Glass laminate and method of manufacturing the same

Abstract

The present invention provides a glass laminate that can favorably shield infrared rays and has favorable heat resistance, moisture resistance, and abrasion resistance. A glass laminate (1) comprising an infrared rays shielding film (20) containing silica and infrared rays shielding particles (20P) formed on a surface (10S) of a glass plate (10), wherein, when the thickness of the infrared rays shielding film (20) is 100% and the infrared rays shielding film (20) is seen in a depth direction from an interface (10S) with the glass plate in at least a partial region of the infrared rays shielding film (20) in a plan view, the ratio of the number of the infrared rays shielding particles (20P) existing between the interface and a 50% depth position from the interface to the total number of the infrared rays shielding particles (20P) is 52% or more, and the ratio of the number of the infrared rays shielding particles (20P) existing between the interface and a 5% depth position from the interface to the number of the infrared rays shielding particles (20P) existing between the 5% depth position from the interface and a 10% depth position from the interface is 1.2 or less.

Description

[Technical Field]

[0001] The present invention relates to a glass laminate and a method for making the same. [Background technology]

[0002] For use in vehicles such as automobiles, a glass laminate is known in which an infrared-shielding film having high transmittance for visible light but low transmittance for infrared light is formed on the surface of a glass plate. The infrared-shielding film is, for example, a film containing 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 thereof (Claim 1). The composition for forming the ultraviolet-shielding film contains an ultraviolet absorber and a curable silane, and more preferably contains an infrared absorber such as ITO (indium tin oxide) and a solvent (Paragraphs 0035, 0041, 0047). The ultraviolet-shielding film can be formed by applying the composition to a glass plate, drying it, and curing it (Paragraph 0042). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] International Publication No. 2020 / 141601 Summary of the Invention [Problem to be solved by the invention]

[0004] The inventors' research has revealed that a glass laminate having an infrared-shielding film containing infrared-shielding particles such as ITO may experience a decrease in infrared-shielding performance in a heat resistance test or a moisture resistance test, and may experience peeling of the infrared-shielding film from the glass plate in an abrasion resistance test.

[0005] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a glass laminate that can effectively shield infrared rays and has good heat resistance, moisture resistance, and abrasion resistance. [Means for solving the problem]

[0006] The present invention provides the following glass laminate and method for producing the same. [1] A glass laminate in which an infrared-shielding film containing silica and infrared-shielding particles is formed on the surface of a glass plate, In a plan view, in at least a part of the infrared shielding film, When the thickness of the infrared shielding film is taken as 100%, and the infrared shielding film is viewed in the depth direction from the interface with the glass plate, a ratio of the number of the infrared-shielding particles present between the interface and a depth of 50% from the interface to the total number of the infrared-shielding particles is 52% or more, a ratio of the number of the infrared shielding particles present between the interface and a depth of 5% from the interface to the number of the infrared shielding particles present between a depth of 5% from the interface and a depth of 10% from the interface is 1.2 or less.

[0007] [2] A step (S1) of preparing a liquid composition containing a curable silane and the infrared shielding particles; The temperature of the glass plate is T S [°C], and the temperature of the liquid composition is T L When [℃], T S <T L a step (S2) of adjusting the temperature of the glass plate and / or the liquid composition so that a step (S3) of applying the liquid composition, which has a temperature higher 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 placing the glass plate with the coating film substantially horizontally so that the coating film side faces upward; and (S5) heating the glass sheet with a coating film to cure the coating film. [Effects of the Invention]

[0008] The glass laminate of the present invention has a configuration in which, in a plan view, in at least a part of the infrared-shielding film, when viewed in the thickness direction, the infrared-shielding particles are distributed unevenly toward the interface with the glass plate, and no excess infrared-shielding particles are present in the vicinity of the interface with the glass plate. The glass laminate of the present invention can effectively shield infrared rays and has good heat resistance, moisture resistance and abrasion resistance. [Brief explanation of the drawings]

[0009] [Figure 1] 1 is an example of a schematic plan view of a glass laminate according to an embodiment of the present invention. [Figure 2] 1 is a schematic cross-sectional view of a glass laminate according to one embodiment of the present invention. [Figure 3] FIG. 3 is a partially enlarged schematic cross-sectional view of FIG. 2. [Figure 4] FIG. 1 is a partially enlarged schematic cross-sectional view showing a first comparative glass laminate (left figure) in which infrared-shielding particles are distributed substantially uniformly, and a second comparative glass laminate (right figure) in which infrared-shielding particles are distributed at a high concentration near the interface with the glass plate. [Figure 5A] FIG. 3 is a schematic cross-sectional view showing step (S3) of the method for producing a glass laminate according to one embodiment of the present invention. [Figure 5B] FIG. 3 is a schematic cross-sectional view showing step (S4) of the method for producing a glass laminate according to one embodiment of the present invention. [Figure 6A] 1 is an XPS spectrum of the infrared shielding film of Example 1. [Figure 6B] 1 is an XPS spectrum of the infrared shielding film of Example 11. [Figure 7] FIG. 1 is a diagram showing a method for measuring the abundance ratio of infrared-shielding particles in an infrared-shielding film. [Figure 8] 1 shows examples of images after trimming and binarization of cross-sectional SEM photographs of the glass laminates obtained in Examples 1, 11, and 13. DETAILED DESCRIPTION OF THE INVENTION

[0010] Generally, thin film structures are referred to as "films" or "sheets" depending on their thickness. In this specification, no clear distinction is made between these terms. Therefore, in this specification, "films" 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 state of use). 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 symbol "to" indicating a range of values ​​is used to mean that the values ​​before and after it are included as the lower and upper limits. Hereinafter, an embodiment of the present invention will be described.

