Glass substrate with functional film

Abstract

To provide a novel glass substrate with a functional film that can inhibit film degradation during a manufacturing process without requiring the silylation of organic substances.SOLUTION: A glass substrate 1 with a functional film is provided which comprises a glass substrate 1 and a functional film 2 on the glass substrate 1. The functional film 2 includes: an inorganic substance; an organic substance A for imparting, to the functional film 2, at least one function selected from the group consisting of ultraviolet shielding, infrared absorption, fog resistance, water repellency and light modulation; and an organic substance B that is a light stabilizer for inhibiting deterioration due to ultraviolet irradiation of the functional film 2.SELECTED DRAWING: Figure 1

Description

[Technical field]

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

[0002] Various functions are required to be added to glass substrates, such as glass plates. For example, in the use of window glass for vehicles, such as automobiles, there is a high demand for glass substrates with ultraviolet shielding properties, due to the need to prevent sunburn. For this reason, glass substrates are known that have a functional film formed thereon to which an organic ultraviolet shielding component is added in order to sufficiently 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 light control properties. Depending on the required functions, the functional film may contain various organic substances.

[0003] Functional films containing organic substances may lose their function or may be altered due to long-term use. A typical example of film alteration is the occurrence of cracks. In order to address this problem, Patent Document 1 discloses a technology that uses a silylated benzophenone-based compound as an ultraviolet shielding component. The silylated ultraviolet shielding component reacts with other silane compounds and is incorporated into the Si-O network composed of silicon atoms and oxygen atoms in the functional film. In other words, in the technology disclosed in Patent Document 1, the organic substance is included in the functional film in a state integrated with the inorganic substance, and the occurrence of cracks is suppressed. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] International Publication No. 2010 / 131744 Summary of the Invention [Problem to be solved by the invention]

[0005] The technique disclosed in Patent Document 1 requires silylation of an organic substance, and therefore cannot be applied to organic substances that are not suitable for silylation, or brings about undesirable changes in the properties of the organic substance, and even if these circumstances are not present, the manufacturing process becomes complicated. Therefore, the present invention aims to provide a new glass substrate with a functional film that can suppress the occurrence of cracks in the film without requiring silylation of an organic substance in the manufacturing process. [Means for solving the problem]

[0006] Since cracks do not occur in a film composed only 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 the occurrence of cracks in the functional film. However, according to the inventor's investigation, unexpectedly, the occurrence of cracks in the functional film is suppressed by adding organic substance B, which corresponds to a light stabilizer.

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

[0008] From another aspect, the present invention provides a method for producing a method for manufacturing a semiconductor device comprising the steps of: The present invention provides a dispersion for application to a glass substrate, which 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 ultraviolet shielding properties, (ii) a dispersion medium, and (iii) a light stabilizer, wherein the organic compound exists as particles. Effect of the Invention

[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. [Brief description of the drawings]

[0010] [Figure 1] FIG. 1 is a cross-sectional view showing one embodiment of a glass substrate according to the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] Hereinafter, preferred embodiments of the present invention will be described, but the following description is not intended to limit the present invention to a specific embodiment. In this specification, the term "main component" means a component that occupies 50% or more by mass, and in some cases 55% or more. The term "particles" is used to include not only solid particles but also liquid particles. In addition, "room temperature" is a term that means 25°C.

[0012] The functional film-coated glass substrate of this embodiment shown in Fig. 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 undercoat film (not shown). The undercoat film 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. The functional film 2 may be vitreous. Note that vitreous means that the main component of the film is amorphous, and 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 which corresponds to a light stabilizer. These components will be described below.

[0015] <Functional membrane components> (inorganic substance) The inorganic material may contain silicon oxide. The inorganic material may be the main component of the functional film. The inorganic material may be mainly composed of silicon oxide. Silicon oxide may be the main component of the functional film. The inorganic material may contain a component other than silicon oxide, such as aluminum oxide, titanium oxide, or zirconium oxide. However, the inorganic material is not limited to oxide. The inorganic material may contain nitrides and other substances, such as polysilazane. The inorganic material may contain a functional inorganic material to supplement the function of the organic material A or to impart a function different from the function of the organic material A. An example of the functional inorganic material is indium tin oxide (ITO) fine particles. ITO fine particles are suitable for imparting infrared absorbing properties to the functional film.

