WO2023100710A1

WO2023100710A1 - Glass substrate equipped with film

Info

Publication number: WO2023100710A1
Application number: PCT/JP2022/043077
Authority: WO
Inventors: 直己上村
Original assignee: Ａｇｃ株式会社
Priority date: 2021-11-30
Filing date: 2022-11-21
Publication date: 2023-06-08

Abstract

The present invention relates to a glass substrate equipped with a film, comprising a glass substrate and a film positioned on the glass substrate, wherein the glass substrate has a first surface and a second surface facing each other, the film is installed on the first surface of the glass substrate, and the skewness of the outermost surface of the film is 0 or less.

Description

glass substrate with film

The present invention relates to a film-coated glass substrate.

Film-coated glass substrates, which are laminated with functional films on glass substrates, are widely used in various fields as materials that satisfy various required properties.

For example, in the window glass used in vehicles and buildings, low-emissivity glass (Low-E glass) with heat insulation and heat shielding properties is used due to the recent heightened awareness of energy conservation. Low-emissivity glass is constructed by laminating one or more functional layers made of metal oxide or the like on a glass substrate. It has a light absorption layer, an optical adjustment layer, and the like.

In addition, regarding a film-coated glass substrate provided with a functional layer made of a metal oxide or the like similarly to these, Patent Document 1 discloses that the glass plate is coated with a tin oxide film, and the surface Ra of the tin oxide film is set to 3 nm or less. A top plate glass for a copier is described. Patent Document 1 describes that when a lubricant is applied to the surface of a tin oxide film having an Ra of 3 nm or less, a top plate glass for a copying machine having a very small coefficient of friction can be obtained.

Japanese Patent Laid-Open No. 9-208264

However, in conventional film-coated glass substrates, when the film surface is stained with fingerprints or the like, rubbing it with an article containing fibers such as clothes, cloth products, paper products, etc. may cause the fibers to adhere. There is a demand for improved stain resistance against such stains.

Therefore, an object of the present invention is to provide a film-coated glass substrate that has excellent stain resistance, particularly against stains caused by adhesion of fibers and the like.

As a result of extensive studies, the present inventors have found that the above problems can be solved by specifying the properties of the outermost surface of the film in the film-coated glass substrate, and have completed the present invention.

That is, the present invention relates to 1 to 16 below.
1. A film-coated glass substrate comprising a glass substrate and a film disposed on the glass substrate,
the glass substrate has a first surface and a second surface facing each other;
the film is disposed on the first surface of the glass substrate;
A film-coated glass substrate, wherein the skewness of the outermost surface of the film is 0 or less.
2. 2. The film-coated glass substrate according to 1 above, wherein the surface roughness of the outermost surface of the film is greater than 0.4 nm.
3. 2. The film-coated glass substrate according to 1 above, wherein adhesion of fibers is not confirmed when the outermost surface of the film is rubbed with a cloth.
4. 2. The film-coated glass substrate according to 1 above, wherein the outermost surface of the film has an emissivity of 0.3 or less.
5. 2. The film-coated glass substrate according to 1 above, wherein the film comprises a crystalline infrared reflective layer.
6. 6. The film-coated glass substrate according to 5 above, wherein the film includes a crystalline crystal growth base layer and the infrared reflective layer from the side closer to the glass substrate.
7. 6. The film-coated glass substrate according to 5 above, wherein the infrared reflective layer contains a doped metal oxide in which at least one metal oxide of tin oxide and titanium oxide is doped with another element.
8. 6. The film-coated glass substrate according to 5 above, wherein the infrared reflective layer comprises a fluorine-doped tin oxide film.
9. 7. The film-coated glass substrate according to 6 above, wherein the crystal growth base layer comprises an antimony-doped tin oxide film, and the infrared reflective layer comprises a fluorine-doped tin oxide film.
10. 6. The film-coated glass substrate according to 5 above, wherein the infrared reflective layer is arranged on the outermost surface of the film.
11. 6. The film-coated glass substrate according to 5 above, wherein the film further includes an overcoat layer, and the overcoat layer is disposed on the outermost surface of the film.
12. 6. The film-coated glass substrate according to 5 above, wherein the film further includes an optical adjustment layer, and the optical adjustment layer is arranged at a position in contact with the first surface.
13. 13. The film-coated glass substrate according to 12 above, wherein the optical adjustment layer comprises a SiOC film.
14. 2. The film-coated glass substrate according to 1 above, wherein the film includes a layer formed by a thermal CVD method.
15. 2. The film-coated glass substrate according to 1 above, wherein the film includes a layer formed by a thermal CVD method on a glass substrate production line.
16. 16. The film-coated glass substrate according to any one of 1 to 15 above, which is used for vehicle window glass or laminated glass for vehicle window glass.

The film-coated glass substrate of the present invention has excellent stain resistance because the skewness of the outermost surface of the film is 0 or less. According to the film-coated glass substrate of the present invention, contamination of the film surface, particularly due to adhesion of fibers, can be suitably suppressed.

FIG. 1 is a diagram showing a configuration example of a film-coated glass substrate according to this embodiment. FIG. 2 is a diagram showing a configuration example of the film-coated glass substrate according to this embodiment. FIG. 3 shows the film-coated glass substrate of Example 12 after the stain resistance test. FIG. 4 shows the film-coated glass substrate of Example 23 after the stain resistance test. FIG. 5 is a diagram showing the relationship between Sa and Ssk of a film-coated glass substrate and stain resistance.

Embodiments of the present invention will be described below, but the present invention is not limited to these.

A film-coated glass substrate according to the present embodiment is a glass substrate with a film provided with a glass substrate and a film disposed on the glass substrate, wherein the glass substrate has a first surface and a second surface facing each other. The film has a surface, the film is placed on the first surface of the glass substrate, and the skewness of the outermost surface of the film is 0 or less.

FIG. 1 is a diagram showing a configuration example of a film-coated glass substrate according to this embodiment. As shown in FIG. 1 , the film-coated glass substrate 10 includes a glass substrate 1 and a film 2 placed on the glass substrate 1 . The glass substrate has a first surface 1a and a second surface 1b facing each other, and a film 2 is placed on the first surface 1a of the glass substrate 1. As shown in FIG. The membrane 2 may consist of one layer or may consist of a plurality of layers. In FIG. 1, the film 2 is a laminated film composed of a plurality of layers.