[0011] [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, and 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 infrared shielding film 20 containing silica and infrared shielding particles 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 infrared shielding film 20 side, and is also referred to as the interface between the glass plate 10 and the infrared shielding film 20.

[0012] The glass laminate 1 of the present embodiment can be preferably applied to glass for vehicles such as automobiles (for example, windshields, side glass, and rear glass). In applications such as vehicles, the infrared shielding film 20 is formed on the inner surface side of the glass plate 10 (the side where passengers are present, usually the concave side). The infrared shielding film 20 may be formed over the entire surface of one surface 10S of the glass plate 10, or may be formed over substantially the entire surface 10S of the glass plate 10 except for at least a part of the peripheral edge (for example, an area within 30 mm from an edge). The infrared shielding film 20 only needs to be formed in an area that is visible in use (for example, when fitted into a vehicle or the like), and does not necessarily have to be formed in the peripheral edge that is not visible in use.

[0013] 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 made up of four sides: 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 infrared shielding film 20 has an outer periphery consisting of four sides: an upper side 21, a lower side 22, a front side side 23, and a rear side side 24. For easier visibility, the portion of the outer periphery of the 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 side 21 of the infrared shielding film 20 is located approximately 15 mm inward from the upper side 11 of the glass plate 10, the front side side 23 of the infrared shielding film 20 coincides with the front side side 13 of the glass plate 10, and the rear side side 24 of the infrared shielding film 20 coincides with the rear side side 14 of the glass plate 10. The planar shape of the glass plate 10 and the area where the infrared shielding film 20 is formed can be designed appropriately depending on the shape of the vehicle or the like to which it is to be attached.

[0014] (glass plate) Examples of the glass plate 10 include tempered glass, laminated glass formed by bonding multiple glass plates 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 plate 10 is illustrated as flat, but for applications such as vehicles, the glass plate 10 is processed into a shape having a curved surface. The type of glass plate that is the material for tempered glass and laminated glass is not particularly limited, and examples include soda lime glass, borosilicate glass, aluminosilicate glass, lithium silicate glass, quartz glass, sapphire glass, and alkali-free glass. Tempered glass is obtained by subjecting the above-mentioned glass plate to tempering processing by a known method such as an ion exchange method or an air-cooling tempering method, etc. As the tempered glass, air-cooling tempered glass is preferred. The thickness of the tempered glass is not particularly limited and is designed depending on the application, and is preferably 2 to 6 mm for applications such as windshields, side windows, and rear windows of vehicles. There are no particular restrictions on the thickness of the laminated glass, and it 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.

[0015] 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 can effectively bond multiple glass sheets. 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 resins exemplified above is preferred.

[0016] 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 area of ​​the surface. The laminated glass may have a film having functions such as low reflectivity, low emissivity, and coloring in at least a portion of its interior. At least a portion of the interlayer film of the laminated glass may have functions such as coloring. The interlayer film of the laminated glass may be a single-layer film or a multilayer film.

[0017] Examples of 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.

[0018] (Infrared shielding film) 3, the infrared shielding film 20 contains silica and infrared shielding particles 20P. The infrared shielding film 20 contains the infrared shielding particles 20P, and therefore can effectively shield infrared rays. The infrared shielding film 20 can contain an ultraviolet shielding agent as needed, and in this case, the infrared shielding film 20 can effectively shield infrared rays and ultraviolet rays. The infrared shielding particles 20P may be of known types, and may be of either an infrared absorbing type or an infrared reflecting type.

[0019] The infrared shielding particles 20P are preferably metal compound particles containing one or more metal compounds, such as indium tin oxide (ITO), antimony-doped tin oxide (ATO), cesium-doped tungsten oxide (CWO®), fluorine-doped tin oxide (FTO), lanthanum hexaboride (LaB6), and vanadium pentoxide (VO5).

[0020] As the infrared shielding particles 20P, metal compound particles containing cesium-doped tungsten oxide (CWO (registered trademark)) and / or lanthanum hexaboride (LaB6) are particularly preferred. When using these metal compound particles, the absorbance of the infrared shielding film for light with a wavelength of 800 to 1500 nm is 2The value obtained by dividing the mass of the infrared-shielding particles contained per unit area by the mass of the infrared-shielding particles can be made relatively large, for example, 1.5 or more. In this case, the content of the infrared-shielding particles 20P in the infrared-shielding film can be reduced. This reduces the absolute number of particles present in the portion of the infrared-shielding film 20 near the interface 10S with the glass plate 10, thereby improving the adhesion between the glass plate 10 and the infrared-shielding film 20 and improving the abrasion resistance.

[0021] As the ultraviolet shielding agent, known agents can be used, and they may be of either an ultraviolet absorbing or ultraviolet reflecting type. Preferred 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. The infrared shielding film 20 may contain one or more optional components other than those mentioned above, as needed.

[0022] The infrared shielding film 20 can be formed by preparing a liquid composition (LC) containing a curable silane and infrared shielding particles 20P, and which may further contain an ultraviolet shielding agent if necessary, applying this liquid composition (LC) to the surface 10S of the glass plate 10, and heating to harden the coated film.

[0023] A curable silane refers to a silicon compound having one or more silicon atoms bonded to one or more hydroxyl groups or one or more hydrolyzable groups. Hydrolyzable groups are groups that can become hydroxyl groups upon hydrolysis, and examples include alkoxy groups, chlorine atoms, acyl groups, and acyloxy groups. Preferred curable silanes are alkoxysilanes having a silicon atom bonded to two or more alkoxy groups, and the alkoxy groups are preferably alkoxy groups having 1 to 4 carbon atoms.

