Glass plate for automobile windows

Abstract

The present disclosure provides a glass plate for automobile windows, which includes: a glass plate that has a first length of 400 mm or more along the main surface; and an ultraviolet absorption film on the glass plate. The ultraviolet absorption film includes an Si-O bond and an ultraviolet absorption component A. The minimum value Tmin of the film thickness of the ultraviolet absorption film is 1.0 μm or more. If a WON-S test specified in Japanese Industrial Standards (JIS) D0205 (1987) is performed on this glass plate for automobile windows for three months, with light irradiation from the ultraviolet absorption film side, no crack is found under a fluorescent lamp after the test.

Description

Automotive window glass

[0001] The present invention relates to a glass sheet for an automobile window, and more particularly to a glass sheet for an automobile window having an ultraviolet absorbing film.

[0002] An ultraviolet absorbing film may be formed on glass sheets. Particularly in the case of automobile windowpane applications, there is a high demand for glass sheets with ultraviolet shielding properties due to the need for sun protection. The ultraviolet shielding properties are imparted to the film by adding an ultraviolet absorbing component. Benzophenone-based, benzotriazole-based, and other organic compounds are known as ultraviolet absorbing components. Patent Document 1 discloses a silylated ultraviolet absorber. In Patent Document 1, the silylated ultraviolet absorber is synthesized by reacting an epoxy group-containing silane coupling agent with a hydroxy group-containing benzophenone-based ultraviolet absorber to silylate the compound.

[0003] UV-absorbing films containing UV-absorbing components are often formed on glass plates using a sol-gel method with a hydrolyzable silicon compound, typically an alkoxysilane, as a raw material. Patent Document 1 also shows a UV-absorbing film formed by the sol-gel method. It is known that when adding an organic substance such as a UV absorber to a film formed by the sol-gel method, a silane coupling agent is used as part of the raw material. The silane coupling agent allows the UV absorber to be added to the film at a higher concentration. In Patent Document 1, the UV-absorbing film is formed by a sol-gel method with a UV absorber, a tetraalkoxysilane, and an epoxy group-containing silane coupling agent as raw materials.

[0004] International Publication No. 2010-131744

[0005] According to the study by the present inventors, there is room for improvement in the light resistance of the ultraviolet absorbing film.

[0006] An object of the present invention is to provide a new glass plate for automobile windows which has improved light resistance when continuously exposed to ultraviolet rays.

[0007] The present invention provides an automotive window glass sheet comprising: a glass sheet having a first length of 400 mm or more along a main surface; and an ultraviolet absorbing film on the glass sheet, wherein the ultraviolet absorbing film contains a Si—O bond and an ultraviolet absorbing component A, the ultraviolet absorbing film has a minimum film thickness Tmin of 1.0 μm or more, and no cracks are observed under fluorescent light after a WON-S test specified in Japanese Industrial Standards (JIS) D0205-1987 is performed for three months while irradiating the glass sheet with light from the ultraviolet absorbing film side.

[0008] According to the present invention, it is possible to sufficiently improve the light resistance of glass sheets for automobile windows that have been exposed to ultraviolet rays for a long period of time.

[0009] 1 is a cross-sectional view showing one embodiment of a glass plate according to the present invention. 2 is a schematic diagram showing an example of a silicon oxide network structure in an ultraviolet absorbing film containing an organic compound P. 3 is a schematic diagram showing an example of a silicon oxide network structure in an ultraviolet absorbing film containing an organic compound P and a reaction product of a silane coupling agent.

[0010] 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. "Room temperature" refers to 25°C. The "main surface" of a window glass sheet is the surface of the glass sheet that forms the window surface. The two "main surfaces" are spaced apart in the thickness direction of the glass sheet and face in opposite directions.

[0011] The automotive window glass plate of this embodiment shown in Fig. 1 includes a glass plate 1 and an ultraviolet absorbing film 2 disposed on the glass plate 1. The ultraviolet absorbing film 2 may be formed directly on the surface of the glass plate 1, or may be formed via an underlayer film (not shown). The underlayer film may be a single-layer film or a multilayer film including two or more layers.

