JP7484786B2 - Glass laminate and method for producing same - Google Patents

Description

The present invention relates to a glass laminate and a method for manufacturing the same.

2. Description of the Related Art For use in vehicles such as automobiles, a glass laminate is known in which an ultraviolet/infrared shielding film having high transmittance for visible light but low transmittance for ultraviolet and infrared light is formed on the surface of a glass sheet.
The ultraviolet and infrared shielding film is, for example, a film containing an ultraviolet shielding agent such as an ultraviolet absorber and an infrared shielding agent such as an infrared absorber.
For example, Patent Document 1 discloses an ultraviolet shielding glass comprising a glass plate and an ultraviolet shielding film formed on the surface of the glass plate (claim 1). The composition for forming the ultraviolet shielding film contains an ultraviolet absorber and a curable silane, and preferably contains an infrared absorber such as ITO (indium tin oxide) and a solvent (paragraphs 0035, 0041, and 0047). The ultraviolet shielding film can be formed by applying the composition onto a glass plate, drying, and curing the composition (paragraph 0042).

International Publication No. 2020/141601

In the above-mentioned applications, an ultraviolet/infrared shielding film is generally formed on the inner surface of a glass plate (the side where passengers and the like are present). Sunlight is incident on the outer surface of the glass plate, and the light transmitted through the glass plate is incident on the ultraviolet/infrared shielding film formed on the inner surface of the glass plate.
The inventors have found through their research that in a glass laminate having an ultraviolet and infrared shielding film, the infrared shielding agent may deteriorate in weather resistance and light resistance tests, resulting in a decrease in visible light transmittance.

The present invention has been made in consideration of the above circumstances, and aims to provide a glass laminate that can effectively block ultraviolet and infrared rays, has improved weather resistance and light resistance, and can suppress a decrease in visible light transmittance during use.

The present invention provides the following glass laminate and method for producing the same.
[1] A glass laminate having an ultraviolet and infrared shielding film formed on a surface of a glass plate, the ultraviolet and infrared shielding film including silica, an ultraviolet shielding agent, and infrared shielding particles including a metal compound,
In a plan view, in at least a part of an upper end portion of the ultraviolet and infrared ray shielding film located within 5 cm from the upper end edge of the glass plate,
When the concentration of one or more arbitrarily selected metal elements contained in all of the infrared shielding particles present in the ultraviolet and infrared shielding film is taken as 100 atomic %, the thickness of the ultraviolet and infrared shielding film is taken as 100%, and the ultraviolet and infrared shielding film is viewed in the depth direction from the film surface,
the concentration of the one or more metal elements contained in the infrared shielding particles present between the film surface and a depth of 50% from the film surface is 55 atomic % or more;
a concentration of the one or more metal elements contained in the infrared shielding particles present between the film surface and a depth of 10% from the film surface is 12 to 20 atomic %.

[2] A step (S1) of preparing a liquid composition containing a curable silane, the ultraviolet ray shielding agent, and the infrared ray shielding particles;
a step (S2) of adjusting the temperature of the glass plate and/or the liquid composition so that T _S >T _L , where T _S is the temperature of the glass plate [°C] and T _L is the temperature of the liquid composition [°C];
A step (S3) of applying the liquid composition having a temperature lower than that of the glass plate onto a surface of the glass plate to form a coating film, thereby obtaining a glass plate with a coating film;
A step (S4) of disposing the glass sheet with the coating film substantially horizontally so that the coating film side faces downward;
and (S5) heating the glass sheet with the coating film to harden the coating film.

In the glass laminate of the present invention, the infrared shielding particles are distributed unevenly toward the film surface side in the ultraviolet/infrared shielding film. In the glass laminate of the present invention, the number of infrared shielding particles that are exposed to relatively strong ultraviolet radiation is relatively small, so that deterioration of the infrared shielding particles due to ultraviolet radiation and the resulting decrease in the visible light transmittance of the ultraviolet/infrared shielding film can be effectively suppressed. According to the present invention, it is possible to provide a glass laminate that has improved weather resistance and light resistance and suppresses the decrease in visible light transmittance during use.

1 is an example of a schematic plan view of a glass laminate according to an embodiment of the present invention. 1 is a schematic cross-sectional view of a glass laminate according to one embodiment of the present invention. FIG. 3 is a partially enlarged schematic cross-sectional view of FIG. 2 . FIG. 2 is a partially enlarged schematic cross-sectional view showing a comparison between a comparative glass laminate (left diagram) and a glass laminate of the present invention (right diagram). FIG. 2 is a schematic cross-sectional view showing a step (S3) of the method for producing a glass laminate according to the embodiment of the present invention. FIG. 2 is a schematic cross-sectional view showing a step (S4) of the method for producing a glass laminate according to the embodiment of the present invention. FIG. 2 is a schematic cross-sectional view showing a step (S4) of the method for producing a glass laminate according to the embodiment of the present invention. 1 is an XPS spectrum of the ultraviolet and infrared shielding film obtained in Example 1. 1 is an XPS spectrum of the ultraviolet and infrared shielding film obtained in Example 2. 1 is an XPS spectrum of the ultraviolet and infrared ray shielding film obtained in Example 13. 1 is an example of a SEM cross-sectional photograph of the glass laminate obtained in Example 1. 7B is an image after the cropping process and the binarization process of FIG. 7A. 1 is an example of a SEM cross-sectional photograph of the glass laminate obtained in Example 2. 8B is an image after the cropping process and the binarization process of FIG. 8A.

Generally, thin film structures are referred to as "films" and "sheets" depending on their thickness. In this specification, there is no clear distinction between them. Therefore, in this specification, "film" may include "sheets".
In this specification, unless otherwise specified, the terms "upper and lower" refer to the "upper and lower" in a state in which the glass laminate is fitted into a vehicle or the like (actual use state).
In this specification, unless otherwise specified, ultraviolet light is light in the wavelength range of 300 to 380 nm, infrared light is light in the wavelength range of 780 to 2500 nm, and visible light is light in the wavelength range of 380 to 780 nm.
In this specification, unless otherwise specified, the term "to" indicating a range of values is used to mean that the range includes the values before and after it as the lower and upper limits.
Hereinafter, an embodiment of the present invention will be described.

[Glass laminate]
The structure of a glass laminate according to one embodiment of the present invention will be described with reference to the drawings.
Fig. 1 is an example of a schematic plan view of a glass laminate of the present embodiment. Fig. 2 is a schematic cross-sectional view of the glass laminate of the present embodiment. Fig. 3 is a partially enlarged schematic cross-sectional view of Fig. 2.
As shown in FIG. 2 , the glass laminate 1 of the present embodiment is a laminate in which an ultraviolet and infrared shielding film 20 containing silica, an ultraviolet shielding agent, and infrared shielding particles containing a metal compound is formed on one surface 10S of a glass plate 10.
The surface 10S of the glass plate 10 is the surface of the glass plate 10 on the ultraviolet and infrared ray shielding film 20 side, and is also referred to as the interface between the glass plate 10 and the ultraviolet and infrared ray shielding film 20.