[0016] (Organic substance A) The organic substance A is a substance capable of imparting at least one function selected from the group consisting of ultraviolet shielding, infrared absorbing, anti-fogging, water repellency, and light control to the film. 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 shielding properties. The organic compound A1 may include at least one 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. 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. As an ultraviolet shielding component that is solid at room temperature, a polymer obtained by polymerizing a polymerizable ultraviolet absorber is also known. However, since an ultraviolet shielding polymer is produced by polymerizing an ultraviolet absorber into which a polymerizable functional group such as a (meth)acrylic group has been introduced, the ultraviolet shielding effect is inferior to that of an ultraviolet absorber having a low molecular weight when compared per unit mass. It is preferable that the organic compound A1 is other than a polymer.

[0019] The molecular weight of the organic compound A1 may be 5000 or less, 3000 or less, 2000 or less, 1500 or less, 1300 or less, further 1200 or less, particularly 900 or less, and especially 800 or less. The molecular weight of the organic compound A1 may be 200 or more, particularly 300 or more. The organic compound A1 may not contain a silicon atom. Not limited to the organic compound A1, the organic substance A may not contain a silicon atom.

[0020] The organic substance A may be an organic compound A2 having infrared absorbing properties. The organic compound A2 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 squarium dye, a quinone compound, a diimmonium compound, and an azo compound.

[0021] The organic substance A may be an organic compound A3 having anti-fogging 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 may be, for example, an alkyl group or an aryl group. The alkyl group may be linear or branched, and may have, for example, 1 to 10 carbon atoms.

[0023] The organic substance A may be an organic compound A5 having a dimming property. 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 may 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 be a factor for improving the durability of the function of the organic substance A. From the viewpoint of suppressing the haze ratio of the film, it is preferable that the average particle size of the particles is 150 nm or less, particularly 10 nm to 150 nm. Among the organic substances A, it is particularly preferable that the organic compound A1 exists as particles. Examples of the organic compound 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, the organic substance A may be present in the film as solid particles or liquid particles (particulate droplets). The solid or liquid particles can be introduced into the film from the coating liquid in that state. 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, particularly preferably 15 nm or more and 35 nm or less.

[0027] The "average particle size" can be defined as a particle size measured by dynamic light scattering, a type of photon correlation method, specifically, a particle size with a cumulative frequency of 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 Nikkiso's "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 length 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. In addition, the average value b of the bottom 10% of the length in the direction perpendicular to the direction that defines 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" can 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"). It is known that HALS generates a nitroxy radical (-NO·) when oxidized, and this radical functions as an active species to detoxify deterioration factors. In general, the mechanism of detoxification is presumed to be as follows. When a nitroxy radical captures an alkyl radical (R·), it changes to 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, and generates a ketone (R=O) and an alcohol (ROH) that are not involved in the decomposition of organic substances, while returning to a nitroxy radical itself. In this way, HALS functions as a radical scavenger and can contribute to the suppression of cracks in functional films.

[0030] Specifically, HALS is a secondary or tertiary amine in which the carbon 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, 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] [ka]

[0032] In formula (1), R 1 is an oxy radical, a hydrogen atom, a hydroxy group, or an alkyl group, a hydroxyalkyl group, a hydroxyalkoxy group, or an 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; R x is any organic group, and n is 0 or 1. More specifically, HALS may be a compound represented by the following formulas (2) to (5).