[0012] The ultraviolet absorbing film 2 may be a film formed by applying a coating liquid. The film quality of the ultraviolet absorbing 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.

[0013] The ultraviolet absorbing film 2 may contain an ultraviolet absorbing component A and an organic component P that does not fall under the ultraviolet absorbing component A. The ultraviolet absorbing film 2 may be formed from a film-forming raw material containing a silane coupling agent. The ultraviolet absorbing film 2 formed from this film-forming raw material contains a reaction product of the silane coupling agent. The ultraviolet absorbing film 2 may contain an oxide such as silicon oxide in addition to the above components. Silicon oxide may be the main component of the ultraviolet absorbing film. Each component that makes up the ultraviolet absorbing film will be described below.

[0014] <Components of the UV-Absorbing Film> [Silicon Oxide] Silicon oxide may be the main component of the UV-absorbing film 2. Silicon oxide is a typical inorganic component in films formed by the sol-gel method. As is well known, silicon oxide formed by the sol-gel method forms a network structure containing silicon atoms and oxygen atoms in the film. This network contains Si—O bonds and is basically amorphous. However, the inorganic component may further contain oxides other than silicon oxide, such as aluminum oxide, titanium oxide, zirconium oxide, and sodium oxide. Furthermore, the inorganic component is not limited to oxides and may include nitrides and the like, for example, polysilazane.

[0015] [UV-Absorbing Component A; Organic Compound A] The UV-absorbing component A may be an organic compound A having UV-absorbing properties. The organic compound A may be 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 A may be a benzotriazole-based and / or benzophenone-based organic compound.

[0016] The organic compound A may be an organic compound A1 containing a silicon atom. The organic compound A1 can be obtained by silylation of an ultraviolet absorber, more specifically, by alkoxysilylation of the ultraviolet absorber, and adding the ultraviolet absorber to the film. An example of a method for silylation of an ultraviolet screening agent is disclosed in Patent Document 1. An example of a silylated ultraviolet absorber is represented by the following formula:

[0017] RUV(-O-CH2-CH(OH)-CH2-O-R 2 -Si(OR 1 ) 3) m (1)

[0018] Here, R 1 is an alkyl group having 1 to 4 carbon atoms, particularly 1 or 2 carbon atoms. 2 is an alkylene group having 1 to 6 carbon atoms, particularly 2 or 3 carbon atoms. m is an integer of 1 or more, particularly an integer of 1 to 3. RUV is a residue of an ultraviolet absorber, for example, at least one residue 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. RUV is a residue of a benzotriazole-based and / or benzophenone-based organic compound, particularly a benzophenone-based organic compound.

[0019] An example of a silylated compound represented by formula (1) is 4-(2-hydroxy-3-(3-trimethoxysilyl)propoxy-propoxy)-2,2,4-trihydroxybenzophenone. 1 is a methyl group, R 2 represents a propylene group, m represents 1, and RUV represents a residue of a benzophenone compound.

[0020] The organic compound A1 is added to the ultraviolet absorbing film by a sol-gel method using a silylated ultraviolet absorber as represented by formula (1) as a raw material.

[0021] However, the organic compound A may not be silylated. In other words, the organic compound A may be an organic compound A2 that does not contain a silicon atom. In this embodiment, silylation of the organic compound A is not essential.

[0022] The organic compound A may be an organic compound A3 in the form of particles. The organic compound A in the form of particles preferably maintains a crystalline state in the film. In other words, the organic compound A may be crystalline. The fact that the organic compound maintains a crystalline state can be confirmed by X-ray diffraction. From the viewpoint of suppressing the haze ratio of the film, the average particle size of the particles is preferably 150 nm or less.

[0023] 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.

[0024] The organic compound A3 may be an organic compound that is solid at room temperature. 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 per unit mass is inferior to that of low-molecular-weight ultraviolet absorbers. The organic compound A3 can be dispersed in a film-forming solution and introduced into the film. The organic compound A3 may be a benzotriazole-based and / or benzophenone-based organic compound, particularly a benzotriazole-based organic compound.