The glass laminate 1 of the present embodiment can be preferably applied to glass for vehicles such as automobiles (for example, a front glass, a side glass, and a rear glass).
In applications such as vehicles, the ultraviolet and infrared shielding film 20 is formed on the inner surface side of the glass plate 10 (the side where passengers and the like are present, usually the concave side).
The ultraviolet and infrared shielding film 20 may be formed on the entire surface of one surface 10S of the glass plate 10, or may be formed on substantially the entire surface except for at least a part of the peripheral portion (e.g., a region within 30 mm from an edge) of one surface 10S of the glass plate 10. The ultraviolet and infrared shielding film 20 needs to be formed at least in a region that is visible when the glass plate is in use (e.g., when the glass plate is fitted into a vehicle or the like), and does not need to be formed on the peripheral portion that is not visible when the glass plate is in use.

1 is a schematic plan view of a glass laminate 1 according to an embodiment of the present invention. In this example, the glass laminate 1 is a side glass located next to the driver's seat or passenger seat of an automobile.
In the illustrated example, the glass plate 10 has an outer periphery consisting of four sides, namely, an upper side 11, a lower side 12, a front side 13, and a rear side 14, and the lower side 12 has an uneven surface.
In the illustrated example, the ultraviolet and infrared shielding film 20 has an outer periphery consisting of four sides, namely, an upper side 21, a lower side 22, a front side side 23, and a rear side side 24. For easy visual recognition, the part of the outer periphery of the ultraviolet and infrared shielding film 20 that does not coincide with the outer periphery of the glass plate 10 is shown by a two-dot chain line.
In the illustrated example, the upper edge 21 of the ultraviolet and infrared ray shielding film 20 is located approximately 15 mm inside the upper edge 11 of the glass plate 10, the front side edge 23 of the ultraviolet and infrared ray shielding film 20 coincides with the front side edge 13 of the glass plate 10, and the rear side edge 24 of the ultraviolet and infrared ray shielding film 20 coincides with the rear side edge 14 of the glass plate 10.
The planar shape of the glass plate 10 and the area in which the ultraviolet and infrared ray shielding film 20 is formed can be appropriately designed according to the shape of the vehicle or the like to which it is to be attached.

(Glass plate)
Examples of the glass sheet 10 include tempered glass, laminated glass in which a plurality of glass sheets are bonded together via an interlayer film, and organic glass, and tempered glass or laminated glass is preferred for applications such as vehicles. In Figures 1 and 2, the glass sheet 10 is illustrated as being flat, but for applications such as vehicles, the glass sheet 10 is processed into a shape having a curved surface.
The type of glass plate that is the material for the tempered glass and laminated glass is not particularly limited, and examples thereof include soda-lime glass, borosilicate glass, aluminosilicate glass, lithium silicate glass, quartz glass, sapphire glass, and non-alkali glass.
The tempered glass is obtained by subjecting the above-mentioned glass plate to tempering processing by a known method such as an ion exchange method, an air-cooling tempering method, etc. As the tempered glass, air-cooling tempered glass is preferable.
The thickness of the tempered glass is not particularly limited and is designed depending on the application. For applications such as windshields, side windows and rear windows of vehicles, the thickness is preferably 2 to 6 mm.
The thickness of the laminated glass is not particularly limited and is designed according to the application. For applications such as the windshield, side glass, and rear glass of a vehicle, the thickness is preferably 2 to 6 mm.

The interlayer film of the laminated glass is made of a resin film. There are no particular limitations on the constituent resin as long as it is a resin that can bond a plurality of glass sheets well. For example, the interlayer film preferably contains one or more resins selected from the group consisting of polyvinyl butyral (PVB), ethylene vinyl acetate copolymer (EVA), cycloolefin polymer (COP), polyurethane (PU), and ionomer resin.
The interlayer film may contain one or more additives other than the resin, if necessary.
As the material for the intermediate film, a resin film containing the above-exemplified resin is preferable.

The tempered glass and laminated glass may have a coating having functions such as water repellency, low reflectivity, low radiation, and coloring, on at least a partial region of the surface.
The laminated glass may have a film having functions such as low reflectivity, low emissivity, coloring, etc. in at least a part of the inner region. At least a part of the region of the interlayer of the laminated glass may have functions such as coloring, etc. The interlayer of the laminated glass may be a single layer film or a laminated film.

Materials for organic glass include engineering plastics such as polycarbonate (PC); acrylic resins such as polyethylene terephthalate (PET) and polymethyl methacrylate (PMMA); polyvinyl chloride; polystyrene (PS); and combinations of these, with engineering plastics such as polycarbonate (PC) being preferred.

(UV/IR shielding film)
3, the ultraviolet and infrared shielding film 20 contains silica, an ultraviolet shielding agent, and infrared shielding particles 20P containing a metal compound. Since the ultraviolet and infrared shielding film 20 contains an ultraviolet shielding agent and infrared shielding particles 20P, it can effectively shield ultraviolet and infrared rays.
The ultraviolet shielding agent may be a known agent, and may be either an ultraviolet absorbing type or an ultraviolet reflecting type. It is preferable to use one or more ultraviolet absorbers selected from the group consisting of benzophenone-based ultraviolet absorbers, benzotriazole-based ultraviolet absorbers, benzodithiol-based ultraviolet absorbers, azomethine-based ultraviolet absorbers, indole-based ultraviolet absorbers, and triazine-based ultraviolet absorbers.

The infrared shielding particles 20P may be any known type, and may be either an infrared absorbing type or an infrared reflecting type. Metal compound particles containing one or more metal compounds selected from the group consisting of indium tin oxide (ITO), antimony doped tin oxide (ATO), cesium doped tungsten oxide (CWO (registered trademark)), fluorine doped tin oxide (FTO), lanthanum hexaboride (LaB ₆ ), and vanadium pentoxide (V ₂ O ₅ ) are preferred.

As the infrared shielding particles 20P, metal compound particles containing cesium-doped tungsten oxide (CWO (registered trademark)) and/or lanthanum hexaboride (LaB ₆ ) are particularly preferred. When these metal compound particles are used, the value obtained by dividing the absorbance of the ultraviolet and infrared shielding film for light with wavelengths of 800 to 1500 nm by the mass of the infrared shielding particles contained per cm ² of the ultraviolet and infrared shielding film can be made relatively large, for example, 1.5 or more. In this case, the content of the infrared shielding particles 20P in the ultraviolet and infrared shielding film can be reduced. In this case, the thermal expansion of the coating film is increased, convection in the coating film is more likely to occur, and the infrared shielding particles 20P can be distributed more effectively biased toward the film surface side.
The ultraviolet and infrared shielding film 20 may contain one or more optional components other than those described above, as necessary.

The ultraviolet/infrared shielding film 20 can be formed by preparing a liquid composition (LC) containing a curable silane, an ultraviolet shielding agent, and infrared shielding particles 20P, applying this liquid composition (LC) to the surface 10S of the glass plate 10, and heating to harden the coating film.