[0033] [ka]

[0034] In formulas (2) to (5), R 1 ~R 5 and n are as above, 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 each independently a hydrogen atom, or an alkyl group, an acyl group, or an aryl group having 1 to 10 carbon atoms; R 9 From R 11 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an acyl group, an amino group, an alkoxy group, a hydroxyl 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 hydroxyl 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); N-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-piperidinol and succinic acid oligomers (T inuvin® 622; oligomers 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 -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; α-methylstyrene-N-(2,2,6,6-tetramethyl-4-piperidinyl)maleimide and N-stearylmaleimide copolymer; 1,2,3,4-butanetetracarboxylic acid, β,β,β',β'-tetramethyl-2,4,8 ,10-Tetraoxaspiro[5.5]undecane-3,9-diethanol, polymer with 1,2,2,6,6-pentamethyl-4-piperidinyl ester (Mark® LA63); 2,4,8,10-Tetraoxaspiro[5.5]undecane-3,9-diethanol, polymer with 1,2,3,4-butanetetracarboxylic acid, 2,2,6,6-tetramethyl-4-piperidinyl ester (Mark® LA68); D-glucitol, 1,3:2,4-bis-O-(2,2 ,6,6-tetramethyl-4-piperidinylidene)-(HALS7);7-oxa-3,20-diazadispiro[5.1.11.2]-heneicosan-21-one-2,2,4,4-tetramethyl-20-(oxiranylmethyl) oligomer (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 MW2286);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 SA);Nylostab® S-EED (Clariant Huningue SA; 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® 3150); and 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] In addition, 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. In addition, when forming a functional film, it is possible and preferable to incorporate a light stabilizer such as HALS in advance into a coating liquid such as a dispersion of an organic substance.

[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, further 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 Ingredients) The functional film may contain other components, such as a component derived from a silane coupling agent.

[0039] Other components can be appropriately selected and added 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 the deterioration of the organic substance A. In addition, when forming a relatively thick functional film (for example, a thickness of more than 300 nm, and in some cases a thickness of 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 hydroxyl 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 polyol compound produced by reaction of the epoxy group of a polyether-type surfactant or a polyepoxy compound. Examples of the polymer P include polycaprolactone polyol, bisphenol A polyol, polyethylene glycol, polypropylene glycol, polyoxyalkylene derivatives, and acrylic copolymers of control polymerization.

[0041] The functional film may contain a component derived from a silane coupling agent. A solution for forming the functional film, i.e., a film forming solution, may contain a silane coupling agent. The silane coupling agent is LSiM 3 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 the organic substance in the film, and the M group is hydrolyzed and reacts with the inorganic substance in the film. Through these reactions, the silane coupling agent can contribute to improving the dispersibility of the organic substance in the film.

[0042] -SiM in silane coupling agents 3 In the film, the part indicated by is -Si(-O-) 3 It exists in a structure that changes to -SiO 1.5and constitutes a part of the inorganic substance. On the other hand, the part represented by L- usually constitutes a part of the organic substance after reacting with an organic substance according to its type. In the functional film, a part of the inorganic substance and the organic substance may be derived from a silane coupling agent.

[0043] <Characteristics of functional films> (Functional film as a UV shielding film / UV 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 the functional film has an ultraviolet transmittance T of 2% or less, preferably 1% or less, and more preferably 0.5% or less, as specified by ISO 9050:2003. UV (Hereinafter referred to as “T UV (2003)”), the functional film-coated glass substrate may have an ultraviolet transmittance of 2.5% or less, preferably 1.3% or less, and more preferably 0.7 or less. The functional film-coated glass substrate may have a visible light transmittance of 70% or more, as measured by YA using a CIE standard A light source.

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

[0045] 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 78.5W / m2 with a wavelength of 300-400nm. 2 After irradiating the glass substrate from the surface side opposite the functional film for 2000 hours under the condition ofUV can be 0.45% or less, 0.40% or less, 0.35% or less, or even 0.30% or less, or 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 applied at a black panel temperature of 83±2°C, relative humidity of 50%, and an illuminance of 150W / m with a wavelength of 300-400nm. 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, and particularly 1.0% or less. After irradiation under similar conditions, ΔT UV (2003) may 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 applied at a black panel temperature of 83±2°C, relative humidity of 50%, and an illuminance of 150W / m with a wavelength of 300-400nm. 2 Under the above conditions, 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 the functional film.