[0025] The molecular weight of organic compound A3 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 A3 may be 200 or more, or 300 or more. It is preferable that organic compound A3 does not contain a polymerizable carbon-carbon double bond in the molecule. Examples of polymerizable carbon-carbon double bonds include double bonds contained in polymerizable functional groups such as vinyl groups, vinylene groups, and vinylidene groups.

[0026] The organic compound A may be a non-particle organic compound A4. The organic compound A4 can be introduced into the film by, for example, dissolving it in a film-forming solution.

[0027] Organic compound A is classified into organic compound A1 or A2 depending on whether it contains a silicon atom, and into organic compound A3 or A4 depending on whether it is a particle. Organic compound A may contain a nitrogen atom, as typified by benzotriazole-based organic compounds.

[0028] [Organic Component P] The organic component P is an organic component that does not fall under the category of the ultraviolet absorbing component A. The organic component P may be an organic compound P that does not fall under the category of the organic compound A. The organic compound P may be a polymer.

[0029] The organic compound P may be at least one selected from the group consisting of polyether compounds, polyol compounds, polyvinylpyrrolidones, and polyvinylcaprolactams. Polyether compounds are compounds containing two or more ether bonds. Polyol compounds are compounds containing two or more hydroxy groups. Polyvinylpyrrolidones are polymers containing vinylpyrrolidone and its derivatives as monomers. Polyvinylcaprolactams are polymers containing vinylcaprolactam and its derivatives as monomers. Specifically, the organic compound P may be a polyether surfactant or a polyol compound produced by the reaction of the epoxy group of a polyepoxy compound. Examples of the organic compound P include polyether phosphate esters, polycaprolactone polyols, bisphenol A polyols, polyethylene glycols, and polypropylene glycols. Examples of polyethylene glycols include diethylene glycol and triethylene glycol, and examples of polypropylene glycols include dipropylene glycol and tripropylene glycol.

[0030] The organic compound P is a component that can improve the light resistance of the UV-absorbing film. Silicon oxide, which is the main component of the film, can have an irregular network structure composed of silicon atoms and oxygen atoms. As shown in Figure 2, when the organic compound P is incorporated into the network structure 10, it can support the network from the inside and suppress its deformation.

[0031] The organic substances contained in the ultraviolet absorbing film, particularly the ultraviolet absorbing component A with high ultraviolet absorption, gradually decompose with long-term irradiation with ultraviolet light. The film becomes sparse due to the decomposition of component A, and cracks occur as the film shrinks. Organic compound P is more resistant to ultraviolet light than component A, and is thought to suppress the film shrinkage and thereby suppress the occurrence of cracks.

[0032] [Silane Coupling Agent] The silane coupling agent may be represented by 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 such as chlorine, or an alkoxy group such as a methoxy group or an ethoxy group. The M group of the silane coupling agent is hydrolyzed and fixed to the network structure in the film or the surface of the glass plate. The silane coupling agent can contribute to improving the dispersibility of organic components containing the ultraviolet absorbing component A in the film.

[0033] 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, for example, part of a network structure.

[0034] As is well known, silicon oxide constituting the network structure can be supplied by the sol-gel method from a tetrafunctional silane represented by SiM4, together with a silane coupling agent, where M is as defined above.

[0035] <Atomic ratio Si / C in ultraviolet absorbing film> The atomic ratio Si / C, which is the ratio of the number of Si atoms to the number of C atoms in the ultraviolet absorbing film, is, for example, 0.6 or more, and may be 0.7 or more, 0.8 or more, 0.9 or more, 1.0 or more, 1.1 or more, 1.2 or more, or even 1.3 or more. The atomic ratio Si / C may be, for example, 2.0 or less, 1.9 or less, or even 1.8 or less. If the atomic ratio Si / C is too small or too large, the resistance to ultraviolet rays is likely to be low. The atomic ratio Si / C is preferably 0.6 or more and 2.0 or less, more preferably 1.2 or more and 1.8 or less, and even more preferably 1.3 or more and 1.8 or less.