A curable silane is a silicon compound having one or more silicon atoms bonded to one or more hydroxyl groups or one or more hydrolyzable groups. The hydrolyzable group is a group that can become a hydroxyl group by hydrolysis, and examples of such groups include an alkoxy group, a chlorine atom, an acyl group, and an acyloxy group. As the curable silane, an alkoxysilane having a silicon atom bonded to two or more alkoxy groups is preferred, and as the alkoxy group, an alkoxy group having 1 to 4 carbon atoms is preferred.

As the curable silane, tetraalkoxysilane and bisalkoxysilane are preferable. As the tetraalkoxysilane, tetraethoxysilane (TEOS) and tetramethoxysilane are preferable. As the bisalkoxysilane, a compound represented by the following formula (1) is preferable.
R ¹ _n X ¹ _3-n Si-Q-SiR ² _m X ² _3-m ... (1)
In the above formula, ^R1 and ^R2 are each independently a monovalent hydrocarbon group having 1 to 3 carbon atoms. ^X1 and ^X2 are each independently an alkoxy group. Q is a linear or branched divalent hydrocarbon group having 3 to 8 carbon atoms. n and m are each independently an integer of 0 to 2.

When the liquid composition (LC) containing the curable silane is heated, silica is generated through hydrolysis and polycondensation of the curable silane. However, after the curing reaction is completed, some intermediate products such as partial hydrolysis condensation products of the curable silane may remain in the ultraviolet and infrared shielding film 20.
Unless otherwise specified, "silica" as used herein is a reaction product of a curable silane and may include a partial hydrolysis condensate of the curable silane.

(Distribution of infrared shielding particles and ultraviolet shielding agents)
As shown in FIG. 3, in the glass laminate 1 of the present embodiment, the ultraviolet and infrared shielding film 20 has a distribution in the number of infrared shielding particles 20P when viewed in the thickness direction.
One or more kinds of metal elements are arbitrarily selected from the infrared shielding particles 20P, and the concentration of the selected one or more kinds of metal elements contained in all the infrared shielding particles 20P present in the ultraviolet and infrared shielding film 20 is set to 100 atomic %. Also, the thickness of the ultraviolet and infrared shielding film 20 is set to 100%.
For example, when the infrared shielding particles 20P are indium tin oxide (ITO) particles, indium (In) and/or tin (Sn) can be selected as the one or more metal elements.
When viewed in the thickness direction, the ultraviolet and infrared shielding film 20 has a distribution of concentrations of the selected one or more metal elements contained in the infrared shielding particles 20P.
The concentration distribution of one or more metal elements contained in the infrared shielding particles 20P in the depth direction of the ultraviolet and infrared shielding film 20 can be measured by X-ray photoelectron spectroscopy (XPS).

In the glass laminate 1 of the present embodiment, in a plan view, in at least a part of an upper end portion of the ultraviolet and infrared ray shielding film 20 located within 5 cm from the upper end side of the glass plate 10,
When the ultraviolet and infrared shielding film 20 is viewed in the depth direction from the film surface 20S,
The concentration of one or more selected metal elements contained in the infrared shielding particles 20P present between the film surface 20S and a depth of 50% from the film surface 20S is 55 atomic % or more;
The concentration of the one or more selected metal elements contained in the infrared shielding particles 20P present between the film surface 20S and a depth of 10% from the film surface 20S is 12 to 20 atomic %.

The concentration of the one or more selected metal elements contained in the infrared shielding particles 20P present between the film surface 20S and a depth of 50% from the film surface 20S is preferably 58 atomic% or more, more preferably 60 atomic% or more. The upper limit is preferably 80 atomic%, more preferably 75 atomic%.
The concentration of the one or more selected metal elements contained in the infrared shielding particles 20P present between the film surface 20S and a depth of 10% from the film surface 20S is preferably 15 to 20 atomic %, more preferably 16 to 18 atomic %.
In this specification, unless otherwise specified, the concentration of two or more metal elements refers to the total concentration of the two or more metal elements.

In the figure, the symbol 0.1t indicates a depth of 10% from the film surface 20S, and the symbol 0.5t indicates a depth of 50% from the film surface 20S. The symbol 20T indicates the range between the film surface 20S and a depth of 50% from the film surface 20S (upper half of the figure), and the symbol 20B indicates the range between a depth of 50% from the film surface 20S and the surface 10S of the glass plate 10 (lower half of the figure).

In the glass laminate 1 of the present embodiment, in a plan view, at least in a part of an upper end portion of the ultraviolet and infrared shielding film 20 that is located within 5 cm from the upper edge of the glass plate 10, the infrared shielding particles 20P are distributed biased toward the film surface 20S side when viewed in the thickness direction, as shown in FIG. 3 .
The particle distribution in Fig. 3 is merely an image. The particle shape and size may be arbitrary and may be uniform or non-uniform. The particle number distribution is not limited to that shown in the figure.

Figure 4 is a partially enlarged schematic cross-sectional view showing a comparison between a comparative glass laminate 101 (left figure) in which the infrared shielding particles 20P are distributed approximately uniformly in the thickness direction, and a glass laminate 1 of this embodiment (right figure) in which the infrared shielding particles 20P are distributed unevenly toward the film surface 20S side. In the figure, the thickness of the white thick arrows shows the UV intensity, with the thicker arrows showing higher UV intensity.

Sunlight containing ultraviolet rays UV enters the glass laminate 101, 1 from the outer surface of the glass plate 10. The ultraviolet ray intensity at the time of entering the glass plate 10 is "high intensity". The ultraviolet ray UV that entered the glass plate 10 decreases in intensity while passing through the glass plate 10, and the ultraviolet ray intensity at the time of entering the ultraviolet and infrared ray shielding film 20 is "medium intensity". The ultraviolet ray intensity in the range 20B (lower half of the figure) between the 50% depth from the film surface 20S and the surface 10S of the glass plate 10 is "medium intensity". The ultraviolet ray UV is shielded (specifically absorbed or reflected) by the ultraviolet ray shielding agent contained in the ultraviolet and infrared ray shielding film 20 while passing through the ultraviolet and infrared ray shielding film 20. The ultraviolet ray intensity in the range 20T between the film surface 20S and the 50% depth from the film surface 20S is "low intensity". Here, "high intensity", "medium intensity", and "low intensity" represent the relative intensity relationship.

In the comparative glass laminate 101 in which the infrared shielding particles 20P are distributed approximately uniformly, approximately half of the infrared shielding particles 20P are present in a range 20B (the lower half in the figure) between a depth of 50% from the film surface 20S and the surface 10S of the glass plate 10. Approximately half of the infrared shielding particles 20P are irradiated with medium-intensity ultraviolet rays UV.
In the glass laminate 1 of this embodiment, in which the infrared shielding particles 20P are distributed unevenly toward the film surface 20S, the number of infrared shielding particles 20P present in the range 20B (the lower half of the illustration) between a depth of 50% from the film surface 20S and the surface 10S of the glass plate 10 is relatively small, and the number of infrared shielding particles 20P exposed to medium-intensity ultraviolet rays UV is relatively small.