[0024] The curable silane is preferably a tetraalkoxysilane or a bisalkoxysilane. Examples of the tetraalkoxysilane include tetraethoxysilane (TEOS) and tetramethoxysilane. Examples of the bisalkoxysilane include a compound represented by the following formula (1): R 1 n X 1 3-n Si-Q-SiR 2 m X 2 3-m ···(1) In the above formula, R 1 and R 2 are each independently a monovalent hydrocarbon group having 1 to 3 carbon atoms. 1 and X 2 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.

[0025] When the liquid composition (LC) containing the curable silane is heated, silica is produced through hydrolysis and polycondensation of the curable silane. However, after the curing reaction is completed, some intermediate products such as partial hydrolysis and condensation products of the curable silane may remain in the infrared shielding film 20. Unless otherwise specified, "silica" as used herein refers to a reaction product of a curable silane, and may include a partial hydrolysis condensate of the curable silane.

[0026] (Distribution of infrared shielding particles) 3, in the glass laminate 1 of the present embodiment, the infrared shielding film 20 has a distribution in the number of infrared shielding particles 20P when viewed in the thickness direction. The thickness of the infrared shielding film 20 is taken as 100%.

[0027] In the glass laminate 1 of the present embodiment, in a plan view, in at least a partial region of the infrared shielding film 20, When the infrared shielding film 20 is viewed in the depth direction from the interface 10S with the glass plate 10, The ratio of the number of infrared-shielding particles 20P present between the interface 10S and a depth 50% from the interface 10S to the total number of infrared-shielding particles 20P is 52% or more, The ratio of the number of infrared-shielding particles 20P present between the interface 10S and a depth of 5% from the interface 10S to the number of infrared-shielding particles 20P present between a depth of 5% from the interface 10S and a depth of 10% from the interface 10S is 1.2 or less. The number of infrared shielding particles 20P present in a certain depth range when viewed in the thickness direction is measured by the method described in the section [Examples] below.

[0028] In the figure, symbol 0.1t indicates a depth of 10% from the interface 10S, symbol 0.5t indicates a depth of 50% from the interface 10S, 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 symbol 20B indicates the range between a depth of 50% from the film surface 20S and the interface 10S (lower half of the figure).

[0029] FIG. 4 is a partially enlarged schematic cross-sectional view showing a first comparative glass laminate 101 (left diagram) in which the infrared-shielding particles 20P are distributed approximately uniformly in the thickness direction, and a second comparative glass laminate 102 (right diagram) in which the infrared-shielding particles 20P are distributed at a high concentration near the interface 10S with the glass plate 10.

[0030] In the first comparative glass laminate 101 in which the infrared-shielding particles 20P are distributed substantially uniformly, a relatively large number of the infrared-shielding particles 20P are present in the vicinity of the film surface 20S. The infrared-shielding particles 20P present in the vicinity of the film surface 20S may be degraded by oxygen and / or moisture in the air, resulting in a decrease in the infrared-shielding performance. Therefore, the infrared-shielding performance of the infrared-shielding film 20 may be reduced in a heat resistance test or a moisture resistance test. In the second comparative glass laminate 102 in which infrared shielding particles 20P are distributed at a high concentration near the interface 10S with the glass plate 10, the adhesion between the glass plate 10 and the infrared shielding film 20 is reduced, resulting in reduced abrasion resistance.

[0031] In the glass laminate 1 of the present embodiment, in a plan view, in at least a portion of the infrared shielding film 20, when viewed in the thickness direction, as shown in FIG. 3 , the infrared shielding particles 20P are distributed unevenly toward the interface 10S with the glass plate 10, and no excess infrared shielding particles 20P are present in the vicinity of the interface 10S with the glass plate 10. The particle distribution in Figure 3 is an image. The particle shape and particle size are arbitrary and may be uniform or non-uniform. The particle number distribution is not limited to that shown in the figure.

[0032] In the glass laminate 1 of the present embodiment, the number of infrared shielding particles 20P present in the vicinity of the film surface 20S is relatively small, and therefore few infrared shielding particles 20P come into contact with oxygen and / or moisture in the air, effectively preventing deterioration of the infrared shielding particles 20P due to oxygen and / or moisture in the air and resulting deterioration in the infrared shielding performance of the infrared shielding film 20. The glass laminate 1 of the present embodiment has improved heat resistance and moisture resistance, and can effectively prevent deterioration in the infrared shielding performance of the infrared shielding film 20 in heat resistance tests and moisture resistance tests.

[0033] The ratio of the number of infrared shielding particles 20P present between the film surface 20S and a depth of 5% from the film surface 20S to the total number of infrared shielding particles 20P is preferably 0.1% or more and 10% or less, more preferably 0.5% or more and 7% or less, and particularly preferably 0.5% or more and less than 5%. The ratio of the number of infrared shielding particles 20P present between the interface 10S and a depth of 50% from the interface 10S to the total number of infrared shielding particles 20P is preferably 54% or more, more preferably 57% or more, and particularly preferably 59% or more. In the infrared shielding particle film 20P, the volume concentration of the infrared shielding particles 20P present between the film surface 20S and a depth of 5% from the film surface 20S is preferably 0.1 vol% or more and 10 vol% or less, more preferably 0.1 vol% or more and 5 vol% or less, and particularly preferably 0.1 vol% or more and 2 vol% or less.

[0034] In the glass laminate 1 of this embodiment, the number of infrared-shielding particles 20P present in the vicinity of the interface 10S with the glass plate 10 is relatively small, so that the adhesion between the glass plate 10 and the infrared-shielding film 20 is good and the abrasion resistance is good. The ratio of the number of infrared-shielding particles 20P present between the interface 10S and a depth of 5% from the interface 10S to the number of infrared-shielding particles 20P present between a depth of 5% from the interface 10S and a depth of 10% from the interface 10S is preferably 1.1 or less, more preferably 1.0 or less, and particularly preferably 0.9 or less.