[0036] The atomic ratio Si / C can be measured by X-ray photoelectron spectroscopy (XPS). Specifically, the atomic ratio Si / C can be measured from the peak intensities of the Si2p spectrum and the C1s spectrum of the ultraviolet absorbing film using a commercially available X-ray photoelectron spectroscopy analyzer. When measuring the atomic ratio Si / C, first, the concentration distributions of Si atoms and C atoms in the thickness direction are obtained by repeatedly performing sputter etching of the ultraviolet absorbing film with Ar ions and elemental analysis by XPS at arbitrary measurement points using X-ray photoelectron spectroscopy. Next, the average concentrations of Si atoms and C atoms are calculated from the obtained concentration distributions. The atomic ratio Si / C can then be obtained by dividing the average concentration of Si atoms by the average concentration of C atoms.

[0037] <Thickness of UV-Absorbing Film> The thickness of the UV-absorbing film may be adjusted as appropriate. For example, the thickness may be in the range of 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.

[0038] The minimum film thickness Tmin may be 1 μm or more, 1.2 μm or more, or even 1.5 μm or more. If Tmin is too small, sufficient ultraviolet shielding ability cannot be imparted. The maximum film thickness Tmax may be 5 μm or less, 4 μm or less, or even 3.5 μm or less. If Tmax is too large, it becomes difficult to suppress cracks occurring in the film. The maximum film thickness Tmax may be 2.0 μm or more, or even 2.5 μm or more. The maximum film thickness Tmax is preferably 2.0 μm or more and less than 5.0 μm, and more preferably 2.5 μm or more and 3.5 μm or less.

[0039] The thickness of the ultraviolet absorbing film may have a thickness distribution that monotonically increases from the first side to the second side of the glass plate, where the first side is, for example, the side corresponding to the top side of the window glass, and the second side is, for example, the side corresponding to the bottom side of the window glass.

[0040] <Glass Plate> The glass plate is not particularly limited, and for example, a soda-lime silicate glass plate can be used. From the viewpoint of further improving the ultraviolet shielding property, a glass plate 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.

[0041] The glass sheet has a first length of 400 mm or more along the main surface. The first length may be 450 mm or more, or even 500 mm or more. When the glass sheet has a curved surface, the first length is determined along the curved surface. The first length can be determined along any first direction of the main surface of the glass sheet. The glass sheet may have a second length of 400 mm or more along the main surface. The second length is determined along a second direction perpendicular to the first direction when the main surface of the glass sheet is viewed in plan. The second length may be 450 mm or more, 500 mm or more, 600 mm or more, or even 700 mm or more. When the glass sheet has a curved surface, the second length is determined along the curved surface. The first length may be a length along the direction in which the membrane-forming solution is flowed along the main surface. Since the film thickness gradually increases along the direction in which the membrane-forming solution is flowed, this direction is also a direction in which the film thickness increases monotonically and gradually. Even when the first length is as long as described above and the maximum film thickness and film thickness distribution of the ultraviolet absorbing film tend to become large, this embodiment is suitable for improving the light resistance of the ultraviolet absorbing film.

[0042] A ceramic shielding layer may be formed on the periphery of the main surface of a window glass plate to improve the design of the automobile and to suppress deterioration of adhesives, foaming agents, etc. that bond the glass plates. The area where the ceramic shielding layer is formed imparts opacity to the glass plate. The ceramic shielding layer is usually formed by applying a ceramic paste and then firing it. However, the window glass plate does not necessarily have to have a ceramic shielding layer on its main surface.

[0043] <Characteristics of Window Glass Plate> The window glass plate has good light resistance to the extent that no cracks are observed under fluorescent lamp after performing the WON-S test specified in JIS D0205-1987 for three months while irradiating light from the ultraviolet absorbing film side. Furthermore, the window glass plate may have good light resistance to the extent that no cracks are observed under fluorescent lamp after performing the same test for three months while irradiating light from the ultraviolet absorbing film side.

