite to the functional film for 2000 hours under the conditions of UV The change in ΔT UV The functional film-attached glass substrate according to Technology A2, wherein the content of the functional film is 0.45% or less.

[0072] (Technology A5) In an accelerated weathering tester, light from a xenon arc lamp was irradiated at a black panel temperature of 83±2°C, a relative humidity of 50%, and an illuminance of 150 W / m with a wavelength of 300 to 400 nm. 2 After irradiating the functional film on the side for 300 hours under the conditions of UV The change in ΔT UV The functional film-coated glass substrate according to Technology A2, wherein the content of the functional film is 4.0% or less.

[0073] (Technology A6) In an accelerated weathering tester, light from a xenon arc lamp is irradiated at a black panel temperature of 83±2°C, a relative humidity of 50%, and an illuminance of 150 W / m with a wavelength of 300 to 400 nm. 2 A glass substrate with a functional film according to any one of Techniques A1 to A5, wherein after irradiating the functional film from the side on which the functional film is formed for 300 hours under the conditions of (a) to (c), no cracks are observed in the functional film.

[0074] (Technology A7) The functional film-provided glass substrate according to any one of Techniques A1 to A6, wherein the light stabilizer is a radical scavenger.

[0075] (Technology A8) The glass substrate with a functional film according to any one of Techniques A1 to A7, wherein the light stabilizer does not contain silicon atoms.

[0076] (Technology A9) The functional film-provided glass substrate according to any one of Techniques A1 to A8, wherein the light stabilizer includes a hindered amine-based light stabilizer.

[0077] (Technology A10) The glass substrate with a functional film according to any one of Technologies A1 to A9, wherein the content of the light stabilizer is 1.0 part by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the organic substance A.

[0078] The present disclosure also provides the following technology regarding a coating liquid: Hereinafter, the coating liquid is a dispersion containing organic compound A1 as particles, particularly solid particles.

[0079] (Technology B1) A dispersion for application to a glass substrate, containing at least (i) at least one organic compound selected from the group consisting of benzotriazole-based compounds, benzophenone-based compounds, triazine-based compounds, benzodithiol-based compounds, azomethine-based compounds, and indole-based compounds as an organic compound A1 having ultraviolet screening properties, (ii) a dispersion medium, and (iii) a light stabilizer, wherein the organic compound exists as particles. However, Technology B1 can be rewritten as follows: A dispersion for application to a glass substrate, containing at least (i) at least one organic compound selected from the group consisting of benzotriazole-based compounds, benzophenone-based compounds, triazine-based compounds, benzodithiol-based compounds, azomethine-based compounds, and indole-based compounds as an organic compound A1 having ultraviolet screening properties, (ii) a dispersion medium, (iii) a dispersant, and (iv) a light stabilizer, wherein the organic compound exists as particles.

[0080] (Technology B2) The dispersion for application to a glass substrate according to Technology B1, wherein the organic compound is a benzotriazole-based compound.

[0081] (Technology B3) The dispersion for application to a glass substrate according to Technology B2, wherein the organic compound is a compound represented by the following formula (I):

[0082]

[0083] In formula (I), R1 and R1' may be the same or different and are a hydrogen atom, a halogen atom, a nitro group, a cyano group, a perfluoroalkyl group having 1 to 12 carbon atoms, an R3SO- group, or an R3O2- group. R2 and R2' may be the same or different and are an alkyl group having 1 to 12 carbon atoms, an alkyl group having 1 to 12 carbon atoms in which a hydrogen atom is substituted with a CO2H group, a phenyl group, a phenylalkyl group containing 1 to 4 carbon atoms in the alkyl moiety, or a cycloalkyl group having 5 to 8 carbon atoms. R3 is C1-C20 alkyl, C2-C20 hydroxyalkyl, C2-C9 alkyl in which hydrogen atoms are substituted by C2-C9 alkoxycarbonyl, C3-C18 alkenyl, C5-C12 cycloalkyl, C7-C15 phenylalkyl, C6-C10 aryl, or the above aryl in which hydrogen atoms are substituted by one or two C1-C alkyl groups, or 1,1,2,2-tetrahydroxyperfluoroalkyl (the perfluoroalkyl portion of this group contains from 6 to 16 carbon atoms).

[0084] (Technology B4) The dispersion for application to a glass substrate according to Technology B3, wherein the organic compound is a compound in which R1 and R1' in the formula (I) are chlorine atoms, and R2 and R2' are tert-octyl groups.

[0085] (Technology B5) The dispersion for application to a glass substrate according to any one of Techniques B1 to B4, wherein the organic compound is in the form of particles having an average particle size of 150 nm or less.