In the film-coated glass substrate according to this embodiment, the skewness (Ssk) of the outermost surface of the film is 0 or less. Here, the outermost surface of the film means the surface of the film 2 opposite to the glass substrate, and hereinafter this is also referred to as the film surface. As a result of intensive studies, the present inventors have found that by setting the skewness of the outermost surface of the film to 0 or less, it is possible to suppress the adhesion of dirt to the film surface of the film-coated glass substrate. Skewness is a parameter relating to the height distribution of a target surface, and refers to the value of Ssk (skewness of the scale-limited surface) defined in ISO25178. For example, Ssk is obtained by processing surface analysis data measured with an atomic force microscope (AFM) using image analysis software (for example, SPIP manufactured by Image Metrology), and in this case is calculated from the following formula: . More specific measurement and processing methods will be described later in Examples.

In the formula, M is the number of measurement points in the X-axis direction, N is the number of measurement points in the Y-axis direction, Sq is the root mean square roughness, and z (x _k , y _l ) is the coordinate (x _k , y _l ) at Represents height (where x _k represents the kth x coordinate and y _l represents the lth y coordinate). Here, Sq is defined by the following formula. In the following formula, M, N, z(x _k , y _l ) are the same as above.

A skewness greater than 0 means that the distribution is biased toward areas with relatively low heights. On the other hand, a skewness of 0 means that relatively high and relatively low height portions are symmetrically distributed, and a skewness of less than 0 means that the distribution is biased toward relatively high height portions. means that

In other words, a surface with a skewness greater than 0 tends to have relatively sharp protrusions and relatively flat recesses. On such a surface, dirt tends to adhere because the contacting object is easily scraped off by the uneven shape, and dirt is likely to be trapped by the uneven shape, making it difficult to remove the dirt. On the other hand, in the present embodiment, the skewness is 0 or less, so that the number of protrusions with relatively sharp shapes is reduced, thereby suppressing scraping of contact objects and trapping of dirt due to uneven shapes. can.

The skewness is preferably less than 0, more preferably -0.10 or less, and even more preferably -0.15 or less from the viewpoint of further improving stain resistance. The lower limit of the skewness is not particularly limited, but from the viewpoint of ensuring productivity, it is preferably -2.0 or more, for example. The skewness may be -2.0 to 0, for example. The method for reducing the skewness to 0 or less is not particularly limited, but an example thereof includes a method of polishing the film surface as described later.

In this specification, stain resistance means resistance to stain adhesion. The type of dirt is not particularly limited, but the film-coated glass substrate according to the present embodiment is particularly excellent in resistance to adherence of fibers, etc. when in contact with articles containing fibers, such as clothes, cloth products, and paper products. is. The stain resistance can be evaluated, for example, by a stain resistance test in which the outermost surface of the film is rubbed with a cloth. In the film-coated glass substrate according to the present embodiment, it is preferable that adhesion of fibers is not confirmed when the outermost surface of the film is rubbed with a cloth. As the procedure and conditions for the stain resistance test, for example, the procedures and conditions described later in Examples can be adopted.

The present inventors found the relationship between skewness and stain resistance as described above, and at the same time found that the degree of stain resistance does not depend on the value of surface roughness (Sa). That is, from the viewpoint of improving the stain resistance, it is sufficient that the skewness is 0 or less, and for example, it is not essential to make the surface roughness relatively small. Attempting to excessively reduce the surface roughness may increase the production cost or make the production difficult depending on the required film properties. On the other hand, setting the surface roughness to a relatively large value is preferable because it facilitates the production of the film-coated glass substrate and improves the productivity. That is, the surface roughness of the outermost surface of the film is preferably greater than 0.4 nm, more preferably 3 nm or more, even more preferably 5 nm or more, and particularly preferably 10 nm or more. On the other hand, from the viewpoint of improving the appearance, the surface roughness is preferably 30 nm or less, more preferably 28 nm or less, even more preferably 25 nm or less, and particularly preferably 20 nm or less. The surface roughness may be, for example, 0.4-30 nm. The surface roughness refers to the value of Sa (arithmetic mean height of the scale limited surface) defined in ISO25178. Sa is obtained, for example, by processing surface analysis data measured with an atomic force microscope (AFM) using image analysis software (for example, SPIP manufactured by Image Metrology), in which case it is calculated from the following formula: . More specific measurement and processing methods will be described later in Examples. In the following formula, M, N, z(x _k , y _l ) are the same as above.

A specific configuration of the film-coated glass substrate according to the present embodiment will be described in more detail below.

(glass substrate)
The glass substrate 1 serves as a framework for the film-coated glass substrate 10 and has self-supporting properties. Examples of glass constituting the glass substrate include soda lime silicate glass, aluminosilicate glass, borate glass, lithium aluminosilicate glass, quartz glass, borosilicate glass, alkali-free glass, and the like. The glass substrate may be subjected to a known treatment such as air-cooling tempering or chemical strengthening as long as the effects of the present invention are not impaired.

The glass substrate can be transparent, translucent, or opaque, depending on the intended use and purpose of the film-coated glass substrate. Further, the glass substrate may be colorless or colored.

The shape of the glass substrate is not particularly limited, and any shape is possible depending on the intended use. For example, it is preferably plate-shaped for use in vehicle members and construction members. The glass substrate may have a flat plate shape, or may have a plate shape having a curved surface by bending or the like.

The size of the glass substrate is not particularly limited, and may be appropriately adjusted according to the application and purpose of use of the film-coated glass substrate. For example, when a film-coated glass substrate is used in a vehicle, the glass substrate preferably has a thickness of 1 mm to 5 mm and a main surface area of 0.5 to 5 m ² . When the film-coated glass substrate is used for a building, the glass substrate preferably has a thickness of 4 mm to 8 mm and a main surface area of 0.5 to 10 m ² .

(film)
In the film-coated glass substrate, the type of film is not particularly limited, and the film may be various functional films. The film is preferably a functional film comprising a layer containing metal oxide as a main component, for example. As an example, a preferred configuration example of the film when the film-coated glass substrate is used as low-emissivity glass (Low-E glass) imparted with heat insulating properties and heat shielding properties will be described below.