[0035] In the infrared shielding film 20, the volume concentration of the infrared shielding particles 20P present between the interface 10S and a depth of 5% from the interface 10S is preferably 0.1 vol% to 10 vol%, more preferably 0.1 vol% to 5 vol%. In the infrared shielding film 20, the volume concentration of the infrared shielding particles 20P present between a depth of 5% from the interface 10S and a depth of 10% from the interface 10S is preferably 0.1 vol% or more and 10 vol% or less, more preferably 0.1 vol% or more and 5 vol% or less.

[0036] According to this embodiment, it is possible to provide a glass laminate 1 that can effectively shield infrared rays and has excellent heat resistance, moisture resistance, and abrasion resistance. In plan view, it is preferable that the area of ​​the region in the infrared shielding film 20 that satisfies the above-mentioned number distribution requirement is large. In plan view, the region of the infrared shielding film 20 that satisfies the above-mentioned number distribution requirement preferably includes the center or central portion of the infrared shielding film 20. By having at least the center or central portion satisfy the above-mentioned number distribution requirement, the area of ​​the region of the infrared shielding film 20 that satisfies the above-mentioned number distribution requirement can be made relatively large, and the above-mentioned effects can be effectively obtained, which is preferable. Depending on the shape of the glass plate 10, it may not be possible to clearly define the "center." In this case, a similar shape is drawn by shrinking the same distance inward from the periphery to make the area as small as possible, and the region of this similar shape is defined as the center or central portion.

[0037] The infrared shielding film 20 may contain an ultraviolet shielding agent as needed. In this case, the ultraviolet shielding agent is preferably distributed substantially uniformly in the thickness direction in the infrared shielding film 20. The ultraviolet shielding agent may be distributed biased toward the glass plate 10 in the thickness direction. If a sufficient amount of ultraviolet blocking agent is present in the range 20B (lower half of the illustration) between a depth of 50% from the film surface 20S and the surface 10S of the glass plate 10, ultraviolet rays contained in sunlight that enter from the outer surface of the glass plate 10 and pass through the glass plate 10 to enter the infrared blocking film 20 are blocked at an early stage, thereby suppressing deterioration of the infrared blocking particles 20P due to ultraviolet rays, which is preferable.

[0038] [Method of manufacturing glass laminate] The method for producing a glass laminate of the present invention comprises: A step (S1) of preparing a liquid composition containing a curable silane and infrared shielding particles; The temperature of the glass plate is T S [°C], and the temperature of the liquid composition is T L When [℃], T S <T L a step (S2) of adjusting the temperature of the glass plate and / or the liquid composition so that the temperature of the glass plate and / or the liquid composition is such ... a step (S4) of placing the glass plate with the coating film substantially horizontally with the coating film side facing upward; and a step (S5) of heating the glass sheet 1C with the coating film to harden the coating film 20C. In this specification, "substantially horizontal" means a range of ±10° from the perfectly horizontal direction relative to the ground.

[0039] Each step will be described with reference to the drawings, in which: Figures 5A to 5C are partial schematic cross-sectional views corresponding to Figure 3; (Process (S1)) In step (S1), a liquid composition (LC) containing a curable silane and infrared shielding particles 20P, and optionally containing an ultraviolet shielding agent, is prepared. The liquid composition (LC) may optionally 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.

[0040] (Process (S2)) In step (S2), the temperature of the glass plate 10 is set to T S [°C], and the temperature of the liquid composition (LC) is T L When [℃], T S <T L The temperature of the glass plate 10 and / or the liquid composition (LC) is adjusted so that T S +5≦T L , more preferably T S +10≦T L is. 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 ambient temperature, which is approximately the same. Temperature T of glass plate 10 S and the temperature T of the liquid composition (LC) L is not particularly limited as long as it satisfies the above-mentioned conditions. S is, for example, in the range of 0 to 50°C, preferably in the range of 15 to 25°C, and the temperature T L The temperatures T of the glass plate 10 can be set within a range of, for example, 5 to 60°C, preferably within a range of 15 to 25°C, so as to satisfy the above-mentioned requirements. S and the temperature T of the liquid composition (LC) L can be adjusted using a thermostatic bath or the like.

[0041] (Process (S3)) In step (S3), as shown in FIG. 5A, a liquid composition (LC) at a temperature higher 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. When used in vehicles or the like, 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, symbol 0.1tc indicates a depth of 10% from the interface 10S of the coating film 20C with the glass plate 10, and symbol 0.5tc indicates a depth of 50% from the interface 10S of the coating film 20C with the glass plate 10. Symbol 20CT indicates the range between the film surface 20CS and a depth of 50% from the film surface 20CS, and symbol 20CB indicates the range between a depth of 50% 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.

[0042] (Process (S4)) In step (S4), as shown in FIG. 5A, the glass plate 1C with a coating film is placed substantially horizontally (also referred to as being laid flat) with the coating film 20C side facing upward. The ambient temperature in step (S4) is not particularly limited, and may be normal room temperature, for example, 10 to 30°C.

[0043] At the start of this process, the infrared-shielding particles 20P are distributed in a substantially uniform concentration in the coating film 20C, as shown in Fig. 5A. When the coating film 20C is placed flat with the coating film 20C side facing up, the infrared-shielding particles 20P settle overall in the coating film 20C due to gravity. By optimizing the settling of the infrared-shielding particles 20P, as shown in Fig. 5B, it is possible to bias the infrared-shielding particles 20P toward the interface 10S with the glass plate 10, while preventing excess infrared-shielding particles 20P from being present in the vicinity of the interface 10S with the glass plate 10.