[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, the glass substrate preferably contains 0.2% or more, 0.4% or more, or in some cases 0.6% or more of T-Fe on a mass basis. 2 O 3 As is well known, a glass substrate containing T-Fe may be used. 2 O 3 is Fe 2 O 3The glass substrate is typically a glass plate, but is not limited thereto and may have a shape other than a plate.

[0049] <Functional film formation> The functional film can be formed on the glass substrate by a known liquid phase film forming method, specifically a sol-gel method. The coating liquid for forming the film may contain a metal alkoxide such as silicon alkoxide as a component for generating an inorganic substance (inorganic substance precursor) together with the organic substance A and the organic substance B. As described above, the inorganic substance may contain silicon oxide, and the inorganic substance precursor may be a silicon oxide precursor represented 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 coating the coating liquid on the glass substrate and drying the applied coating liquid.

[0050] In addition, when the organic substance A is added as particles, the following method can be followed. First, it is preferable to prepare a dispersion containing the organic substance A as a dispersoid, mix this with the inorganic substance and the silane coupling agent described above to form a coating liquid (coating liquid), and apply this to a glass substrate to prepare a glass substrate having a functional film. However, an inorganic substance precursor may be used together with the inorganic substance or instead of the inorganic substance. To prepare such a dispersion of the organic substance A, it is preferable to mix at least the organic substance A, a lower alcohol, a dispersion medium mainly composed of water (lower alcohol, water may be 100%), and a dispersant, and wet grind the organic compound A with a media mill or the like until it has the above average particle size. As the lower alcohol, an alcohol having 1 to 3 carbon atoms is suitable. At this time, it is preferable to have a dispersant present in order to prepare a coating liquid that is dispersed to a preferred particle size and is stable. As the dispersant, one or more types can be selected and used from surfactants and polymer dispersants such as those described in JP-A-2022-115764, for example, and it is preferable. The surfactant is not particularly limited, but a polyoxyalkylene derivative is preferred. The HLB of the surfactant may be 9 to 16, more preferably 11 to 15, and particularly preferably 13.2. The surfactant may have 1 to 3 benzyl groups, and 1 to 3 benzyl groups may be bonded to any part of the phenyl ether group. The polymer dispersant is not particularly limited, but the aforementioned polymer P may be used, and in particular, an acrylic copolymer obtained by controlled polymerization is preferred. In addition to the organic substance A, the dispersion medium, and the dispersant, a light stabilizer may be contained in the dispersion, 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 mass%, particularly 8 to 12 mass%, and of these 10 mass% is preferable, the content of the polymer dispersant is 1 to 100 mass parts, particularly 50 to 90 mass parts, and even more preferably 75 to 85 mass parts, and of these 80 mass parts, per 100 mass parts of the organic substance such as organic substance A, and the content of the surfactant is 1 to 100 mass parts, particularly 5 to 40 mass parts, and even more preferably 10 to 30 mass parts, and of these 20 mass parts is preferable, per 100 mass parts 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 that contains organic substance A and a light stabilizer and is 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 the 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] <Functional film thickness> The thickness of the functional film may be appropriately adjusted depending on the function to be imparted. When the functional film is an ultraviolet ray shielding film, the thickness may be more than 300 nm and not more than 15 μm, furthermore, 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> An example of an organic compound A1 that is particularly suitable for addition as solid particles is a benzotriazole compound. The benzotriazole compound may have the structure shown below.

[0053] [ka]

[0054] In the formula, R 1 and R 1 ' may be the same or different and are each a hydrogen atom, a halogen atom, a nitro group, a cyano group, a perfluoroalkyl group having 1 to 12 carbon atoms, R 3 SO- group or R 3 O 2 - group. 2 and R 2 ' may be the same or different, and each represents an alkyl group having 1 to 12 carbon atoms, CO 2 R is an alkyl group having 1 to 12 carbon atoms in which a hydrogen atom is substituted with an H group, a phenyl group, a phenylalkyl group containing 1 to 4 carbon atoms in the alkyl group portion, or a cycloalkyl group having 5 to 8 carbon atoms. 2 and R 2R' is preferably an alkyl group having 1 to 12 carbon atoms. Most preferably, it is a tert-octyl group. 3 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 by 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 the above aryl group in which a hydrogen atom is substituted by 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). 1 and R 1 is preferably a hydrogen atom or a halogen atom, more preferably a halogen atom, and most preferably a chlorine atom. 1 and R 1 ' is a chlorine atom, and R 2 and R 2 The compound where ' is a tert-octyl group, namely 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 prepared and evaluated. An ultraviolet ray shielding film was formed as the functional film. The evaluation items were as follows.