[0044] The window glass is T based on ISO9050 (1990 edition). UV The glazing may have an ultraviolet transmittance of 2% or less, preferably 1% or less, expressed as YA, measured using the CIE standard A illuminant. The glazing may have a visible light transmittance of 70% or more, expressed as YA, measured using the CIE standard A illuminant.

[0045] <Area where ultraviolet absorbing film is formed> The ultraviolet absorbing film may be formed on the entire main surface of the window glass plate. However, the ultraviolet absorbing film may be formed on only a part of the main surface. For example, the main surface of the window glass plate may have an uncoated area including an area of ​​a predetermined width from the upper edge of the window glass plate, and a coated area whose upper edge is the lower edge of the uncoated area. The ultraviolet absorbing film is formed in the coated area. The uncoated area may be an area where the glass surface is exposed. When the coated area is divided into a first coated area located within 100 mm from the upper edge of the first coated area and a second coated area located 100 mm or more from the upper edge of the second coated area, the ultraviolet absorbing film may be formed on the second coated area according to T according to ISO 9050 (1990 edition). UV The difference may be 2% or less, preferably 1% or less. The coating area may have a length of 400 mm or more, or even 450 mm or more, along the first length direction.

[0046] (Example) Window glass plates having an ultraviolet absorbing film formed thereon were produced and evaluated. The evaluation items were as follows. Note that the glass plates used below did not have a ceramic shielding layer formed thereon.

[0047] <Optical Properties> Optical properties were measured using a spectrophotometer (Shimadzu Corporation, UV-3100PC). The measured properties were the visible light transmittance YA measured using the CIE standard A light source according to JIS R3212, and the ultraviolet light transmittance T calculated according to ISO 9050 (1990 edition). UV When a film is formed by a flow coating method, the film thickness distribution in the coating area is taken into consideration, and T is set at multiple locations. UV However, areas where the film was relatively thin, that is, areas less than 100 mm from the upper edge of the applied area in the direction in which the film-forming solution was poured, were excluded from the measurement.

[0048] <Lightfastness (UV Resistance Characteristics)> Lightfastness (UV Resistance Characteristics) was measured by exposure test WON-S specified in JIS D0205-1987 for two or three months, with light being incident from the UV absorbing film side. After the test, the UV absorbing film was visually observed and evaluated based on the following evaluation criteria. Visual observation was performed in a darkroom, with the window glass plate placed directly under a 72 W fluorescent lamp at a distance of 200 cm from the fluorescent lamp, from a position 50 cm away from the window glass plate.

[0049] ◯: No cracks observed under fluorescent light. ×: Many cracks observed under fluorescent light.

[0050] <Atomic Ratio Si / C> The atomic ratio Si / C was measured at a predetermined measurement point of the ultraviolet absorbing film using an X-ray photoelectron spectrometer "Quantera SX" manufactured by ULVAC-PHI, Inc. The average values ​​of the concentrations of Si atoms and C atoms in the thickness direction of the ultraviolet absorbing film were calculated by repeating sputter etching of the ultraviolet absorbing film with Ar ions and elemental analysis by XPS at arbitrary measurement points using X-ray photoelectron spectroscopy. The atomic ratio Si / C was obtained from the calculated average values ​​of the concentrations of Si atoms and C atoms.

[0051] <Thickness of UV-Absorbing Film> The thickness of the UV-absorbing film was measured using a laser microscope (Keyence Corporation, VK-9500). The film thickness was measured along the direction in which the film-forming solution was flowed from the upper edge of the coating area using the flow coating method. The maximum film thickness Tmax was taken as the second or subsequent maximum film thickness value, excluding the first maximum film thickness value, in the direction in which the film-forming solution flowed down. The minimum film thickness Tmin was taken as the minimum film thickness value adjacent to the maximum film thickness value in the direction in which the film-forming solution flowed down.