Infrared shielding particles 20P that have been exposed to relatively strong (medium to high) ultraviolet light for a long period of time may deteriorate, and if the number of deteriorated infrared shielding particles 20P increases, the visible light transmittance of the ultraviolet/infrared shielding film 20 may decrease.
In the glass laminate 1 of the present embodiment in which the infrared shielding particles 20P are distributed unevenly toward the film surface 20S side, the number of the infrared shielding particles 20P exposed to relatively strong (medium to high) intensity ultraviolet rays UV is relatively small, which effectively suppresses deterioration of the infrared shielding particles 20P due to ultraviolet radiation and the resulting decrease in the visible light transmittance of the ultraviolet/infrared shielding film 20. According to the present embodiment, it is possible to provide a glass laminate 1 in which the weather resistance and light resistance are improved and the decrease in visible light transmittance during use is suppressed.

When the glass laminate is used upright, such as in the application of side glass for vehicles such as automobiles, a relatively large amount of sunlight is irradiated onto the upper side and the area adjacent thereto.
In the schematic plan view shown in FIG. 1, the area indicated by the symbol UP is the upper end portion located within 5 cm from the upper edge 11 of the glass plate 10.
In a plan view, in at least a portion of the upper end portion UP located within 5 cm from the upper edge 11 of the glass plate 10, the infrared shielding particles 20P are distributed in the thickness direction as described above, thereby effectively suppressing deterioration of the infrared shielding particles 20P and the resulting decrease in the visible light transmittance of the ultraviolet and infrared shielding film 20.
In plan view, at the upper end UP, it is preferable that the area of the region where the concentration distribution in the thickness direction of the infrared shielding particles 20P satisfies the above-mentioned regulation is large.
In plan view, it is preferable that the concentration distribution of the infrared shielding particles 20P in the thickness direction satisfies the above-mentioned regulation over substantially the entire area of the upper end portion UP.

In the ultraviolet and infrared shielding film 20, the ultraviolet shielding agent is preferably distributed approximately uniformly in the thickness direction. The ultraviolet shielding agent may be distributed biased toward the glass plate 10 in the thickness direction.
If a sufficient amount of the ultraviolet shielding agent is present in the range 20B (lower half in the figure) between a 50% depth from the film surface 20S and the surface 10S of the glass plate 10, deterioration of the infrared shielding particles 20P present in this range can be effectively suppressed. This effect can be obtained more effectively when the ultraviolet shielding agent is distributed biased toward the glass plate 10 side in the thickness direction.

[Method of manufacturing glass laminate]
The method for producing a glass laminate of the present invention comprises the steps of:
A step (S1) of preparing a liquid composition containing a curable silane, an ultraviolet ray shielding agent, and infrared ray shielding particles;
a _{step (S2) of adjusting the temperature of the glass plate and/or the liquid composition so that T S >} T L , where T _S is the temperature of the glass plate [°C] and T _L is the temperature of the liquid composition [°C]; and a step (S3) of applying the liquid composition, which has a temperature lower than that of the glass plate, onto the surface of the glass plate to form a coating film, thereby obtaining a glass plate with a coating film.
A step (S4) of disposing the glass sheet with the coating film substantially horizontally so that the coating film side faces downward;
and a step (S5) of heating the glass sheet with the coating film to harden the coating film.
In this specification, "substantially horizontal" means within a range of ±10° in the completely horizontal direction with respect to the ground.

Each step will be described with reference to the drawings. Figures 5A to 5C are partial schematic cross-sectional views corresponding to Figure 3.
(Step (S1))
In step (S1), a liquid composition (LC) containing a curable silane, an ultraviolet shielding agent, and infrared shielding particles 20 P is prepared. The liquid composition (LC) may contain one or more optional components other than those described above, such as a resin, a surface conditioner, a chelating agent, a curing catalyst, an acid, and a solvent, as necessary.

(Step (S2))
In step (S2), when the temperature of the glass plate 10 is T _S [° C.] and the temperature of the liquid composition (LC) is T _L [° C.], the temperatures of the glass plate 10 and/or the liquid composition (LC) are adjusted so that T _S >T _L. Preferably, T _S ≧T _L +5, more preferably T _S ≧T _L +10.
In the conventional method, the temperatures of the glass plate 10 and the liquid composition (LC) are not particularly adjusted, and both are at the environmental temperature, which is approximately the same.
The temperature T _S of the glass plate 10 and the temperature T _L of the liquid composition (LC) are not particularly limited as long as they satisfy the above-mentioned requirements. The temperature T _S of the glass plate 10 and the temperature T _L of the liquid composition (LC) can be set, for example, within a range of 10 to 30° C., preferably within a range of 15 to 25° C., so as to satisfy the above-mentioned requirements. The temperature T _S of the glass plate 10 and the temperature T _L of the liquid composition (LC) can be adjusted using a thermostatic bath or the like.

(Step (S3))
In step (S3), as shown in FIG. 5A, a liquid composition (LC) at a temperature lower than that of the glass plate 10 is applied onto the surface 10S of the glass plate 10 to form a coating film 20C, thereby obtaining a glass plate 1C with a coating film.
In applications such as vehicles, the glass plate 10 is processed into a shape having a curved surface, and the coating film 20C is formed on the inner surface side (usually the concave surface side).
In the figure, the symbol 0.1tc indicates a 10% depth from the film surface 20CS of the coating film 20C, the symbol 0.5tc indicates a 50% depth from the film surface 20CS of the coating film 20C, the symbol 20CT indicates a range between the film surface 20CS and a 50% depth from the film surface 20CS, and the symbol 20CB indicates a range between a 50% depth from the film surface 20CS and the surface 10S of the glass plate 10 (the lower half of the figure).
The coating method is not particularly limited, and examples thereof include flow coating, dip coating, spin coating, spray coating, flexographic printing, screen printing, gravure printing, roll coating, meniscus coating, and die coating.
The environmental temperature in step (S3) is not particularly limited, and may be normal room temperature, for example, 10 to 30°C.

(Step (S4))
In step (S4), as shown in Fig. 5B, the glass plate 1C with the coating film is arranged substantially horizontally (also referred to as laid flat) with the coating film 20C side facing downward. For example, the glass plate 10 is held using a holding member such as a suction chuck, and the glass plate 1C with the coating film is arranged substantially horizontally so that the film surface 20CS of the coating film 20C does not come into contact with other members.
The environmental temperature in step (S4) is not particularly limited, and may be normal room temperature, for example, 10 to 30°C.

At the start of this process, as shown in FIG. 5B, the infrared shielding particles 20P are distributed in a substantially uniform concentration in the coating film 20C. The ultraviolet shielding agent is also distributed in a substantially uniform concentration. When the coating film 20C is laid flat with the coating film 20C side facing down, the infrared shielding particles 20P settle overall in the coating film 20C due to gravity and convection in the coating film. By optimizing the settling of the infrared shielding particles 20P, the infrared shielding particles 20P can be biased toward the film surface 20CS as shown in FIG. 5C.