When the film-coated glass substrate is used as low-emissivity glass, the film 2 placed on the glass substrate 1 preferably includes a crystalline infrared reflective layer 5 . Also, the film 2 preferably further includes at least one or more of a crystalline crystal growth base layer 3, an optical adjustment layer 7 and an overcoat layer (not shown). FIG. 1 is a diagram showing a configuration example in which the film 2 includes an optical adjustment layer 7 and an infrared reflective layer 5 from the side closer to the glass substrate 1. As shown in FIG. FIG. 2 is a diagram showing a configuration example in which the film 2 includes the optical adjustment layer 7, the crystal growth base layer 3, and the infrared reflecting layer 5 from the side closer to the glass substrate 1. As shown in FIG.

(Infrared reflective layer)
The infrared reflective layer 5 is a layer that reflects infrared rays, imparts heat insulation to the film-coated glass substrate, and has crystallinity.

Materials for forming the infrared reflective layer include, for example, at least one metal oxide selected from the group consisting of tin oxide, indium oxide, zinc oxide, titanium oxide, tantalum oxide, and niobium oxide, and other elements (impurity elements). doped metal oxides.
Impurity elements to be doped include, for example, fluorine, antimony, tin, potassium, aluminum, tantalum, niobium, nitrogen, boron, and indium.

Specific doped metal oxides include, for example, fluorine-doped tin oxide (FTO, a metal oxide in which F is added to _SnO2 ), antimony-doped tin oxide (ATO, a metal oxide in which Sb is added to _SnO2 ). , tin-doped indium oxide (ITO, metal oxide in which Sn is added to In ₂ O ₃ ), gallium-doped zinc oxide (GZO, metal oxide in which Ga is added to ZnO), aluminum-doped zinc oxide (AZO, ZnO to which Al is added doped metal oxide), tantalum-doped tin oxide (metal oxide in which Ta is added to _SnO2 ), niobium-doped tin oxide (metal oxide in which Nb is added to _SnO2 ), tantalum-doped titanium oxide (Ti added with Ta niobium-doped titanium oxide (metal oxide in which Nb is added to Ti), aluminum-doped tin oxide (metal oxide in which Al is added to _SnO2 ), fluorine-doped titanium oxide (metal oxide in which F is added to Ti) oxide), nitrogen-doped titanium oxide (a metal oxide in which N is added to Ti), and the like.

Among them, the infrared reflective layer preferably contains a doped metal oxide in which at least one metal oxide of tin oxide and titanium oxide is doped with another element, and the other element is fluorine, tantalum, niobium and At least one selected from the group consisting of aluminum is preferred.
Specifically, the infrared reflective layer contains at least one dope selected from the group consisting of fluorine-doped tin oxide (FTO), tantalum-doped tin oxide, niobium-doped tin oxide, tantalum-doped titanium oxide, niobium-doped titanium oxide, and aluminum-doped tin oxide. It is more preferable to be formed from a type metal oxide, and from the viewpoint of obtaining higher heat insulation properties, it is further preferable to have a fluorine-doped tin oxide (FTO) film.

The infrared reflective layer may consist of a single layer film, or may consist of two or more layers of films with different materials, element contents, and the like.

The content of impurity elements contained in the infrared reflective layer is preferably 0.01 to 20 mol % in concentration. When the concentration of the impurity element contained in the infrared reflective layer is 0.01 mol % or more, a heat insulating effect can be exhibited, and when it is 20 mol % or less, good crystallinity can be maintained.
The concentration of the impurity element contained in the infrared reflective layer is preferably 0.01 mol % or more, more preferably 0.1 mol % or more, still more preferably 0.5 mol % or more, and more preferably 10 mol % or less. It is preferably 8 mol % or less, more preferably 5 mol % or less.
In addition, the concentration of the impurity element is the total amount when the infrared reflective layer contains a plurality of impurity elements.

The composition of the infrared reflective layer and the concentration of impurity elements can be identified by X-ray photoelectron spectroscopy (XPS) or secondary ion mass spectroscopy (SIMS).
For example, the antimony (Sb) concentration can be examined from the intensity ratio of Sb and Sn by analyzing the depth direction by X-ray photoelectron spectroscopy (XPS). The fluorine (F) concentration is analyzed in the depth direction by secondary ion mass spectrometry (SIMS), and can be examined from the intensity ratio of F and Sn. For SIMS, fluorine-added tin SnO ₂ with a known concentration is measured, and a coefficient for converting the intensity ratio of F/Sn into concentration is obtained.

The thickness of the infrared reflective layer is preferably 50-1000 nm. When the thickness of the infrared reflective layer is 50 nm or more, the heat insulation performance of the film-coated glass substrate is improved, and when it is 1000 nm or less, the transparency of the glass substrate in the visible light region can be secured while maintaining heat insulation.
The thickness of the infrared reflective layer is preferably 50 nm or more, more preferably 80 nm or more, still more preferably 130 nm or more, and preferably 1000 nm or less, more preferably 500 nm or less, and 450 nm or less. More preferably, 400 nm or less is particularly preferable.

The thickness of the infrared reflective layer can be measured by depth direction analysis by X-ray photoelectron spectroscopy.
When the infrared reflective layer is composed of multiple layers of different materials, the "thickness" of the infrared reflective layer is represented by the total thickness of each layer.
In addition, when the "thickness" of the infrared reflective layer differs depending on the location, the maximum thickness of the infrared reflective layer in the measurement area shall be indicated in the present embodiment.

The infrared reflective layer is formed from metal oxide crystal grains. The size of the crystal grains in the infrared reflective layer is preferably 30 nm or more. When the crystal grain size is 30 nm or more, the grain boundary scattering of electrons is reduced and the electrical conductivity is increased, so that the emissivity can be lowered.
The size of the crystal grain is more preferably 30 nm or more, more preferably 50 nm or more, and particularly preferably 80 nm or more. Since the larger the crystal grain shape, the better, there is no particular upper limit, but it is generally 1000 nm. It is more preferably 800 nm or less, particularly preferably 500 nm or less. For example, the size of the crystal grains in the infrared reflective layer may be 30-1000 nm.

The size of the crystal grains can be measured by observing a cross section obtained by cutting the film-coated glass substrate in the thickness direction with a scanning electron microscope (SEM).

(Crystal growth base layer)
The crystal growth base layer 3 is a layer that accelerates the crystal growth in the infrared reflective layer 5 laminated on the crystal growth base layer 3 to grow large crystal grains, and has crystallinity. A crystal growth base layer is not essential, but when the film includes a crystal growth base layer, as shown in FIG. preferable. As described above, the infrared reflective layer 5 is formed of metal oxide crystal grains. Since the crystal grains grown in the infrared reflective layer 5 are grown based on the crystal grains 3, the crystal grains in the infrared reflective layer 5 can be grown large. This makes it easier to reduce the emissivity of the outermost surface of the film.