[0052] (Preparation of Composition A) In Composition A, a benzotriazole-based ultraviolet absorber, TINUVIN 360 (manufactured by BASF Japan Ltd.), was used as organic compound A. Specifically, a dispersion (content of ultraviolet-blocking component: 10 wt %, average particle size: 100 nm) containing organic compound A, an ultraviolet-blocking component, as a dispersoid, and water as a dispersion medium was prepared. This dispersion was mixed and stirred with pure water, Solmix (registered trademark) AP-11 (manufactured by Japan Alcohol Sales Co., Ltd.), tetraethoxysilane (TEOS), glycidoxypropyltrimethoxysilane (GPTMS; 3-glycidyloxypropyltrimethoxysilane) as a silane coupling agent, polyether phosphate ester polymer (SOL) (manufactured by Lubrizol Japan Co., Ltd., "Solsperse 41000") as a polyether compound, an ITO fine particle dispersion (ITO fine particle content: 40 wt %, average particle size: 100 nm or less), and concentrated hydrochloric acid (35 mass %) to obtain Composition A having the composition shown in Table 1 as a film-forming solution for an ultraviolet-absorbing film. SOL corresponds to the organic compound P.

[0053] (Preparation of Composition B) 2-propyl alcohol, 1-methoxy-2-propanol, tetramethoxysilane (TMOS), 3-glycidoxypropyltrimethoxysilane (GPTMS), an ITO fine particle dispersion (ITO fine particle content 40 wt %, average particle size 100 nm or less), and 0.1 mol / L of nitric acid were weighed and introduced into a reaction vessel and stirred. Next, 2,2',4,4'-tetrahydroxybenzophenone (THBP) was added and dissolved with stirring to obtain Composition B having the composition shown in Table 1.

[0054] (Preparation of Compositions C to M) Compositions D to L were prepared in the same manner as composition A, except that the components and contents of the compositions were changed as shown in Table 1, to obtain compositions D to L, respectively.

[0055]

[0056] The content of each component in Table 1 is shown in mass %.

[0057] The abbreviations in Table 1 are as follows: TINUVIN360: "TINUVIN360" manufactured by BASF Japan Ltd. (2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol]) THBP: 2,2',4,4'-tetrahydroxybenzophenone TINUVIN326: "TINUVIN326" manufactured by BASF Japan Ltd. (2-(5-chloro-2H-benzotriazol-2-yl)-6-(1,1-dimethylethyl)-4-methylphenol) TEOS: tetraethoxysilane TMOS: tetramethoxysilane GPTMS: glycidoxypropyltrimethoxysilane MTES: methyltriethoxysilane KBM: "KBM-3066" manufactured by Shin-Etsu Chemical Co., Ltd. (1,6-bis(trimethoxysilyl)hexane) M20G: "M-20G" (methoxydiethylene glycol methacrylate) manufactured by Shin-Nakamura Chemical Co., Ltd. LF4871: "PHENOLITE LF-4871" (bisphenol A novolac compound) manufactured by DIC Corporation EX614B: "Denacol EX-614B" (sorbitol polyglycidyl ether) manufactured by Nagase ChemteX Corporation SOL: "Solsperse 41000" (polyether phosphate ester polymer) manufactured by The Lubrizol Japan Corporation PPG700: polypropylene glycol (molecular weight 700) EtOH: ethyl alcohol IPA+PGME: mixed alcohol of 2-propyl alcohol and 1-methoxy-2-propanol AP11: "Solmix (registered trademark) AP-11" (mixed alcohol of ethyl alcohol, methyl alcohol, and 2-propyl alcohol) manufactured by Japan Alcohol Sales Co., Ltd. BYK307: BYK-307 (polyether-modified polydimethylsiloxane) manufactured by BYK Japan

[0058] Reference Example 1 Composition A was applied to the entire main surface of a washed UV-cut green glass plate (100 × 100 mm, thickness 3.4 mm) manufactured by Nippon Sheet Glass Co., Ltd. by spin coating, followed by heating in a preheated oven and then cooling, thereby forming an ultraviolet-absorbing film on the glass plate.