[0044] Generally, the settling velocity of particles in a fluid is expressed by Stokes' law (below).

number

[0045] When the liquid composition (LC) has the same composition, the higher the liquid temperature, the lower the viscosity and the faster the settling rate of the infrared shielding particles 20P. However, if the liquid temperature becomes too high, the stability of the liquid may decrease. In step (S2), the temperature T L By adjusting the temperature [°C] to a relatively high value within a range in which the stability of the liquid is not reduced, the viscosity of the coating film 20C in the portion close to the film surface 20CS can be relatively reduced, and the settling speed of the infrared shielding particles 20P in this portion can be relatively increased. In step (S2), the temperature T S By adjusting the temperature [°C] relatively low, the temperature of the portion of the coating film 20C close to the glass plate 10 can be relatively lowered, the viscosity of this portion can be relatively increased, and the settling speed of the infrared shielding particles 20P in this portion can be relatively lowered. In step (S2), T S <T L By adjusting the temperature of the glass plate 10 and / or the liquid composition (LC) so as to achieve the above, a difference in sedimentation rate is created in the coating film 20C, and as shown in FIG. 5B , it is possible to create a configuration in which the infrared-shielding particles 20P are biased toward the interface 10S with the glass plate 10, while no excess infrared-shielding particles 20P are present in the vicinity of the interface 10S with the glass plate 10.

[0046] In step (S4), the sedimentation depth of the infrared shielding particles 20P having an average primary particle diameter in the vicinity of the film surface 20CS of the coating film 20C 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 speed of the infrared shielding particles 20P having an average primary particle size in the vicinity of the film surface 20CS of the coating film 20C 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.

[0047] 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-standing time, the sedimentation depth and sedimentation velocity of the infrared shielding particles 20P having an average primary particle diameter in the vicinity of the film surface 20CS of the coating film 20C can be adjusted to within the above ranges. In this specification, the "portion of the coating film near the film surface" refers to the area from the film surface to a depth of 20% from the film surface.

[0048] 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, a density of 5 g / cm is preferable. 3 More preferably, 5 to 10 g / cm 3 is. 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 infrared shielding film 20. From the viewpoint of optimizing the sedimentation rate and the transparency of the 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. In this specification, the "average primary particle size of the infrared shielding particles" is measured by the method described in the section [Examples] below.

[0049] There are no particular limitations on the time (flat laying time) for which the coated glass plate 1C is placed substantially horizontally with the coating film 20C side facing upward. The longer the time, the greater the sedimentation depth of the infrared shielding particles 20P. From the viewpoints of optimizing the sedimentation depth and productivity, the time is preferably 10 to 60 seconds, more preferably 10 to 50 seconds, and particularly preferably 20 to 40 seconds.

[0050] The density of the ultraviolet shielding agent is not particularly limited. The density of the ultraviolet shielding agent is smaller than the density of the infrared shielding particles 20P, for example, 2.5 g / cm 3 If the concentration is equal to or less than this, sedimentation of the ultraviolet blocking agent can be effectively prevented, and the ultraviolet blocking agent can be maintained in a state of being distributed at a substantially uniform concentration in the coating film 20C. The ultraviolet ray blocking agent may have a density that allows it to settle in the coating film 20 C. In this case, the ultraviolet ray blocking agent can also be distributed unevenly toward the glass plate 10 side. By distributing the ultraviolet blocking agent in a substantially uniform concentration in the coating film 20C or distributing it biased toward the glass plate 10, the resulting glass laminate 1 can effectively block ultraviolet rays in the portion close to the glass plate 10, and can effectively suppress deterioration of the infrared blocking particles 20P due to ultraviolet radiation.

[0051] (drying process) Between steps (S4) and (S5), a drying step may be carried out, if necessary, to dry the coating film 20C under conditions that do not promote the curing reaction. 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.

[0052] (Process (S5)) In step (S5), the glass sheet 1C with the coating film is heated to harden the coating film 20C. Heating is performed at a temperature that hardens the curable silane to silica. Step (S5) (heat hardening step) can be performed in a single step of main baking only, or in two steps of pre-baking and main 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, etc.

[0053] 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 positioned substantially horizontally with the coating film 20C facing upward, as in step (S4). In this case, the infrared shielding particles 20P may settle slightly in these steps as well, but because the coating film 20C becomes solid or nearly so early after the start of the steps, the depth of settling is short and can be considered negligible. In this manner, a glass laminate 1 as shown in FIG. 3 is obtained.

[0054] As described above, according to this embodiment, it is possible to provide a glass laminate 1 that can effectively shield infrared rays and has excellent heat resistance, moisture resistance, and abrasion resistance. [Example]

[0055] The present invention will be described below based on examples, but the present invention is not limited to these. Examples 1 to 5 are examples, and Examples 11 to 14 are comparative examples.

[0056] [Evaluation items and evaluation methods] The evaluation items and evaluation methods are as follows: The infrared shielding film and the glass laminate were evaluated in plan view on the central part of the glass laminate.

[0057] (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.

[0058] (Infrared shielding film thickness) The thickness [μm] of the infrared shielding film was measured using a stylus surface profiler (Dektak150 manufactured by ULVAC).

[0059] (Average primary particle size of infrared shielding particles) The cross section of the glass laminate was observed using a scanning electron microscope (SEM) (Hitachi High-Technologies Corporation, "S-4800"). 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 five cross-sectional SEM images was calculated as the average primary particle diameter.