Materials forming the crystal growth base layer include, for example, at least one metal oxide selected from the group consisting of tin oxide, indium oxide, zinc oxide, titanium oxide, niobium oxide, and tantalum oxide.
The crystal growth underlayer is preferably formed from the same type of metal oxide as the metal oxide contained in the infrared reflective layer. For example, if the infrared reflective layer comprises a fluorine-doped tin oxide (FTO) film, the crystal growth substrate is preferably a tin oxide film.
If the metal oxide is of the same type as the metal oxide contained in the infrared reflective layer, the crystal grains in the infrared reflective layer can grow large without discontinuing the growth of the crystal grains when forming the infrared reflective layer.

Also, the metal oxide forming the crystal growth base layer may be a doped metal oxide doped with another element (impurity element). By forming the crystal growth base layer from a doped metal oxide, the crystal growth base layer can be given a desired function.
The impurity metal with which the doped metal oxide is doped is the same as described above, and examples thereof include fluorine, antimony, tin, potassium, aluminum, tantalum, niobium, nitrogen, boron, and indium. Among others, antimony-doped tin oxide (ATO, a metal oxide obtained by adding Sb to SnO ₂ ) forms the base layer for crystal growth (antimony-doped tin oxide film). A glass substrate with a heat shield is provided. That is, it is more preferable that the crystal growth base layer comprises an antimony-doped tin oxide film and the infrared reflecting film comprises a fluorine-doped tin oxide film.

When a doped metal oxide is used to form the crystal growth base layer, the concentration of the impurity element to be doped is preferably 30 mol % or less. When the concentration of the metal to be doped is 30 mol % or less, the crystal structure before doping can be maintained.
The concentration of the doped metal is preferably 30 mol % or less, more preferably 25 mol % or less, even more preferably 20 mol % or less.

The composition of the crystal growth base layer and the concentration of the impurity element to be doped can be identified by X-ray photoelectron spectroscopy (XPS) or secondary ion mass spectrometry (SIMS), as described above.

The crystal growth base layer may consist of a single-layer film, or may consist of two or more layers of films with different materials, metal contents, and the like.

In this embodiment, the thickness of the crystal growth base layer is preferably 200 nm or more. When the thickness of the crystal growth base layer is 200 m or more, the crystal grain size of the infrared reflective layer can be easily grown, and the crystal grains of the infrared reflective layer can be grown to a desired size. Crystal growth of the metal oxide is ensured during film formation, and the crystal grains of the infrared reflective layer become large.
The thickness of the crystal growth base layer is more preferably 250 nm or more, more preferably 300 nm or more. From the viewpoint of surface flatness, the thickness of the crystal growth base layer is preferably 1000 nm or less, more preferably 900 nm or less, and even more preferably 700 nm or less. The thickness of the crystal growth underlayer may be, for example, 200-1000 nm.

The thickness of the crystal growth base layer can be measured by analysis in the depth direction by X-ray photoelectron spectroscopy.
Since the crystal growth base layer is formed of metal oxide crystal grains, the surface opposite to the glass substrate side has an uneven shape. Therefore, although the "thickness" of the crystal growth base layer varies depending on the location, in this embodiment, it represents the maximum thickness of the crystal growth base layer in the measurement region.

The crystal grain size in the crystal growth base layer is preferably 30 to 1500 nm. When the crystal grain size is 30 nm or more, the crystal grain shape of the infrared reflective layer formed on the crystal growth base layer can be made sufficiently large.
The size of the crystal grains is more preferably 30 nm or more, more preferably 50 nm or more, and particularly preferably 80 nm or more. Since the larger the crystal grain shape, the better, there is no particular upper limit, but generally 1500 nm. It is more preferably 1200 nm or less, particularly preferably 1000 nm or less.

The size of the crystal grains is the same as above, and can be measured by cross-sectional observation with a scanning electron microscope.

In this embodiment, when the film includes a crystal growth underlayer, the total thickness of the infrared reflective layer and the crystal growth underlayer is preferably 250-1500 nm. When the total thickness of each layer is 250 nm or more, the crystal grains in the infrared reflective layer can be sufficiently grown, and when it is 1500 nm or less, the film-coated glass substrate does not become too thick.
The total thickness of the infrared reflecting layer and the crystal growth base layer is preferably 300 nm or more, more preferably 400 nm or more, particularly preferably 500 nm or more, and preferably 1500 nm or less, more preferably 1100 nm or less. , 900 nm or less.

(Optical adjustment layer)
In the film-coated glass substrate according to this embodiment, the film may further include an optical adjustment layer 7 . When the film 2 includes the optical adjustment layer 7 , the optical adjustment layer 7 is preferably arranged at a position in contact with the first surface 1 a of the glass substrate 1 .

Materials constituting the optical adjustment layer include, for example, silicon carbide oxide (SiOC), silicon oxide (SiO ₂ ), titanium oxide (TiO ₂ ), tin oxide (SnO ₂ ), silicon nitride oxide (SiON), and the like. . The optical adjustment layer may consist of one layer, or may consist of two or more layers. It may also be a mixture of any two or more of the above materials.

Specifically, the optical adjustment layer includes a SiOC film, a SiOC/ _SiO2 laminated film in which the SiOC film and the _SiO2 film are laminated in this order from the glass substrate side, and a _TiO2 film and _{a SiO2} film in this order from the glass substrate side. and a SnO ₂ /SiO ₂ laminated film _in _which the SnO ₂ film and the SiO ₂ film are laminated in this order from the glass substrate side.
Above all, from the standpoint of alkali barrier properties, the optical adjustment layer preferably contains silicon, and is a group consisting of a SiOC film, a SiOC/SiO ₂ laminated film, a TiO ₂ /SiO ₂ laminated film, and a SnO ₂ /SiO ₂ laminated film. and more preferably comprising a SiOC film.

The amount of silicon contained in the entire optical adjustment layer is preferably in the range of 5 to 40 mol%, more preferably 10 to 33 mol%.

The thickness of the optical adjustment layer is preferably 20-100 nm. When the thickness of the optical adjustment layer is 20 nm or more, the glass substrate surface can be uniformly coated. A desired effect can be exhibited.
The thickness of the optical adjustment layer is preferably 20 nm or more, more preferably 25 nm or more, still more preferably 30 nm or more, and preferably 100 nm or less, more preferably 90 nm or less, and even more preferably 80 nm or less.