[0059] (Reference Example 2) Composition A was applied to the entire main surface of a cleaned UV-cut green glass plate (100 × 100 mm, thickness 3.4 mm) manufactured by Nippon Sheet Glass Co., Ltd., by a flow coating method at room temperature and a relative humidity of 30%. The applied composition A was air-dried at room temperature, then heated by placing it in a preheated oven, and then cooled, thereby forming an ultraviolet-absorbing film on the glass plate.

[0060] Example 1 Composition A was applied to the entire main surface of a cleaned UV-cut green glass plate (600 × 600 mm, thickness 3.4 mm) manufactured by Nippon Sheet Glass Co., Ltd., by a flow coating method at room temperature and a relative humidity of 30%. The applied Composition A was air-dried at room temperature, then heated by placing it in a preheated oven, and then cooled, thereby forming an ultraviolet-absorbing film on the glass plate.

[0061] Example 2 A nozzle for ejecting composition A was moved along the upper edge of a coating area set on the main surface of a UV-cut green glass plate (600 x 600 mm, 3.4 mm thick) manufactured by Nippon Sheet Glass. Composition A ejected along the upper edge of the coating area flowed downward along the main surface for 550 mm or more, thereby coating composition A on the coating area, which was part of the main surface. An area (uncoated area) where composition A was not applied was present near the upper edge of the glass plate. The applied forming solution was air-dried at room temperature, then heated by placing it in a preheated oven, and then cooled, thereby forming an ultraviolet-absorbing film on part of the main surface of the glass plate.

[0062] Example 3 An ultraviolet absorbing film was formed on a part of the main surface of a glass plate in the same manner as in Example 2, except that the amount of ink ejected from the nozzle was changed to change the thickness of the ultraviolet absorbing film.

[0063] Example 4 An ultraviolet absorbing film was formed on a glass plate in the same manner as in Example 2, except that composition B was used instead of composition A.

[0064] Examples 5 to 14 An ultraviolet absorbing film was formed on a glass plate in the same manner as in Example 2, except that at least one of the composition and the film thickness was changed as shown in Table 2.

[0065] Comparative Example 1 An ultraviolet absorbing film was formed on a part of the main surface of a glass plate in the same manner as in Example 2, except that Composition I was used instead of Composition A and the amount of the ink discharged from the nozzle was changed to change the thickness of the film.

[0066] Comparative Examples 2 to 7 An ultraviolet absorbing film was formed on a glass plate in the same manner as in Example 2, except that the composition and film thickness were changed as shown in Table 2.

[0067] The above measurements were carried out on each of the thus obtained film-coated glass plates. The results are shown in Table 2. In Table 2, "Max Tuv380" indicates the T obtained within the measurement area. UV "Top edge" indicates that there is an area near the top edge of the glass where no film is formed (uncoated area).

[0068]

[0069] As explained above, the present disclosure provides the following technologies: (Technology 1) An automotive window glass sheet comprising: a glass sheet having a first length of 400 mm or more along a main surface; and an ultraviolet absorbing film on the glass sheet, wherein the ultraviolet absorbing film contains a Si—O bond and an ultraviolet absorbing component A, the minimum film thickness Tmin of the ultraviolet absorbing film is 1.0 μm or more, and no cracks are observed under fluorescent light after performing the WON-S test specified in Japanese Industrial Standards (JIS) D0205-1987 for three months while irradiating the ultraviolet absorbing film side with light.

[0070] (Technology 2) The glass plate for an automobile window according to Technology 1, wherein the maximum film thickness Tmax of the ultraviolet absorbing film is 5 μm or less.

[0071] (Technology 3) The glass plate for an automobile window according to Technology 1 or 2, wherein the ultraviolet absorbing component A is a crystal.

[0072] (Technology 4) The glass plate for an automobile window according to any one of Technologies 1 to 3, wherein the ultraviolet absorbing component A contains a nitrogen element.