上記式中の各符号は、以下のパラメータを示す。
ｖ_ｓ：沈降速度［ｃｍ／ｓ］、
Ｄ_ｐ：粒子径［ｃｍ］、
ρ_ｐ：粒子の密度［ｇ／ｃｍ^３］、
ρ_ｆ：流体の密度［ｇ／ｃｍ^３］、
ｇ：重力加速度［ｃｍ／ｓ^２］、
η：流体の粘度［ｇ／(ｃｍ・ｓ)］。 In general, the settling velocity of particles in a fluid is expressed by Stokes' law (below).

The symbols in the above formula represent the following parameters.
v _s : Sedimentation velocity [cm / s],
D _p : particle diameter [cm],
ρ _p : particle density [g/cm ³ ],
ρ _f : density of the fluid [g/cm ³ ],
g: gravitational acceleration [cm/s ² ]
η: Viscosity of fluid [g/(cm s)].

Under the same compositional conditions, the higher the liquid temperature of the liquid composition (LC), the lower the viscosity and the faster the settling rate of the infrared shielding particles 20P. However, if the liquid temperature becomes too high, there is a risk that the stability of the liquid will decrease.
In step (S2), by adjusting the temperature T _S [°C] of the glass plate 10 to be higher than the temperature T _L [°C] of the liquid composition (LC), the temperature of the portion of the coating film 20C close to the glass plate 10 (this portion is a portion where the infrared shielding particles 20P are likely to deteriorate during use) is relatively increased, the viscosity of this portion is effectively reduced, and the settling speed of the infrared shielding particles 20P in this portion is effectively increased. In addition, since convection occurs from the high temperature side to the low temperature side due to the temperature gradient in the coating film 20C, the infrared shielding particles 20P are more likely to move to the surface side of the coating film 20C. The infrared shielding particles 20P that have moved to the film surface 20CS side of the coating film 20C have a relatively high specific gravity, so they are less likely to float up to the interface side with the glass plate 10. Due to the combination of these effects, even if the temperature of the liquid composition (LC) at the time of coating is not high, the infrared shielding particles 20P can be unevenly distributed on the film surface 20CS side as shown in FIG. 5C.

In step (S4), the sedimentation depth of the infrared shielding particles 20P having an average primary particle diameter in the portion of the coating film 20C in the vicinity of the interface with the glass plate 10 is not particularly limited, and is preferably 0.1 to 0.4 μm, more preferably 0.1 to 0.3 μm, and particularly preferably 0.1 to 0.2 μm.
In step (S4), the settling velocity of the infrared shielding particles 20P having an average primary particle diameter in the portion of the coating film 20C in the vicinity of the interface with the glass plate 10 is not particularly limited and is preferably 1 to 50 nm/s, more preferably 1 to 20 nm/s, and particularly preferably 5 to 10 nm/s.
The settling depth and settling velocity can be calculated based on the Stokes equation above.

For example, by adjusting the density of the infrared shielding particles 20P, the average primary particle diameter of the infrared shielding particles 20P, the concentration of the infrared shielding particles 20P in the liquid composition (LC), the viscosity of the liquid composition (LC) before coating, the temperature relationship between the glass plate 10 and the liquid composition (LC), and the flat laying time, the settling depth and settling velocity of the infrared shielding particles 20P having the average primary particle diameter in the portion of the coating film 20C near the interface with the glass plate 10 can be adjusted to within the above range.
In this specification, unless otherwise specified, the "portion of the coating film in the vicinity of the interface with the glass sheet" refers to the range from the interface with the glass sheet to a depth of 20% from the interface with the glass sheet.

The density of the infrared shielding particles 20P is not particularly limited. The higher the density, the faster the settling speed tends to be. From the viewpoint of optimizing the settling speed, the density is preferably 5 g/ ^cm3 or more, more preferably 5 to 10 g/ ^cm3 .
The average primary particle size of the infrared shielding particles 20P is not particularly limited. The larger the average primary particle size, the faster the sedimentation rate tends to be. However, if the average primary particle size is too large, haze may occur in the ultraviolet and infrared shielding film 20. From the viewpoint of optimizing the sedimentation rate and the transparency of the ultraviolet and infrared shielding film 20, the average primary particle size is preferably 10 to 150 nm, more preferably 10 to 100 nm, and particularly preferably 50 to 100 nm.
The infrared shielding particles 20P have sufficient density and size, so that they can settle well in the coating film 20C, and an ultraviolet and infrared shielding film 20 having good transparency can be obtained.
In this specification, the "average primary particle size of the infrared shielding particles" is measured by the method described in the section [Examples] below.

There is no particular limit to the time (flat lay time) for which the glass plate 1C with the coating film is placed substantially horizontally with the coating film 20C side facing downward. The longer the time, the greater the settling depth of the infrared shielding particles 20P can be. From the viewpoint of optimizing the settling depth and productivity, the time is preferably 10 to 60 seconds, more preferably 10 to 50 seconds, and particularly preferably 20 to 40 seconds.

The density of the ultraviolet shielding agent is not particularly limited, and is preferably 2.5 g/cm ³ or less. When the density of the ultraviolet shielding agent is smaller than the density of the infrared shielding particles 20P, and is preferably 2.5 g/cm ³ or less, the sedimentation of the ultraviolet shielding agent can be effectively suppressed, and the ultraviolet shielding agent can be maintained in a state of being distributed at a substantially uniform concentration in the coating film 20C.
If the density of the ultraviolet shielding agent is sufficiently low, at least a part of the ultraviolet shielding agent may float due to the settling of the infrared shielding particles 20P and migrate to the glass plate 10. In this case, the ultraviolet shielding agent can be distributed unevenly toward the glass plate 10.
By distributing the ultraviolet ray blocking agent in a substantially uniform concentration in the coating film 20C or distributing the agent biased toward the glass plate 10, the obtained glass laminate 1 can effectively block ultraviolet rays in the portion close to the glass plate 10 and effectively suppress deterioration of the infrared ray blocking particles 20P due to ultraviolet ray exposure.

(Drying process)
Between steps (S4) and (S5), a drying step may be performed as necessary to dry the coating film 20C under conditions in which the curing reaction does not proceed. The drying method is not particularly limited, and examples thereof include heat drying at about 40 to 60°C, drying under reduced pressure, and heat drying under reduced pressure at about 40 to 60°C.

(Step (S5))
In step (S5), the glass sheet 1C with the coating film is heated to cure the coating film 20C. The heating is performed under temperature conditions where the curable silane cures to silica. Step (S5) (heat curing step) can be performed in one step of baking only or in two steps of pre-baking and baking.
The firing temperature is not particularly limited. When the glass plate 10 is tempered glass, the firing temperature is preferably 80 to 230° C., more preferably 100 to 230° C., particularly preferably 150 to 230° C., and most preferably 180 to 210° C. When the glass plate 10 is laminated glass, the firing temperature is preferably 80 to 110° C., more preferably 90 to 110° C. The heating time can be appropriately designed depending on the composition of the liquid composition (LC), the heating temperature, and the like.