When the optical adjustment layer is composed of multiple layers of different materials, the "thickness" of the optical adjustment layer is represented by the total thickness of each layer.

(Other layers)
The film may further include other layers as long as the effects of the present invention are not impaired. Other layers include, for example, an overcoat layer.
The overcoat layer is typically a layer provided to adjust the reflectance of light on the side having the film. That is, by adjusting the refractive index difference between the overcoat layer and the layer adjacent thereto, the reflectance of light on the surface of the film-coated glass substrate on the side having the film can be adjusted. More specifically, the reflectance can be reduced by providing a layer having a smaller refractive index than the infrared reflective layer on the infrared reflective layer. For glass used in vehicles and the like, it is preferable to keep the reflectance low so that the outside of the vehicle can be clearly seen. From this point of view, it is preferable to provide an overcoat layer. Examples of materials for forming a layer having a lower refractive index than the infrared reflective layer include silicon oxide (SiO ₂ ), silicon nitride, a mixture of silicon oxide and titanium oxide, a mixture of silicon oxide and tin oxide, and a mixture of silicon oxide and alumina oxide. , SiOC, etc., and silicon oxide (SiO ₂ ) is preferable from the viewpoint of ease of film formation. Specifically, it is preferable to include a SiO ₂ film as the overcoat layer. The overcoat layer may consist of one layer, or may consist of a film of two or more layers. It may also be a mixture of any two or more of the above materials.

If the film further comprises an overcoat layer, its thickness is preferably between 20 and 1000 nm. When the thickness is 20 nm or more, the effect of reducing the reflectance can be made sufficient, and when the thickness is 1000 nm or less, a decrease in infrared reflectance can be prevented.
More preferably, the overcoat layer has a thickness of 30 nm or more, more preferably 50 nm or more. Also, the thickness is more preferably 300 nm or less, and even more preferably 200 nm or less.

(Layer structure of film)
When the film is a laminated film, the skewness of the outermost surface of the film being 0 or less means that the skewness of the surface of the layer disposed on the outermost surface of the film is 0 or less.
Considering the preferred configurations of each layer described above, when the film does not include an overcoat layer, it is preferred that the infrared reflective layer is disposed on the topmost surface of the film. Moreover, when the film includes an overcoat layer, the overcoat layer is preferably arranged on the outermost surface of the film.

(Physical properties of film-coated glass substrate)
In the film-coated glass substrate according to the present embodiment, the emissivity of the outermost surface of the film is preferably 0.3 or less. When the emissivity is 0.3 or less, excellent heat insulation can be obtained.
The emissivity is more preferably 0.25 or less, even more preferably 0.2 or less. In addition, since the lower the emissivity, the better the heat insulating property, the lower limit of the emissivity is not particularly limited, but it is preferably 0.01 or more, more preferably 0.03 or more, and further preferably 0.10 or more. The emissivity may be, for example, 0.01-0.3.
Emissivity is the reflectance for visible light measured according to ISO9050:2003.

Moreover, the sheet resistance value of the film-coated glass substrate is preferably 30 ohm/square (ohm/sq.) or less. There is a correlation between emissivity and sheet resistance, and the sheet resistance is 30 ohm/sq. When it is less than that, electricity flows easily, so the emissivity is low, and therefore excellent heat insulation can be obtained.
The value of sheet resistance is 30 ohm/sq. below, preferably 25 ohm/sq. The following is more preferable, and 20 ohm/sq. More preferred are: Also, the lower the sheet resistance value, the easier the flow of electricity and the lower the emissivity. Therefore, the lower limit of the sheet resistance value is not particularly limited. 2 ohm/sq. 3 ohm/sq. The above is more preferable. The sheet resistance value is, for example, 1 to 30 ohm/sq. may be
The sheet resistance value can be measured by Hall measurement.

(Manufacturing method of film-coated glass substrate)
The method for manufacturing the film-coated glass substrate according to the present embodiment is not particularly limited, but for example, a film forming step of forming the film 2 on the glass substrate 1 by a known method, and a polishing step of polishing the film after the film forming step. is preferred. An example of obtaining the film-coated glass substrate 20 having the configuration shown in FIG. 2 by this method will be described below.

(Film formation process)
In the film forming process, a film is formed on the glass substrate. When the film is a laminated film, it is preferable to form each layer in order from the one closest to the glass substrate, although it depends on the film formation method.

Each layer included in the film can be formed using various film formation methods such as chemical vapor deposition (CVD), electron beam deposition, vacuum deposition, sputtering, and spraying. Among them, the thermal CVD method is preferable as the film forming method because, as will be described later, it is easy to improve the performance of the layer formed of the doped metal oxide. Alternatively, the film formation may be performed by an on-line method during the process of producing the glass substrate with a float facility. Alternatively, film formation may be performed by reheating the glass substrate manufactured by the float method by an off-line method. From the viewpoint of manufacturing efficiency, it is preferable to form the film by a thermal CVD method on a glass substrate manufacturing line.

For example, when the film includes an optical adjustment layer, the optical adjustment layer is first deposited on the first surface of the glass substrate. When the optical adjustment layer includes a silicon carbide oxide (SiOC) layer, the optical adjustment layer may be deposited by a thermal CVD method. In this case, for example, a mixed gas containing monosilane (SiH ₄ ), ethylene and carbon dioxide can be used as the raw material. When such a carbon-containing gas is used, a particulate silicon compound is easily formed together with a film-like silicon compound, and the haze ratio can be increased.

When the optical adjustment layer includes a silicon oxide (SiO ₂ ) layer, the raw material can be, for example, monosilane (SiH ₄ ), tetraethoxysilane, mixed gas such as ethylene and oxygen.

Then, if desired, a crystal growth base layer is deposited, and then an infrared reflective layer is deposited. Here, doped metal oxides are sometimes used as materials for forming the crystal growth base layer and the infrared reflective layer. Therefore, it is preferable that the impurity element is incorporated into the crystal structure. For this purpose, it is preferable to form the film by a high-temperature process. Therefore, the crystal growth base layer and the infrared reflective layer are preferably formed by thermal CVD. Furthermore, if it can be formed by the atmospheric pressure thermal CVD method, a large-scale vacuum apparatus becomes unnecessary, and productivity can be improved. For example, the infrared reflective layer is composed of fluorine-doped tin oxide (FTO), and the crystal growth base layer is composed of antimony-doped tin oxide (ATO) containing tin oxide, which is the same material as the metal oxide forming the infrared reflective layer. , and a case where each layer is formed by thermal CVD.