[0060] (Ratio of infrared shielding particles) Similar to the method for measuring the average primary particle size, the cross section of the glass laminate was observed. Cross-sectional SEM images (magnification: 12,000x, magnification enough to capture the top and bottom edges of the infrared shielding film) were taken at five randomly selected locations. As shown in the example of Fig. 7, the obtained cross-sectional SEM image P1 was subjected to a trimming process to leave only the infrared shielding film portion. In the figure, symbol P2 denotes the image after the trimming process. Next, the trimmed image P2 was binarized by brightness to represent the infrared-shielding particles as "black" and the other parts as "white." In the figure, symbol P3 represents the image after binarization.

[0061] Next, the number and volume concentration [vol%] of infrared shielding particles with a circularity of 0.8 to 1.0 present in the entire infrared shielding film or in a specific portion of the infrared shielding film were determined in the obtained image P3. When determining the number and volume concentration [vol%] of infrared shielding particles present in the specific portion of the infrared shielding film, the portion other than the specific portion was trimmed to leave only the specific portion, and the number and volume concentration [vol%] of the infrared shielding particles were determined.

[0062] in particular, The number of infrared shielding particles present throughout the infrared shielding film, The number of infrared shielding particles present between the interface with the glass plate and a depth of 50% from this interface, the number of infrared shielding particles present between the interface with the glass plate and a depth of 5% from this interface (A), The number (B) of infrared-shielding particles present between a 5% depth from the interface with the glass plate and a 10% depth from the interface with the glass plate was determined. The number of infrared-shielding particles present in the entire infrared-shielding film was taken as 100%, and the percentage [%] of the number of infrared-shielding particles present in a specific portion was calculated. In addition, the volume concentration [vol%] of infrared shielding particles present between the film surface and a depth of 5% from the film surface, The volume concentration of infrared shielding particles present between the interface with the glass plate and a depth of 5% from this interface [vol%]. The volume concentration [vol%] of infrared-shielding particles present between a depth of 5% from the interface with the glass plate and a depth of 10% from the interface with the glass plate was determined. Image processing, counting, and measurement of volume concentration were performed using image analysis software (ImageJ, manufactured by the National Institutes of Health (NIH)). The necessary data was obtained from each of five randomly selected cross-sectional SEM images, and the average value was calculated for each data point.

[0063] (Infrared transmittance of glass laminate) The transmittance (T1500) [%] of the glass laminate at a wavelength of 1500 nm was measured using a spectrophotometer (Hitachi, Ltd., "U-4100"), and this transmittance was defined as the infrared transmittance of the glass laminate in its initial state before the heat resistance test and the moisture resistance test were conducted.

[0064] (Heat resistance of glass laminate) After leaving the glass laminate at a temperature of 80°C for 100 hours, the transmittance (T1500) [%] at a wavelength of 1500 nm was measured using the same method as before the test. The increase in T1500 [%] after the test relative to T1500 [%] before the test (ΔT1500) [%] was calculated. The smaller the increase in ΔT1500, the better the heat resistance.

[0065] (Moisture resistance of glass laminate) After leaving the glass laminate at a temperature of 50°C and a relative humidity of 95% for 100 hours, the transmittance (T1500) [%] of the glass laminate at a wavelength of 1500 nm was measured using the same method as before the test. The increase (ΔT1500) [%] in T1500 [%] after the test relative to T1500 [%] before the test was calculated. The smaller the increase in ΔT1500, the better the moisture resistance.

[0066] (Abrasion resistance of glass laminate) Using a Taber abrasion tester in accordance with JIS-R3212 (1998), an abrasion test was carried out on the surface of the infrared-shielding film side of the glass laminate using a CS-10F abrasion wheel under two conditions: 100 revolutions and 500 revolutions. After this test, the state of peeling of the infrared-shielding film was visually observed and evaluated according to the following criteria. No peeling: No peeling is visible to the naked eye. Peeling: Even slight peeling is visible to the naked eye.

[0067] [material] The abbreviations for the materials used in each example are as follows: <Glass plate> (G1) A flat glass plate (AGC "High Heat Absorption Green Glass") that is 10 mm long, 10 mm wide, and 3.5 mm thick and has a square shape in plan view.

[0068] TEOS: tetraethoxysilane, KBM-403: 3-glycidoxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd. "KBM-403" KBM-3066: 1,6-bis(trimethoxysilyl)hexane, manufactured by Shin-Etsu Chemical Co., Ltd., "KBM-3066" EX-614B: Epoxy resin, Nagase ChemteX "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 Big Chemie Japan Co., Ltd. Al(AcAc)3: aluminum acetylacetonate, CAT-AC: Aluminum-based curing catalyst, "CAT-AC" manufactured by Shin-Etsu Chemical Co., Ltd. AP-1: a mixed solvent of 85.5 mass % ethanol, 1.1 mass % methanol, and 13.4 mass % 2-propanol.

[0069] [Production Example 1] (Preparation of Liquid Composition (LC1)) A round-bottom flask was charged with 32.60 g of methanol, 0.10 g of 63% by weight aqueous nitric acid solution, 6.23 g of pure water, 10.52 g of tetraethoxysilane (TEOS), 11.23 g of epoxysilane (KBM-403), 11.50 g of bisalkoxysilane (KBM-3066), 15.35 g of epoxy resin (EX-614B), 1.87 g of aluminum acetylacetonate (Al(AcAc)3), 4.16 g of aluminum-based curing catalyst (CAT-AC), and 0.06 g of surface conditioner (BYK307), and the mixture was stirred at 28 ° C. for 2.5 hours. Finally, 6.38 g of a 20% by weight indium tin oxide (ITO) dispersion (manufactured by Mitsubishi Materials Corporation, solvent: mixed solvent (AP-1)) was added to obtain a liquid composition (LC1) with a solids concentration of 39.0% by weight. Table 1 shows the main blending composition and the solid content of the resulting liquid composition (LC).