[0073] (Technology 5) The glass plate for an automobile window according to any one of Technologies 1 to 4, wherein the ultraviolet absorbing component A is a benzotriazole-based compound.

[0074] (Technology 6) The glass plate for an automobile window according to any one of Technologies 1 to 5, wherein the ultraviolet absorbing film further contains an organic component P other than the ultraviolet absorbing component A.

[0075] (Technology 7) The main surface has a non-coated area including an area of ​​a predetermined width from the upper side, and a coated area whose upper edge is the lower edge of the non-coated area, the ultraviolet absorbing film is formed in the coated area, the coated area has a first coated area that is less than 100 mm away from the upper edge, and a second coated area that is 100 mm or more away from the upper edge, and in the second coated area, T based on ISO 9050 (1990 edition) is UV 7. The glass plate for an automobile window according to any one of claims 1 to 6, wherein the ultraviolet transmittance expressed by

[0076] (Technology 8) The automotive window glass plate according to any one of Techniques 1 to 7, wherein the atomic ratio Si / C, which is the ratio of the number of Si atoms to the number of C atoms in the ultraviolet absorbing film, is 0.6 or more and 2.0 or less, and the maximum film thickness Tmax of the ultraviolet absorbing film is 2.0 μm or more and less than 5.0 μm.

[0077] (Technology 9) The automotive window glass plate according to Technology 8, wherein the atomic ratio Si / C of the ultraviolet absorbing film is 1.2 or more and 1.8 or less, and the maximum film thickness Tmax of the ultraviolet absorbing film is 2.5 μm or more and 3.5 μm or less.

Claims

1. A glass plate for automobile windows, comprising: a glass plate having a first length of 400 mm or more along a main surface; and an ultraviolet absorbing film on the glass plate, wherein the ultraviolet absorbing film contains a Si-O bond and an ultraviolet absorbing component A, the ultraviolet absorbing film has a minimum film thickness Tmin of 1.0 μm or more, and after a WON-S test specified in Japanese Industrial Standards (JIS) D0205-1987 is performed for three months while irradiating light from the ultraviolet absorbing film side, no cracks are observed under fluorescent lamps.

2. The glass sheet for an automobile window according to claim 1, wherein the maximum thickness Tmax of the ultraviolet absorbing film is 5 μm or less.

3. The glass plate for automobile windows according to claim 1, wherein the ultraviolet absorbing component A is a crystal.

4. The glass sheet for automobile windows according to claim 1, wherein the ultraviolet absorbing component A contains a nitrogen element.

5. The glass sheet for automobile windows according to claim 4, wherein the ultraviolet absorbing component A is a benzotriazole-based compound.

6. The glass sheet for an automobile window according to claim 1, wherein the ultraviolet absorbing film further contains an organic component P other than the ultraviolet absorbing component A.

7. The main surface has a non-coated area including an area of ​​a predetermined width from the upper side, and a coated area whose upper edge is the lower edge of the non-coated area, the ultraviolet absorbing film is formed in the coated area, the coated area has a first coated area that is less than 100 mm away from the upper edge, and a second coated area that is 100 mm or more away from the upper edge, and in the second coated area, T based on ISO9050 (1990 edition) is UV 2. The glass sheet for an automobile window according to claim 1, having an ultraviolet ray transmittance expressed by the formula: 1.0% or less.

8. An automobile window glass sheet according to claim 1, wherein the atomic ratio Si / C, which is the ratio of the number of Si atoms to the number of C atoms in the ultraviolet absorbing film, is 0.6 or more and 2.0 or less, and the maximum film thickness Tmax of the ultraviolet absorbing film is 2.0 μm or more and less than 5.0 μm.

9. The glass sheet for an automobile window according to claim 8, wherein the atomic ratio Si / C of the ultraviolet absorbing film is 1.2 or more and 1.8 or less, and the maximum film thickness Tmax of the ultraviolet absorbing film is 2.5 μm or more and 3.5 μm or less.