When the crystal growth base layer is composed of antimony-doped tin oxide (ATO), a mixture of an inorganic or organic tin compound and an antimony compound is used as a raw material.

Tin compounds _include _monobutyltin trichloride ( _C4H9SnCl3 ) and tin tetrachloride ( _SnCl4 ).
Antimony compounds include antimony trichloride (SbCl ₃ ) and antimony pentachloride (SbCl ₅ ).

When the infrared reflective layer is composed of fluorine-doped tin oxide (FTO), a mixture of an inorganic or organic tin compound and a fluorine compound is used as a raw material.

Tin compounds include monobutyltin trichloride (C ₄ H ₉ SnCl ₃ ) and tin tetrachloride (SnCl ₄ ), as described above.
Fluorine compounds include hydrogen fluoride and trifluoroacetic acid.

When depositing each layer by the thermal CVD method, the source gas containing the above-described source material is blown onto a heated object to be deposited, thereby allowing the source gas to react and form the film. In the film formation of each layer by the thermal CVD method, the raw material gases may be mixed in advance before being conveyed. Alternatively, the source gases may be mixed on the surface of the object to be deposited. When the raw material is liquid, the raw material may be vaporized into a gas by using a bubbling method, a vaporizer, or the like.

Also, an overcoat layer may be further formed. In that case, the film may be formed by the various film forming methods described above. For example, the overcoat layer may be formed by a thermal CVD method using the same raw material gas as that for the optical adjustment layer described above. Alternatively, for example, a film may be formed by a wet method including preparing a coating solution for the overcoat layer, applying it by a method such as spin coating, and heat-treating. When forming a layer containing SiO ₂ by a wet method, for example, the coating solution includes a silica precursor, an organic solvent, and water that forms a layer containing SiO ₂ by heat treatment.

(polishing process)
By polishing the unpolished film-coated glass substrate obtained by the above method, the skewness of the outermost surface of the film can be reduced to 0 or less. The polishing method is not particularly limited, but from the viewpoint of productivity, a method including polishing the outermost surface of the film using a polishing slurry and a polishing pad is preferred.

The polishing slurry contains abrasive grains and a dispersion medium for the abrasive grains, and known abrasive grains and dispersion media can be used.

As abrasive grains, oxide particles such as cerium oxide, silicon oxide, iron oxide, manganese oxide, titanium oxide, zirconium oxide, and aluminum oxide, and diamond can be used. Oxide particles are preferable from the viewpoint of productivity. , silicon oxide is more preferred.

For example, colloidal silica or fumed silica can be used as silicon oxide, and it is preferable that the solid content concentration in the polishing slurry is 1% by mass or more and 20% by mass or less. When the solid content concentration is 1% by mass or more, sufficient polishing can be performed, and when it is 20% by mass or less, aggregation of particles can be suppressed. The average particle diameter of the abrasive grains is preferably 10 nm or more and preferably 200 nm or less when the solid content concentration is 1% by mass or more and 20% by mass or less. When the average particle diameter is 10 nm or more, it is possible to suppress the increase in the viscosity of the polishing slurry due to gelation of the solid content. Easier to maintain dispersibility. When other oxide particles are used, particles obtained by classifying and pulverizing fired powder are often used, and the average particle diameter is preferably 0.1 μm or more, and preferably 10 μm or less. When the average particle size is 0.1 µm or more, the fired powder can be easily pulverized, and when the average particle size is 10 µm or less, it becomes easy to maintain the dispersion stability of the particles in the slurry. Here, the average particle size means the median value of the volume-based particle size distribution.

The dispersion medium can be appropriately selected from, for example, water, organic solvents, mixtures thereof, and the like. Further, a dispersant such as an organic acid salt or a cationic surfactant may be added to the dispersion medium.

The pH of the polishing slurry is preferably 1 to 12 from the viewpoint of suppressing deterioration of the polishing pad. This is because if the pH is less than 1 or greater than 12, the urethane or epoxy polymer constituting the polishing pad may decompose. Further, it is more preferable to use an acidic slurry, since it is easier to reduce the skewness of the film surface in a shorter time.

The skewness of the film surface tends to decrease as the polishing time increases. Here, the specific polishing time can be appropriately adjusted depending on the polishing conditions, the composition of the film surface, and the like. minutes or more is preferable, 0.4 minutes or more is more preferable, 0.6 minutes or more is still more preferable, and 1.8 minutes or more is even more preferable. The polishing time is preferably 30 minutes or less, more preferably 15 minutes or less, from the viewpoint of suppressing fluctuations in film properties due to an excessive amount of polishing. The polishing time in this case may be, for example, 0.3 to 30 minutes. On the other hand, when an alkaline slurry is used to polish the surface of a fluorine-doped tin oxide (FTO) layer, the polishing time is preferably 1 minute or longer, more preferably 1.8 minutes or longer, and even more preferably 5.4 minutes or longer. As in the case of the acid slurry, the polishing time is preferably 100 minutes or less, more preferably 50 minutes or less, from the viewpoint of suppressing fluctuations in film properties due to an excessive amount of polishing. The polishing time in this case may be, for example, 1 to 100 minutes.

The polishing pad is not particularly limited, and known materials such as non-woven fabric, hard urethane, and suede can be used. When using a polishing pad mainly composed of suede or nonwoven fabric, a soft suede or nonwoven fabric having a Shore A hardness of 40 to 60° may be used, or a hard nonwoven fabric having a Shore A hardness of 60 to 80° may be used. Moreover, you may use these pads in piles. A hard urethane pad having a Shore D hardness of 20 to 80° may be used.

In addition, as other conditions, the polishing load, the number of revolutions of the pad, and the like can be adjusted as appropriate. For example, the polishing load is preferably 50 g/cm ² to 150 g/cm ² , the pad rotation speed is preferably 10 rpm to 60 rpm in the case of a double-sided polisher or an Oscar type polisher, and 100 rpm to 500 rpm in the case of a disc brush polisher. preferable.

The device used for polishing is also not particularly limited, and known devices such as a double-sided polishing machine, a disk brush polishing machine, and an Oscar type polishing machine can be used.

The film-coated glass substrate according to the present embodiment is obtained through the film-forming process and the polishing process as described above.