[0070] [Production Examples 2 to 5] (Preparation of Liquid Compositions (LC2) to (LC5)) Liquid compositions (LC2) to (LC5) were obtained in the same manner as in Production Example 1, except that the blending compositions were changed to those shown in Table 1. Table 1 shows the main blending compositions and the solid content concentrations of the obtained liquid compositions. The 20 mass % CWO (registered trademark) dispersion used in Production Examples 2 and 4 was manufactured by Sumitomo Metal Mining Co., Ltd. (solvent: water).

[0071] [Example 1] (Process (S1)) The liquid composition (LC1) obtained in Production Example 1 was prepared.

[0072] (Process (S2)) Using a thermostatic bath, the temperature T S 15°C, and the temperature T L was adjusted to 25°C.

[0073] (Process (S3)) The liquid composition (LC1) at the adjusted temperature in step (S2) was applied onto the surface of the glass plate (G1) by spin coating to obtain a glass plate with a coating film.

[0074] (Process (S4)) The glass plate with the coating film was placed horizontally (laid flat) for 40 seconds with the coating film side facing upward.

[0075] (Process (S5)) The glass plate with the coating film was heated at 100°C for 30 minutes to cure the coating film, thereby obtaining a glass laminate (GL1). In this firing step, the glass plate with the coating film was placed horizontally (laid flat) with the coating film side facing up.

[0076] The main manufacturing conditions and evaluation results are shown in Table 2. The settling velocity and settling depth of the infrared shielding particles having an average primary particle size in the vicinity of the film surface in the coating film were calculated based on Stokes' equation. In the calculation, the temperature of the vicinity of the film surface in the coating film was determined using the preparation temperature of the liquid composition (LC) in step (S2), and the viscosity of the liquid composition (LC) at the preparation temperature of the liquid composition (LC) in step (S2) was used.

[0077] [Examples 2-5, Examples 11-13] Glass laminates (GL2) to (GL5) and (GL11) to (GL13) were obtained in the same manner as in Example 1, except that the conditions were changed as shown in Tables 2 and 3. The main production conditions and evaluation results are shown in Tables 2 and 3. In Tables 2 and 3, conditions not specified were common conditions.

[0078] [Example 14] (Process (S1)) Liquid compositions (LC1) and (LC5) obtained in Production Examples 1 and 5 were prepared. (Process (S2)) Using a thermostatic bath, the temperature T S At 25°C, the temperature T L was adjusted to 25°C. (Process (S3)) By spin coating, the liquid composition (LC5) at the temperature adjusted in step (S2) was applied to the surface of the glass plate (G1) in an amount that would result in a thickness of 1 μm after curing, and then the liquid composition (LC1) at the temperature adjusted in step (S2) was applied thereon in an amount that would result in a thickness of 3 μm after curing, thereby obtaining a glass plate with a coating film. (Process (S4), (S5)) A glass laminate (GL14) was obtained by carrying out steps (S4) and (S5) in the same manner as in Example 1. Table 3 shows the main production conditions and evaluation results.

[0079] [Table 1]

[0080] [Table 2]

[0081] [Table 3]

[0082] [Summary of results] In Examples 1 to 5, a liquid composition (LC) having a temperature higher than that of the glass plate was applied to the surface of the glass plate to form a coating film, thereby obtaining a glass plate with a coating film.The glass plate with a coating film was then horizontally positioned with the coating film side facing upward, and the glass plate with a coating film was then heated to harden the coating film, thereby producing a glass laminate. In these examples, in a plan view, in the central part of the infrared shielding film, the ratio of the number of infrared-shielding particles present between the interface with the glass plate and a depth of 50% from the interface with the glass plate to the total number of infrared-shielding particles is 52% or more, A glass laminate was obtained in which the ratio of the number of infrared-shielding particles present between the interface with the glass plate and a depth of 5% from the interface with the glass plate to the number of infrared-shielding particles present between a depth of 5% from the interface with the glass plate and a depth of 10% from the interface with the glass plate (the (A) / (B) ratio in the table) was 1.2 or less. In the heat resistance and moisture resistance tests, the glass laminates obtained in these examples showed a small increase in infrared transmittance (ΔT1500) after the test compared to before the test, and showed a small decrease in infrared shielding effect, which was favorable. The glass laminates obtained in these examples also had good abrasion resistance. In particular, the glass laminate obtained in Example 2, which used cesium-doped tungsten oxide (CWO (registered trademark)) as the infrared shielding particles, exhibited high abrasion resistance.

[0083] In Examples 11, 12, and 14, the temperature of the glass plate and the temperature of the liquid composition (LC) were the same. In Example 13, the viscosity of the liquid composition (LC) was high, and the settling velocity and settling depth of the infrared shielding particles having an average primary particle size in the vicinity of the film surface in the coating film were too small. In Example 14, a liquid composition (LC) not containing infrared-shielding particles was applied, and then a liquid composition (LC) containing infrared-shielding particles was applied to form a coating film.

[0084] In the glass laminates obtained in Examples 11 and 12, in a plan view, the central portion of the infrared shielding film The ratio of the number of infrared-shielding particles present between the interface with the glass plate and a depth of 5% from the interface with the glass plate to the number of infrared-shielding particles present between a depth of 5% from the interface with the glass plate and a depth of 10% from the interface with the glass plate was greater than 1.2. The glass laminates obtained in these examples had poor abrasion resistance.

[0085] In the glass laminate obtained in Example 13, in a plan view, the central portion of the infrared shielding film The proportion of the number of infrared-shielding particles present between the interface with the glass plate and a depth of 50% from the interface with the glass plate to the total number of infrared-shielding particles was less than 52%. In the heat resistance and moisture resistance test, the glass laminate obtained in this example showed a large increase in infrared transmittance (ΔT1500) after the test compared to before the test, and a large decrease in infrared shielding effect, making it unsatisfactory.