The orientation of the coated glass sheet 1C in the drying step and step (S5) is not particularly limited.
In the drying step and step (S5), the glass plate 1C with the coating film may be arranged substantially horizontally so that the coating film 20C is on the bottom side, as in step (S4). In this case, the infrared shielding particles 20P may settle slightly in these steps as well, but since the coating film 20C becomes solid or nearly so at an early stage after the start of the steps, the settling depth is short and can be considered to be negligible.
In the drying step and step (S5), the glass sheet 1C with the coating film may be arranged substantially horizontally so that the coating film 20C side faces upward.
In this manner, the glass laminate 1 as shown in FIG. 3 is obtained.

As described above, this embodiment can provide a glass laminate 1 that can effectively block ultraviolet and infrared rays, has improved weather resistance and light resistance, and can suppress a decrease in visible light transmittance during use.

The present invention will be described below based on examples, but the present invention is not limited to these. Examples 1 and 2 are examples, and Examples 11 to 13 are comparative examples.

[Evaluation items and evaluation methods]
The evaluation items and evaluation methods are as follows: The ultraviolet and infrared shielding film and the glass laminate were evaluated for the upper end portion of the glass laminate located within 5 cm from the upper end side of the glass plate.

(Viscosity of Liquid Composition (LC))
The viscosity of the liquid composition (LC) was measured using a viscometer ("RE85L" manufactured by Toki Sangyo Co., Ltd.) at 25°C or 15°C.

(Thickness of ultraviolet and infrared shielding film)
The thickness D [μm] of the ultraviolet and infrared shielding film was measured using a stylus surface profiler (Dektak150 manufactured by ULVAC).

(Average primary particle size of infrared shielding particles)
A scanning electron microscope (SEM) ("S-4800" manufactured by Hitachi High-Technologies Corporation) was used to observe the cross section of the glass laminate. Cross-sectional SEM images (magnification: 200,000 times) were obtained at five randomly selected locations. The average value of the primary particle diameters of all the infrared shielding particles observed in the cross-sectional SEM images at the five locations was determined as the average primary particle diameter.

(XPS analysis of ultraviolet and infrared shielding film)
Using XPS (ULVAC's "PHIQuantera SXM"), elemental analysis was performed in the depth direction from the film surface of the ultraviolet and infrared shielding film for one arbitrarily selected metal element (for example, In in the case of ITO) contained in the infrared shielding particles, and an XPS spectrum was obtained. From the area ratio of the spectrum, the concentration [atomic%] of the selected metal element within a certain range viewed in the depth direction was obtained. When the ultraviolet and infrared shielding film was viewed in the depth direction from the film surface, the concentration of the selected metal element contained in the infrared shielding particles present between the film surface and a depth of 50% from the film surface, and the concentration of the selected metal element contained in the infrared shielding particles present between the film surface and a depth of 10% from the film surface were obtained.

(Visible Light Transmittance of Glass Laminate)
The transmission spectrum of the glass laminate in the wavelength range of 300 to 2600 nm was measured using a spectrophotometer ("U-4100" manufactured by Hitachi, Ltd.), and the visible light transmittance (Tv [%]) in the initial state before carrying out the weather resistance and light resistance test was calculated in accordance with JIS R3212 (1998).

(Weather resistance and light resistance of glass laminates)
The glass laminate was placed in a super xenon weather meter (SX75, manufactured by Suga Test Instruments Co., Ltd.) set under the following conditions: wavelength of irradiation light in the range of 300 to 400 nm, irradiation illuminance of 150 W/m ² , black panel temperature of 83°C, and relative humidity of 50%, and a test was performed for 500 hours. After this test, the transmission spectrum was measured and the visible light transmittance (Tv [%]) was calculated using the same method as before the test. The change (ΔTv) [%] in Tv [%] after the test relative to Tv [%] before the test was calculated. The smaller the decrease in ΔTv, the better the weather resistance and light resistance.

(Specific gravity of ultraviolet and infrared shielding film)
An arbitrary area S [ ^cm2 ] of the ultraviolet and infrared shielding film was scraped off from the glass laminate with a razor, and the change in mass [g] of the glass laminate was recorded as the mass W [g] of the ultraviolet and infrared shielding film. If the mass of the glass laminate is much larger than the mass of the ultraviolet and infrared shielding film and the difference is judged to be insignificant, the mass of the scraped off ultraviolet and infrared shielding film may be measured directly. The specific gravity d [g/ ^cm3 ] was calculated from the following formula:
d = W / (S x D) [g/ ^cm3 ]

(Infrared shielding particle content [mg/cm ² ])
Using XPS (ULVAC's "PHIQuantera SXM"), a total element analysis was performed in the ultraviolet and infrared shielding film in the depth direction from the film surface to obtain an XPS spectrum. From the area ratio of the spectrum peak, the mass concentration [mass%] of each element within a certain range in the depth direction was obtained. The average value of the distribution of the mass concentration [mass%] in the depth direction was taken as the mass concentration [mass%] of each element in the entire ultraviolet and infrared shielding film. Next, the mass concentration [mass%] of the infrared shielding particles contained in the ultraviolet and infrared shielding film was obtained from the sum of the mass concentrations [mass%] of each element contained in the infrared shielding particles (for example, In, Sn, and O in the case of ITO).
When the ultraviolet and infrared shielding film excluding the infrared shielding particles contains the same element X (e.g., O in the case of ITO) as the element contained in the infrared shielding particles, the mass concentration of the element X was determined so that the infrared shielding particles as a whole were electrically neutral. At this time, a commonly known value was used as the oxidation number of each element contained in the infrared shielding particles. For example, in the case of ITO, In was 3+, Sn was 4+, and O was 2-, and the mass concentration [mass %] of O was determined. From the mass concentration [mass %] of each element of the infrared shielding particles contained in the ultraviolet and infrared shielding film thus determined, and the thickness and specific gravity of the ultraviolet and infrared shielding film, the content [mg/cm ² ] of the infrared shielding particles contained per 1 cm ² of the ultraviolet and infrared shielding film was determined.

(Absorbance of ultraviolet and infrared shielding film)
Using a spectrophotometer (Hitachi, Ltd., "U-4100"), the transmission spectra of the glass laminate and the glass plate in the wavelength region of 800 to 1500 nm were measured, and the absorbance and simple average of the absorbance of the ultraviolet and infrared shielding film in the wavelength region of 800 to 1500 nm were calculated from the difference between the absorbance of the glass laminate and the glass plate.