The method for manufacturing a film-coated glass substrate according to the present embodiment may further include a step (strengthening step) of air-cooling or chemically tempering the glass substrate. This strengthening step may be performed in any order, for example, before forming a film on the glass substrate, after manufacturing the film-coated glass substrate, or the like. By carrying out the strengthening step, the strength of the glass substrate and the obtained film-coated glass substrate can be increased.

In addition, after placing the film on the glass substrate, the obtained glass substrate with the film may be subjected to bending. Alternatively, when manufacturing laminated glass from a film-coated glass substrate, a step of bonding another glass substrate to the second main surface side of the glass substrate may be performed.

It is obvious to those skilled in the art that various other modifications are possible.

The film-coated glass substrate according to the present embodiment includes, for example, vehicle window glass (front glass, rear glass, side glass, roof glass, etc.), laminated glass for vehicle window glass, building window glass, and laminated glass for building use. It can be suitably used for glass and the like.

The present invention will be described in detail below with reference to Examples, but the present invention is not limited to these. Examples 1 to 19 are working examples, and examples 20 to 32 are comparative examples.

(Film formation process)
A glass substrate having a thickness of 2.1 mm (soda lime silicate glass: manufactured by AGC Co., Ltd.) was used as a glass substrate, and one of the following films A to C was formed as a film to produce a glass substrate with a film. Films A to C are laminated films each composed of a plurality of layers.

(Production Example 1: Membrane A)
A SiOC layer was formed as an optical adjustment layer on a glass substrate by a thermal CVD method. Monosilane, ethylene, and carbon dioxide were used as raw material gases, and nitrogen was used as a carrier gas. The target thickness of the SiOC layer was set to 70 nm.
Next, an infrared reflective layer was formed on the SiOC layer. The infrared reflective layer was a fluorine-doped tin oxide layer (SnO ₂ :F, FTO) and was deposited by thermal CVD. Monobutyltin trichloride (C ₄ H ₉ SnCl ₃ , MBTC), water, air, trifluoroacetic acid (TFA), and nitric acid were used as source gases, and nitrogen was used as carrier gas. The target thickness (maximum thickness) of the infrared reflective layer was 300 nm.

(Production Example 2: Film B)
In the same manner as in Production Example 1, a SiOC layer was formed as an optical adjustment layer on a glass substrate.
Next, a crystal growth base layer was formed on the SiOC layer. Antimony-doped tin oxide (SnO ₂ :Sb, ATO) was used as the crystal growth base layer, and was deposited by a thermal CVD method. Monobutyltin trichloride (C ₄ H ₉ SnCl ₃ , MBTC), antimony trichloride (SbCl ₃ ), water, air, and hydrogen chloride were used as raw material gases, and nitrogen was used as carrier gas. The target thickness (maximum thickness) of the crystal growth base layer was set to 500 nm.
Next, FTO was formed as an infrared reflective layer on the crystal growth base layer in the same manner as in Production Example 1 except that the target thickness (maximum thickness) was changed to 200 nm.

(Production Example 3: Membrane C)
A SiO ₂ layer was formed as an optical adjustment layer on a glass substrate by a thermal CVD method. Monosilane, ethylene, and oxygen were used as raw material gases, and nitrogen was used as a carrier gas. The target thickness of the _SiO2 layer was set to 30 nm.
Next, a SnO ₂ layer was formed on the SiO ₂ layer by a thermal CVD method. Tributyltin (C ₁₂ H ₂₈ Sn, TBT), water, air and oxygen were used as raw material gases, and nitrogen was used as carrier gas. The target thickness (maximum thickness) of the SnO ₂ layer was set to 50 nm.

(polishing process)
The outermost surface of the film of the obtained film-coated glass substrate was polished using a polishing slurry and a polishing pad to obtain film-coated glass substrates of Examples 1 to 28. Polishing conditions are shown below. Table 1 shows the types of films, combinations of polishing conditions, and processing times in each example. In Examples 29 to 32, no polishing was performed, and the film-coated glass substrates obtained in the above production examples were used as they were. In the example using the disk brush polishing machine, polishing was performed by passing the film-coated glass substrate to be polished through the portion to be polished. x Calculated by the number of passes.
(polishing conditions)
Slurry: An acidic slurry containing oxide particles with an average particle size of 0.1 μm or an alkaline slurry containing oxide particles with an average particle size of 0.1 μm was used.
Polishing pad: A soft nonwoven fabric with a Shore A hardness of 50.5 or a hard nonwoven fabric with a Shore A hardness of 73.7 was used.
Polishing device: A double-sided polishing machine (manufactured by Speedfam Co., Ltd.) or a disk brush polishing machine (manufactured by Hiraga Kikai Kogyo Co., Ltd.) was used. The double-side polishing machine was used with a polishing load of 100 g/cm ² , a pad diameter of 640 mmφ, and a pad rotation speed of 30 rpm. The disk brush polishing machine was used with a polishing load of 100 g/cm ² , a pad diameter of 94 mmφ, and a pad rotation speed of 300 rpm.

(Surface roughness Sa, skewness Ssk)
The film surface roughness Sa and skewness Ssk of the film-coated glass substrate of each example were measured.
Using an atomic force microscope (manufactured by Bruker, DIMENSION ICON), a range of 5 μm×5 μm was measured under conditions of 1 Hz and 256 lines. The obtained data was analyzed using SPIP6.7.3 manufactured by Image Metrology. Specifically, the resulting data were tilt-corrected by a second-order polynomial plane fit, then the roughness plane correction option was set to "Subtract Mean." Roughness Sa and skewness Ssk were calculated. Table 1 shows the calculation results.

(Stain resistance test)
A test was conducted by rubbing the outermost surface of the film with a cloth under the following conditions. Then, under a fluorescent lamp of 3000 lux, the area near the rubbed center was visually observed with reflected light, and the stain resistance was evaluated according to the following criteria. Table 1 shows the evaluation results.
(Test condition)
Apparatus: Surface wear tester (PA-300, manufactured by Daiei Kagaku Seiki Seisakusho)
Friction element: Cloth (No. 300 flannel cloth, white)
Scraping speed: 5.6m/min
Number of times of rubbing: 1000 times Load: 4.9 N/cm ²
(evaluation)
Good: Cloth fibers were not adhered at all.
Acceptable: Almost no fibers of the cloth adhered.
Poor: Cloth fibers were clearly attached.