[0086] (Technology B6) The dispersion for application to a glass substrate according to Technology B5, wherein the organic compound is a particle having an average particle size of 150 nm or less, and the light stabilizer includes a hindered amine light stabilizer.

[0087] (Technology B7) A method for producing a glass plate with a functional film, comprising: mixing a dispersion containing at least (i) at least one organic compound selected from the group consisting of benzotriazole-based compounds, benzophenone-based compounds, triazine-based compounds, benzodithiol-based compounds, azomethine-based compounds, and indole-based compounds, (ii) a dispersion medium, and (iii) a light stabilizer with at least one selected from the group consisting of an inorganic substance, an inorganic substance precursor, and a silane coupling agent to prepare a coating liquid, which is then applied to a glass plate and dried. However, Technology B7 can be rewritten as follows: A method for producing a glass plate with a functional film, comprising: mixing a dispersion containing at least one organic compound selected from the group consisting of (i) benzotriazole-based compounds, benzophenone-based compounds, triazine-based compounds, benzodithiol-based compounds, azomethine-based compounds, and indole-based compounds, (ii) a dispersion medium, (iii) a dispersant, and (iv) a light stabilizer with at least one selected from the group consisting of an inorganic substance, an inorganic substance precursor, and a silane coupling agent to prepare a coating liquid, which is then applied to a glass plate and dried. Furthermore, Technology B7 can also be rewritten as follows: A method for producing a glass plate with a functional film, comprising applying to a glass plate a coating liquid containing at least (i) at least one organic compound A1 selected from the group consisting of benzotriazole-based compounds, benzophenone-based compounds, triazine-based compounds, benzodithiol-based compounds, azomethine-based compounds, and indole-based compounds, (ii) a dispersion medium, (iii) a dispersant, (iv) a light stabilizer, and (v) at least one selected from the group consisting of inorganic substances, inorganic substance precursors, and silane coupling agents, and drying the coating liquid.

Claims

1. A glass substrate with a functional film, comprising: a glass substrate; and a functional film on the glass substrate, the functional film comprising: an inorganic substance; an organic substance A that imparts to the functional film at least one function selected from the group consisting of ultraviolet shielding, infrared absorbing, anti-fogging, water repellency, and light control; and an organic substance B that is a light stabilizer that suppresses deterioration of the functional film due to exposure to ultraviolet light.

2. The glass substrate with a functional film according to claim 1, wherein the at least one function includes an ultraviolet ray shielding property.

3. Ultraviolet transmittance T as specified in ISO9050:1990 UV The functional film-coated glass substrate according to claim 2 , wherein the functional film-coated glass substrate has a thickness of 2% or less.

4. In an accelerated weathering tester, simulated sunlight from a carbon arc lamp was applied to the black panel at a temperature of 83±2°C, a relative humidity of 55±5%, and an illuminance of 78.5 W / m2 with a wavelength of 300 to 400 nm. 2 After irradiating the glass substrate from the surface side opposite the functional film for 2000 hours under the above conditions, the ultraviolet transmittance T defined in ISO9050:1990 was UV The change in ΔT UV The functional film-attached glass substrate according to claim 2 , wherein the content of the functional film is 0.45% or less.

5. In an accelerated weathering tester, light from a xenon arc lamp is irradiated at a black panel temperature of 83±2°C, relative humidity of 50%, and an illuminance of 150 W / m2 with a wavelength of 300 to 400 nm. 2 After irradiating the functional film on the side for 300 hours under the above conditions, the ultraviolet transmittance T UV The change in ΔT UV The functional film-coated glass substrate according to claim 2 , wherein the functional film-coated glass substrate has a viscosity of 4.0% or less.

6. In an accelerated weathering tester, light from a xenon arc lamp is irradiated at a black panel temperature of 83±2°C, relative humidity of 50%, and an illuminance of 150 W / m2 with a wavelength of 300 to 400 nm. 2 2. The glass substrate with a functional film according to claim 1, wherein after irradiation for 300 hours from the side on which the functional film is formed under the above-mentioned conditions, no cracks are observed in the functional film.

7. The functional film-attached glass substrate according to claim 1, wherein the light stabilizer is a radical scavenger.

8. The glass substrate with a functional film according to claim 1, wherein the light stabilizer does not contain a silicon atom.

9. The functional film-attached glass substrate according to claim 1, wherein the light stabilizer includes a hindered amine-based light stabilizer.

10. The functional film-attached glass substrate according to claim 1, wherein the content of the light stabilizer is 1.0 part by mass or more and 50 parts by mass or less per 100 parts by mass of the organic substance A.

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