[material]
The abbreviations for the materials used in each example are as follows.
<Glass plate>
(G1) A curved glass plate (vertical radius of curvature of the inner surface (concave surface) = 5,200 mm, horizontal radius of curvature = 300,000 mm) made from a rectangular glass plate ("High heat ray absorbing green glass" manufactured by AGC) measuring 670 mm in height × 910 mm in width × 3.1 mm in thickness in a plan view (vertical radius of curvature of the inner surface (concave surface) = 5,200 mm, horizontal radius of curvature = 300,000 mm).

TEOS: tetraethoxysilane,
KBM-403: 3-glycidoxypropyltrimethoxysilane, Shin-Etsu Chemical Co., Ltd. "KBM-403",
EX-614B: Epoxy resin, Nagase Chemtex Corporation "EX-614B",
Solsperse 41000: polyether phosphate ester polymer, Solsperse 41000 manufactured by Lubrizol Japan,
TINUVIN360: "TINUVIN360" manufactured by Ciba Specialty Chemicals,
BYK307: Surface conditioner, BYK307 manufactured by BYK-Chemie Japan Co., Ltd.
AP-1: a mixed solvent of 85.5% by mass of ethanol, 1.1% by mass of methanol, and 13.4% by mass of 2-propanol.

[Production Example 1] (Preparation of Liquid Composition (LC1))
A beaker was charged with 49.2 g of 2,2',4,4'-tetrahydroxybenzophenone (manufactured by BASF), 123.2 g of 3-glycidoxypropyltrimethoxysilane (KBM-403), 0.8 g of benzyltriethylammonium chloride (BTEAC) (manufactured by Junsei Chemical Co., Ltd.) as a curing catalyst, and 100 g of butyl acetate (manufactured by Junsei Chemical Co., Ltd.). These were heated to 60°C with stirring to dissolve, and then heated to 120°C and reacted for 4 hours to obtain a silylated ultraviolet absorber solution with a solid content concentration of 63% by mass.
In a round-bottom flask, 12.78 g of the above silylated ultraviolet absorber solution, 49.82 g of mixed solvent (AP-1), 11.43 g of tetraethoxysilane (TEOS), 2.81 g of 3-glycidoxypropyltrimethoxysilane (KBM-403), 1.96 g of epoxy resin (EX-614B), 15.60 g of pure water, 0.06 g of surface conditioner (BYK307), and 0.10 g of nitric acid aqueous solution having a concentration of 63% by mass as acid were charged and stirred for 2 hours at 50 ° C. Then, 5.44 g of 20% by mass CWO (registered trademark) dispersion (manufactured by Sumitomo Metal Mining Co., Ltd., solvent is water) was added to obtain a liquid composition (LC1) having a solid content concentration of 14.5% by mass.
The main components and the solids concentration of the resulting liquid composition are shown in Table 1.

[Production Examples 2 and 3] (Preparation of Liquid Compositions (LC2) and (LC3))
Liquid compositions (LC2) and (LC3) were obtained in the same manner as in Production Example 1, except that the blending composition was changed to that shown in Table 1. The main blending composition and the solid content concentration of the obtained liquid composition are shown in Table 1.
The 20% by mass ITO dispersion used in Production Examples 2 to 4 was manufactured by Mitsubishi Materials Corporation (solvent was mixed solvent (AP-1)).

[Production Example 4] (Preparation of Liquid Composition (LC4))
A silylated ultraviolet screening agent solution was not prepared, and all the components except for the 20% by mass ITO dispersion were mixed and reacted at 50° C. for 2 hours, after which the 20% by mass ITO dispersion was added and mixed to obtain a liquid composition (LC4). The main blending composition and the solid content concentration of the obtained liquid composition are shown in Table 1.

[Example 1]
(Step (S1)) (Preparation of Liquid Composition (LC1))
The liquid composition (LC1) obtained in Production Example 1 was prepared.

(Step (S2))
Using a thermostatic bath, the temperature T _S of the glass plate (G1) was adjusted to 25°C, and the temperature T _L of the liquid composition (LC1) was adjusted to 15°C.

(Step (S3))
The glass plate (G1) was placed vertically, and the liquid composition (LC1) at the adjusted temperature in step (S2) was poured onto the inner surface (concave surface) of the glass plate (G1) at a position spaced from the upper edge of the glass plate (G1) by several mm to several tens of mm, along the upper edge of the glass plate (G1). In this manner, a glass plate with a coating film was obtained.

(Step (S4))
The glass plate with the coating film was placed horizontally (laid flat) for 20 seconds with the coating film side facing downward. In this step, the glass plate 10 was held using a suction chuck, and the glass plate with the coating film was placed horizontally so that the surface of the coating film would not come into contact with other members.

(Step (S5))
The glass plate with the coating film was heated at 200° C. for 20 minutes (main baking). In the main baking, the glass plate with the coating film was placed horizontally (laid flat) so that the coating film side was on the upper side. In this way, the coating film was cured to obtain a glass laminate (GL1).

The main production conditions and the evaluation results are shown in Tables 2 and 3. In Tables 2 and 3, conditions not described were common conditions.
The settling velocity and settling depth of the infrared shielding particles having an average primary particle size in the vicinity of the interface between the coating film and the glass plate were calculated based on Stokes' equation. In the calculation, the temperature of the coating film in the vicinity of the interface between the coating film and the glass plate was determined using the temperature of the glass plate adjusted in step (S2), and the viscosity of the liquid composition was determined using the viscosity of the liquid composition at the temperature of the glass plate adjusted in step (S2).

[Example 2, Examples 11 to 13]
Glass laminates (GL2), (GL11) to (GL13) were obtained in the same manner as in Example 1, except that the conditions were changed as shown in Table 2. The main production conditions and evaluation results are shown in Tables 2 and 3.

[Summary of results]
In Examples 1 and 2, a liquid composition having a temperature lower than that of the glass plate was applied onto the surface of the glass plate to form a coating film, thereby obtaining a glass plate with a coating film. The glass plate with the coating film was then horizontally arranged with the coating film side facing downward, and the glass plate with the coating film was then heated to harden the coating film, thereby producing a glass laminate.
In these examples, a glass laminate was obtained in which, in a plan view, at the upper end of the ultraviolet and infrared shielding film located within 5 cm from the upper edge of the glass plate, the concentration of a selected type of metal element contained in the infrared shielding particles present between the film surface and a depth of 50% from the film surface was 55 atomic % or more, and the concentration of a selected type of metal element contained in the infrared shielding particles present between the film surface and a depth of 10% from the film surface was 12 to 20 atomic %.
In the weather resistance and light resistance test, the glass laminates obtained in these examples showed a small decrease in visible light transmittance after the test compared to before the test, which was favorable.

In particular, the glass laminate obtained in Example 1 had a concentration of 60 atomic% or more of the selected metal element contained in the infrared shielding particles present between the film surface and a depth of 50% from the film surface, and a concentration of 15 atomic% or more of the selected metal element contained in the infrared shielding particles present between the film surface and a depth of 10% from the film surface, and was superior in weather resistance and light resistance to the glass laminate obtained in Example 2.