[0056] <Optical properties> The optical properties were measured using a spectrophotometer (Shimadzu Corporation, UV-3100PC). The measured property was the ultraviolet transmittance Tuv, as specified in ISO9050:1990, 2003.

[0057] <Light resistance (UV resistance)> The following two types of tests were conducted: (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%. The glass substrate was irradiated with simulated sunlight from a carbon arc lamp for a specified period of time, and the ultraviolet transmittance T UV Regarding T after irradiation UV T before irradiation UV Subtract ΔT UV The ultraviolet transmittance T stipulated in ISO9050:2003 was also calculated. UV For 2003, T after irradiation UV T before irradiation from 2003 UV Subtract 2003, ΔT UV The figure was calculated as 2003.

[0058] (2nd test / irradiation from the membrane surface) The second test was a test in which light was irradiated from the side on which the functional film was formed. In this test, an accelerated weathering tester, specifically the 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 / m2 with a wavelength of 300 to 400 nm. 2 The black panel temperature was set at 83±2°C and the relative humidity was set at 50%. The light from a xenon lamp was irradiated for a specified period of time, and the ultraviolet transmittance T UV Regarding T after irradiation UV T before irradiation UV Subtract ΔT UV The ultraviolet transmittance T stipulated in ISO9050:2003 was also calculated. UV For 2003, T after irradiation UV T before irradiation from 2003 UV Subtract 2003, ΔT UV The figure was calculated as 2003.

[0059] In the second test, the functional film was visually observed after the irradiation test to determine whether it fell into any of the following categories: The high-intensity lamp used was the Ultra Intensity Halogen-Light "UIH-1H" ultra-high-intensity inspection lighting device manufactured by Intex Co., Ltd. ◎: No film peeling. No cracks were observed in the film even when irradiated with a high-intensity lamp. ◯: No peeling of the film. Cracks can be seen in the film when irradiated with a high-intensity lamp. △: No peeling of the film. Many cracks can be seen in the film under fluorescent light. ×: Film peeling was observed.

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

[0061] For 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 liquid was applied by flow coating onto a cleaned soda-lime silicate glass substrate (UV-cut green glass manufactured by Nippon Sheet Glass, 100×100 mm, thickness 2.8 mm) at room temperature with a humidity of 30%. After drying, the substrate was placed in an oven with a raised temperature and heated, and then cooled to form a functional film. The above measurements were carried out on the thus obtained glass substrate with the film. The results are shown in Tables 2 to 4.

[0063] [Table 1]

[0064] [Table 2]

[0065] [Table 3]

[0066] [Table 4]

[0067] The ultraviolet ray blocking agent was dispersed in the film in such a manner that the average particle size was considered to be 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, which contained light stabilizers, 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 described above, the present disclosure provides the following techniques. (Technology A1) A glass substrate and a functional film on the glass substrate, The functional film is Inorganic substances; an organic substance A that imparts at least one function selected from the group consisting of ultraviolet shielding, infrared absorbing, anti-fogging, water repellency, and light control to the functional film; and an organic substance B which is a light stabilizer that suppresses deterioration of the functional film due to ultraviolet irradiation. Glass substrate with functional film.

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

[0070] (Technology A3) T at wavelength 380 nm as specified in ISO9050:1990 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 applied to the black panel at a temperature of 83±2°C, a relative humidity of 55±5%, and an illuminance of 78.5W / m2 with a wavelength of 300-400nm. 2 After irradiating the glass substrate from the surface side opposite the functional film for 2000 hours under the condition 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 0.45% or less.