3 is the glass substrate of Example 12 after the stain resistance test, and FIG. 4 is the glass substrate of Example 23 after the stain resistance test. A region A surrounded by a dotted line includes a region rubbed with a cloth in the test, and the vicinity of the center of the region A was visually evaluated in the test. The white area below area A is the reflection of the fluorescent lamp used during observation. In Example 23, which is rated "poor", the entire rubbed area is whitish, indicating that the fibers of the cloth are clearly attached. On the other hand, in Example 12, which was evaluated as "good", no fabric fibers adhered to the rubbed area.

From Table 1, the film-coated glass substrates of Examples 1 to 19 with a skewness of 0 or less exhibited excellent stain resistance. On the other hand, the film-coated glass substrates of Examples 20 to 32 with a skewness greater than 0 were inferior in film contamination resistance. FIG. 5 is a graph showing the relationship between the film-coated glass substrates of Examples 1 to 32, Sa on the horizontal axis and Ssk on the vertical axis, and the stain resistance. From FIG. 5, it was confirmed that the value of Ssk correlated with the stain resistance regardless of the value of Sa, and that the stain resistance was excellent when the skewness was 0 or less.

As described above, this specification discloses the following matters.
1. A film-coated glass substrate comprising a glass substrate and a film disposed on the glass substrate,
the glass substrate has a first surface and a second surface facing each other;
the film is disposed on the first surface of the glass substrate;
A film-coated glass substrate, wherein the skewness of the outermost surface of the film is 0 or less.
2. 2. The film-coated glass substrate according to 1 above, wherein the surface roughness of the outermost surface of the film is greater than 0.4 nm.
3. 3. The film-coated glass substrate according to 1 or 2 above, wherein adhesion of fibers is not confirmed when the outermost surface of the film is rubbed with a cloth.
4. 4. The film-coated glass substrate according to any one of 1 to 3 above, wherein the outermost surface of the film has an emissivity of 0.3 or less.
5. 5. The film-coated glass substrate according to any one of 1 to 4 above, wherein the film comprises a crystalline infrared reflective layer.
6. 6. The film-coated glass substrate according to 5 above, wherein the film includes a crystalline crystal growth base layer and the infrared reflective layer from the side closer to the glass substrate.
7. 7. The film-coated glass substrate according to 5 or 6 above, wherein the infrared reflective layer contains a doped metal oxide obtained by doping at least one metal oxide of tin oxide and titanium oxide with another element.
8. 8. The film-coated glass substrate according to any one of 5 to 7 above, wherein the infrared reflective layer comprises a fluorine-doped tin oxide film.
9. 7. The film-coated glass substrate according to 6 above, wherein the crystal growth base layer comprises an antimony-doped tin oxide film, and the infrared reflective layer comprises a fluorine-doped tin oxide film.
10. 10. The film-coated glass substrate according to any one of 5 to 9 above, wherein the infrared reflective layer is arranged on the outermost surface of the film.
11. 10. The film-coated glass substrate according to any one of 5 to 9 above, wherein the film further comprises an overcoat layer, and the overcoat layer is arranged on the outermost surface of the film.
12. 12. The film-coated glass substrate according to any one of 5 to 11 above, wherein the film further includes an optical adjustment layer, and the optical adjustment layer is arranged at a position in contact with the first surface.
13. 13. The film-coated glass substrate according to 12 above, wherein the optical adjustment layer comprises a SiOC film.
14. 14. The film-coated glass substrate according to any one of 1 to 13 above, wherein the film includes a layer formed by a thermal CVD method.
15. 15. The film-coated glass substrate according to any one of 1 to 14 above, wherein the film includes a layer formed by a thermal CVD method on a glass substrate production line.
16. 16. The film-coated glass substrate according to any one of 1 to 15 above, which is used for vehicle window glass or laminated glass for vehicle window glass.

Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention. This application is based on a Japanese patent application (Japanese Patent Application No. 2021-194731) filed on November 30, 2021, the contents of which are incorporated herein by reference.

10, 20 film-coated glass substrate 1 glass substrate 1a first surface 1b second surface 2 film 3 crystal growth base layer 5 infrared reflecting layer 7 optical adjustment layer

Claims

A film-coated glass substrate comprising a glass substrate and a film disposed on the glass substrate,
the glass substrate has a first surface and a second surface facing each other;
the film is disposed on the first surface of the glass substrate;
A film-coated glass substrate, wherein the skewness of the outermost surface of the film is 0 or less.
The film-coated glass substrate according to claim 1, wherein the surface roughness of the outermost surface of the film is greater than 0.4 nm.
The film-coated glass substrate according to claim 1, wherein adhesion of fibers is not confirmed when the outermost surface of the film is rubbed with a cloth.
The film-coated glass substrate according to claim 1, wherein the outermost surface of the film has an emissivity of 0.3 or less.
The film-coated glass substrate according to claim 1, wherein the film includes a crystalline infrared reflective layer.
6. The film-coated glass substrate according to claim 5, wherein the film includes a crystalline crystal growth base layer and the infrared reflective layer from the side closer to the glass substrate.
The film-coated glass substrate according to claim 5, wherein the infrared reflective layer contains a doped metal oxide in which at least one metal oxide of tin oxide and titanium oxide is doped with another element.
The film-coated glass substrate according to claim 5, wherein the infrared reflective layer comprises a fluorine-doped tin oxide film.
The film-coated glass substrate according to claim 6, wherein the crystal growth base layer comprises an antimony-doped tin oxide film, and the infrared reflective layer comprises a fluorine-doped tin oxide film.
The film-coated glass substrate according to claim 5, wherein the infrared reflective layer is arranged on the outermost surface of the film.
The film-coated glass substrate according to claim 5, wherein the film further comprises an overcoat layer, and the overcoat layer is arranged on the outermost surface of the film.
The film-coated glass substrate according to claim 5, wherein the film further includes an optical adjustment layer, and the optical adjustment layer is arranged at a position in contact with the first surface.
The film-coated glass substrate according to claim 12, wherein the optical adjustment layer comprises an SiOC film.
The film-coated glass substrate according to claim 1, wherein the film includes a layer formed by a thermal CVD method.
The film-coated glass substrate according to claim 1, wherein the film includes a layer formed by a thermal CVD method on a glass substrate manufacturing line.
The film-coated glass substrate according to any one of claims 1 to 15, which is used for vehicle window glass or laminated glass for vehicle window glass.