[0086] In the glass laminate obtained in Example 14, in a plan view, the central portion of the infrared shielding film The percentage of infrared shielding particles present between the interface with the glass plate and a depth of 5% from this interface is 0%, The percentage of infrared-shielding particles present between a depth of 5% from the interface with the glass plate and a depth of 10% from the interface with the glass plate was 0%. It was not possible to calculate the ratio of the number of infrared-shielding particles present between the interface with the glass plate and a depth of 5% from the interface with the glass plate to the number of infrared-shielding particles present between a depth of 5% from the interface with the glass plate and a depth of 10% from the interface with the glass plate. The glass laminate obtained in this example had poor abrasion resistance.

[0087] Representative XPS spectra of the infrared shielding films of the glass laminates obtained in Examples 1 and 11 are shown in FIGS. 6A and 6B. An elemental analysis was performed on any one metal element (e.g., In in the case of ITO) contained in the infrared-shielding particles in the infrared-shielding film in the depth direction from the film surface to obtain an XPS spectrum. The concentration [atomic %] of the metal element within a certain range in the depth direction was calculated from the area ratio of the spectrum. The XPS spectrum of the infrared shielding film of the glass laminate obtained in Example 1, shown in FIG. 6A, shows that the infrared shielding particles are unevenly distributed between the interface with the glass plate and a depth of 50% from the interface with the glass plate, but the number of infrared shielding particles present between the interface with the glass plate and a depth of 5% from the interface with the glass plate is small. The XPS spectrum of the infrared shielding film of the glass laminate obtained in Example 11, shown in FIG. 6B, shows that the infrared shielding particles are present, concentrated between the interface with the glass plate and a depth of 5% from the interface with the glass plate.

[0088] Representative examples of images after cropping and binarization of SEM photographs of the cross sections of the glass laminates obtained in Examples 1, 11, and 13 are shown in FIG.

[0089] The present invention is not limited to the above-described embodiments and examples, and various modifications can be made to the design as appropriate without departing from the spirit of the present invention.

[0090] This application claims priority based on Japanese Patent Application No. 2021-054925, filed on March 29, 2021, the disclosure of which is incorporated herein in its entirety. [Explanation of symbols]

[0091] 1: glass laminate, 1C: glass plate with coating film, 10: glass plate, 10S: surface (interface), 20: infrared shielding film, 20C: coating film, 20P: infrared shielding particles, 20S: film surface.

Claims

1. A glass laminate having an infrared shielding film containing silica and infrared shielding particles formed on a surface of a glass plate, In a plan view, in at least a part of the infrared shielding film, When the thickness of the infrared shielding film is taken as 100%, and the infrared shielding film is viewed in the depth direction from the interface with the glass plate, a ratio of the number of the infrared-shielding particles present between the interface and a depth of 50% from the interface to the total number of the infrared-shielding particles is 52% or more, a ratio of the number of the infrared-shielding particles present between the interface and a depth of 5% from the interface to the number of the infrared-shielding particles present between a depth of 5% from the interface and a depth of 10% from the interface is 1.2 or less, a glass laminate in which the ratio of the number of the infrared-shielding particles present between the film surface of the infrared-shielding film and a depth of 5% from the film surface to the total number of the infrared-shielding particles is 0.1% or more and 10% or less.

2. A glass laminate as described in claim 1, wherein the ratio of the number of infrared shielding particles present between the interface and a depth of 50% from the interface to the total number of infrared shielding particles is 54% or more.

3. A glass laminate as described in claim 1 or 2, wherein the infrared shielding film is made of a cured single-layer coating film of a liquid composition containing a curable silane and the infrared shielding particles.

4. The infrared shielding particles have a density of 5 g / cm ３ The glass laminate according to any one of claims 1 to 3.

5. The infrared shielding particles have a density of 5 to 10 g / cm ３ The glass laminate of claim 4 .

6. The glass laminate according to any one of claims 1 to 5, wherein the infrared shielding particles have an average primary particle size of 10 to 150 nm.

7. The glass laminate according to any one of claims 1 to 6, wherein the infrared shielding particles comprise a metal compound.

8. The glass laminate according to any one of claims 1 to 7, wherein the infrared shielding particles are metal compound particles comprising 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.

9. 9. The glass laminate according to claim 8, wherein the infrared shielding particles are metal compound particles comprising one or more metal compounds selected from the group consisting of cesium-doped tungsten oxide and lanthanum hexaboride.

10. A glass plate; A step (S1) of preparing a liquid composition containing a curable silane and infrared shielding particles; The temperature of the glass plate is T Ｓ [°C], and the temperature of the liquid composition is T Ｌ When [°C], T Ｓ <T Ｌ (S2) adjusting the temperature of the glass plate and / or the liquid composition so that a step (S3) of applying the liquid composition having a temperature higher 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 placing the glass plate with the coating film substantially horizontally so that the coating film side faces upward; and (S5) heating the glass sheet with the coating film to harden the coating film.

11. In step (S2), T Ｓ +5≦T Ｌ The method for producing a glass laminate according to claim 10 , wherein the temperature of the glass plate and / or the liquid composition is adjusted so as to satisfy the following condition.

12. The method for producing a glass laminate according to claim 10 or 11, wherein in step (S4), the infrared shielding particles have an average primary particle diameter of 0.1 to 0.4 μm in a sedimentation depth at least in a portion of the coating film near the film surface.

13. The method for producing a glass laminate according to any one of claims 10 to 12, wherein in step (S4), the infrared shielding particles having an average primary particle diameter in at least a portion of the coating film near the film surface have a sedimentation rate of 1 to 50 nm / s.

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