[0072] (Technology A5) In an accelerated weathering tester, light from a xenon arc lamp was applied at a black panel temperature of 83±2°C, relative humidity of 50%, and an illuminance of 150W / m with a wavelength of 300-400nm. 2 After irradiating the functional film side for 300 hours under the conditions of UV The change in ΔT UVThe 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 was applied at a black panel temperature of 83±2°C, relative humidity of 50%, and an illuminance of 150W / m with a wavelength of 300-400nm. 2 The glass substrate with a functional film according to any one of Techniques A1 to A5, wherein after irradiation for 300 hours from the side on which the functional film is formed under the above conditions, no cracks are observed in the functional film.

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

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

[0076] (Technology A9) The functional film-attached 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 Techniques 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: In the following, the coating liquid is a dispersion liquid containing an organic compound A1 as particles, particularly solid particles.

[0079] (Technology B1) The dispersion for application to a glass substrate contains at least: (i) at least one organic compound A1 having ultraviolet shielding properties, 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, wherein the organic compound exists as particles. However, technology B1 can be rewritten as follows: The dispersion for application to a glass substrate 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; (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 technique B2, wherein the organic compound is a compound represented by the following formula (I):

[0082] [ka]

[0083] In formula (I), R 1 and R 1 ' 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, R 3 SO- group or R 3 O 2 - group. 2 and R 2' may be the same or different, and each represents an alkyl group having 1 to 12 carbon atoms, CO 2 R is an alkyl group having 1 to 12 carbon atoms in which a hydrogen atom has been substituted with an H group, a phenyl group, a phenylalkyl group containing 1 to 4 carbon atoms in the alkyl group portion, or a cycloalkyl group having 5 to 8 carbon atoms. 3 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, the hydrogen atom of which is substituted by 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 the above aryl groups, the hydrogen atom of which is substituted by one or two alkyl groups having 1 to 4 carbon atoms, or a 1,1,2,2-tetrahydroxyperfluoroalkyl group, the perfluoroalkyl portion of which contains 6 to 16 carbon atoms.

[0084] (Technology B4) The organic compound is represented by the formula (I) 1 and R 1 ' is a chlorine atom, and R 2 and R 2 The dispersion for application to a glass substrate according to Technology B3, wherein ' is a compound having a tert-octyl group.

[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 Technical 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 liquid 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 inorganic substances, inorganic substance precursors, and silane coupling agents 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 liquid 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 inorganic substances, inorganic substance precursors, and silane coupling agents 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. [Explanation of symbols]

[0088] 1. Glass substrate 2. Functional membranes

Claims

1. A glass substrate and a functional film on the glass substrate, The functional film is Inorganic substances; an organic substance A that imparts ultraviolet shielding properties to the functional film; and an organic substance B which is a light stabilizer that suppresses deterioration of the functional film due to ultraviolet irradiation, The organic substance A is an organic compound A1, which is a benzotriazole-based compound; The organic compound A1 is present as solid particles; Glass substrate with functional film. However, a glass substrate with a functional film, in which a protective film containing a silicone oil represented by the following formula (1) is formed on the functional film, and The present invention excludes a glass substrate with a functional film, in which a protective film having a water-repellent function or an anti-fogging function and not containing fine particles is formed on the functional film. 【Chemistry 1】 In formula (1), R 1 is an amino group, R 2 and R 3 are each independently a methoxy group or an ethoxy group, m is 0 or an integer of 1 or more, and n is an integer of 1 or more.

2. The functional film-coated glass substrate according to claim 1 , wherein the solid particles have an average particle size of 10 nm or more and 150 nm or less.

3. UV transmittance T as specified in ISO9050:1990 UV The functional film-coated glass substrate according to claim 1 , 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 irradiated at a black panel temperature of 83±2°C, 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 1 , wherein the content of the functional film is 0.45% or less.

5. In an accelerated weathering tester, light from a xenon arc lamp was 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 1 , 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 was 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 functional film-attached glass substrate 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 comprises 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 with respect to 100 parts by mass of the organic substance A.

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