In Example 11, the temperature of the glass plate and the temperature of the liquid composition were made the same.
In Example 12, the viscosity of the liquid composition was high, and the settling velocity and settling depth of the infrared shielding particles having an average primary particle size in the portion of the coating film near the interface with the glass plate were too small.
In Example 13, the glass plate with the coating film was horizontally arranged with the coating film side facing upward, and then the glass plate with the coating film was heated to cure the coating film.

In the glass laminates obtained in Examples 11 to 13, in a plan view, at an upper end portion of the ultraviolet and infrared shielding film located within 5 cm from the upper end edge of the glass plate, the concentration of a selected type of metal element contained in the infrared shielding particles present between the film surface and a depth of 10% from the film surface was less than 12 atomic %.
In the glass laminates obtained in Examples 12 and 13, in a plan view, at an upper end portion of the ultraviolet/infrared shielding film located within 5 cm from the upper end edge of the glass plate, the concentration of a selected type of metal element contained in the infrared shielding particles present between the film surface and a depth of 50% from the film surface was less than 55 atomic %.
In Example 11, the settling rate was within a preferred range, and the infrared shielding particles were distributed unevenly over the entire surface 50% of the coating film. However, because the glass plate and the liquid composition had the same temperature, no convection due to the temperature difference occurred in the coating film, and the amount of infrared shielding particles that settled over the surface 10% of the coating film was small.
In the weather resistance and light resistance test, the glass laminates obtained in these examples showed a large decrease in visible light transmittance after the test compared to before the test, and were therefore unsatisfactory.

Representative XPS spectra of the ultraviolet and infrared shielding films of the glass laminates obtained in Examples 1, 2 and 13 are shown in FIGS. 6A to 6C.
As shown in Fig. 6C , the XPS spectrum of the ultraviolet and infrared shielding film of the glass laminate obtained in Example 13 showed that the infrared shielding particles were distributed uniformly overall, whereas as shown in Figs. 6A and 6B , the XPS spectra of the ultraviolet and infrared shielding films of the glass laminates obtained in Examples 1 and 2 showed that the infrared shielding particles were distributed unevenly toward the film surface side.

Representative examples of cross-sectional SEM photographs of the glass laminates obtained in Examples 1 and 2 are shown in Figures 7A and 8A. The film indicated by reference numeral 20 is the ultraviolet and infrared shielding film. The obtained cross-sectional SEM images were subjected to a trimming process to leave only the ultraviolet and infrared shielding film portion, and further subjected to a binarization process by brightness to show the infrared shielding particles as "black" and the other portions as "white", and the images are shown in Figures 7B and 8B.
7A, 7B, 8A, and 8B are cross-sectional photographs or cross-sectional images of a thick film portion near the bottom side of a glass laminate in a plan view, and are reference photographs or images. Although they are reference photographs or images, these figures show that the infrared shielding particles are biased toward the film surface side.

The present invention is not limited to the above-described embodiments and examples, and the design can be modified as appropriate without departing from the spirit of the present invention.

1: Glass laminate, 1C: Glass plate with coating film, 10: Glass plate, 10S: Surface, 11: Top edge, 12: Bottom edge, 13: Front edge, 14: Rear edge, 20: UV/IR shielding film, 20C: Coating film, 20P: Infrared shielding particles, 20S: Film surface, UP: Top end.

Claims (12)

A glass laminate comprising an ultraviolet and infrared shielding film formed on a surface of a glass plate, the ultraviolet and infrared shielding film including silica, an ultraviolet shielding agent, and infrared shielding particles including a metal compound,
In a plan view, in at least a part of an upper end portion of the ultraviolet and infrared ray shielding film located within 5 cm from the upper end edge of the glass plate,
When the concentration of one or more arbitrarily selected metal elements contained in all of the infrared shielding particles present in the ultraviolet and infrared shielding film is taken as 100 atomic %, the thickness of the ultraviolet and infrared shielding film is taken as 100%, and the ultraviolet and infrared shielding film is viewed in the depth direction from the film surface,
the concentration of the one or more metal elements contained in the infrared shielding particles present between the film surface and a depth of 50% from the film surface is 55 atomic % or more;
a concentration of the one or more metal elements contained in the infrared shielding particles present between the film surface and a depth of 10% from the film surface is 12 to 20 atomic %. The glass laminate according to claim 1 , wherein the infrared shielding particles have a density of 5 g/cm ³ or more. The glass laminate according to claim 2, wherein the infrared shielding particles have a density of 5 to 10 g/ ^cm3 . The glass laminate according to any one of claims 1 to 3, wherein the infrared shielding particles have an average primary particle size of 10 to 150 nm. The glass laminate according to any one of claims 1 to 4, wherein the infrared shielding particles are metal compound particles containing one or more metal compounds selected from the group consisting of indium tin oxide, antimony-doped tin oxide, cesium-doped tungsten oxide, fluorine-doped tin oxide, lanthanum hexaboride, and vanadium pentoxide. The glass laminate according to claim 5, wherein the infrared shielding particles are metal compound particles containing one or more metal compounds selected from the group consisting of cesium-doped tungsten oxide and lanthanum hexaboride. The glass laminate according to any one of claims 1 to 6, wherein the ultraviolet ray shielding agent has a density of 2.5 g/ ^cm3 or less. The glass laminate according to any one of claims 1 to 7, wherein the ultraviolet shielding agent is one or more ultraviolet absorbers selected from the group consisting of benzophenone-based ultraviolet absorbers, benzotriazole-based ultraviolet absorbers, benzodithiol-based ultraviolet absorbers, azomethine-based ultraviolet absorbers, indole-based ultraviolet absorbers, and triazine-based ultraviolet absorbers. A step (S1) of preparing a liquid composition containing a curable silane, the ultraviolet ray shielding agent, and the infrared ray shielding particles;
a step (S2) of adjusting the temperature of the glass plate and/or the liquid composition so that T _S >T _L , where T _S is the temperature of the glass plate [°C] and T _L is the temperature of the liquid composition [°C];
A step (S3) of applying the liquid composition having a temperature lower than that of the glass plate onto a surface of the glass plate to form a coating film, thereby obtaining a glass plate with a coating film;
A step (S4) of disposing the glass sheet with the coating film substantially horizontally so that the coating film side faces downward;
The method for producing a glass laminate according to any one of claims 1 to 8, further comprising a step (S5) of heating the glass sheet with the coating film to harden the coating film. The method for producing a glass laminate according to claim 9, wherein in step (S2), a temperature of the glass plate and/or the liquid composition is adjusted so that T _S ≧T _L +5. The method for producing a glass laminate according to claim 9 or 10, wherein in step (S4), the sedimentation depth of the infrared shielding particles having an average primary particle diameter in at least a portion of the coating film near the interface with the glass sheet is 0.1 to 0.4 μm. The method for producing a glass laminate according to any one of claims 9 to 11, wherein in step (S4), the settling velocity of the infrared shielding particles having an average primary particle size in at least a portion of the coating film near the interface with the glass sheet is 1 to 50 nm/s.

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