JP2024066990A - Glass laminate and method for producing same - Google Patents

Abstract

[Problem] To provide a glass laminate for vehicle window glass, which has a coating having a suitable vertical thickness distribution and good crack resistance, and a manufacturing method thereof. [Solution] A glass laminate (1) having a coating (20) having an upper side (21) along the upper side (11) of a glass substrate (10) and a specific dimension region having a vertical dimension of more than 100 mm, in which the coating has a thickness distribution in at least a part of the specific dimension region, in which the thickness of the coating in a region between the upper side of the coating and a first imaginary line (IL1) obtained by translating the upper side of the coating 20 mm downward along the surface of the coating is more than 0 μm and not more than 2.0 μm, and the thickness of the coating in a region on a second imaginary line (IL2) obtained by translating the upper side of the coating 100 mm downward along the surface of the coating and below the second imaginary line (IL2) is 2.0 to 3.0 μm. [Selected Figure] Figure 1

Description

This disclosure relates to a glass laminate and a method for manufacturing the same.

For use as vehicle window glass, a glass laminate is known in which a coating containing a functional component having a function such as blocking ultraviolet and/or infrared rays is formed on one surface of a glass substrate.
A coating containing a functional component is also called a functional film.
2. Description of the Related Art A glass laminate for vehicle window glass such as a windshield, a side glass, or a rear glass is used in an upright state with the upper side facing upward.

The coating can be formed, for example, by applying a liquid composition for forming a coating, which contains one or more hydrolyzable silicon compounds, onto one surface of a glass substrate to form a coating film, and then curing the coating film.
A preferred method for applying the liquid composition is a flow coating method. The specific film formation using the flow coating method can be carried out as follows.
A liquid composition for forming a coating is discharged from a liquid nozzle at a position slightly spaced from the upper side of a glass substrate, which is held upright with the upper side facing upward, onto one surface of the glass substrate, while the liquid nozzle is moved relative to the upper side of the glass substrate. By holding the glass substrate upright, the liquid composition discharged from the liquid nozzle flows downward from above, forming a coating film. This coating film can be cured to form a coating film.

International Publication No. 2015/060445

In the above method, the liquid composition flows downward, so the thickness of the coating tends to increase from the top to the bottom. The lower part of the coating tends to be relatively thick, and if the thickness exceeds the preferred range, the residual stress increases, which may cause cracks.
The term "cracks" as used herein includes initial cracks at the completion of film formation, cracks during environmental tests such as weather resistance tests, and cracks after long-term practical use.
When the viscosity of the liquid composition is reduced by, for example, lowering the concentration of the liquid composition in order to reduce the thickness of the lower part of the coating, the coating tends to be thinner overall. If the coating is thinner overall than the preferred range, there is a risk that the desired function, such as blocking ultraviolet and/or infrared rays, may not be fully exerted.

Patent Document 1 relates to a method for producing a coated glass sheet. This document discloses a coating system (1) having an injection part (2) including a nozzle (22) and an air blowing unit (5) (FIG. 2, etc.). The air blowing system (5) moves relative to the glass sheet together with the injection part (2) including the nozzle (22) (FIGS. 5A and 5B, etc.). Immediately after the coating liquid is injected from the nozzle (22) onto the glass sheet, the air blowing unit (5) blows air onto the part where the coating liquid is injected (paragraphs 0050 and 0060).
In Patent Document 1, in order to prevent the coating liquid from flowing around to the opposite side of the coating surface of the glass plate, the air blowing unit (5) is disposed in contact with the side or top of the injection section (2) or above and away from the injection section (2) (FIGS. 5A, 7 and 8).
Patent Document 1 describes that the thickness of the coating film near the coating line can be increased by air drying immediately after coating, and the vertical thickness distribution of the coating film can be reduced (paragraph 0070).
The reference numerals of the components described in Patent Document 1 are the reference numerals described in this document and have no relation to the reference numerals used for the components in the present disclosure.

FIGS. 12 and 13 of Patent Document 1 are graphs showing the vertical thickness distribution of the coatings obtained in Example 1 in which air was blown from above and in Examples 2 to 4 in which air was blown from the front.
As shown in these figures, the coating obtained by the method described in Patent Document 1 has large up-down peaks indicated by symbols Ma and Mb within a range of 1 mm from the coating line, has localized thick film parts with a film thickness of more than 2.5 μm, and has a film thickness variation of about 0.9 μm or more. In particular, there is a larger film thickness variation in Example 1, in which air was blown from above, compared to Examples 2 to 4, in which air was blown from the front.
The coating obtained by the method described in Patent Document 1 also has a thin thickness of less than 2 μm when the distance from the coating line is 3 mm or more, and the thickness tends to gradually decrease as the distance from the coating line increases.
In the local thick film part that protrudes locally near the coating line, residual stress is large and cracks may occur. The local thick film part extending in the width direction along the coating line is visually recognized as perspective distortion and may deteriorate the appearance. In the range of 3 mm or more away from the coating line, the film thickness is thin at less than 2 μm, and there is a risk that the desired function such as blocking ultraviolet and/or infrared rays may not be fully realized.

The present disclosure has been made in consideration of the above circumstances, and has an object to provide a glass laminate for vehicle window glass, which suppresses localized film thickening near the upper edge and film thickening in the lower part, has a favorable film thickness distribution in the vertical direction, and has a coating with good crack resistance, and a manufacturing method thereof.
Another object of the present disclosure is to provide a glass laminate for vehicle window glass, which contains a functional component, has a coating that is inhibited from localized thickening near the upper edge and thickening at the lower part, has a suitable film thickness distribution in the vertical direction, and has good crack resistance, and is able to stably exhibit desired functions, and a method for manufacturing the same.

The present disclosure provides the following glass laminate and method for producing the same.
[1] A glass laminate for a vehicle window glass, comprising: a glass substrate having an upper side; and a coating formed on one surface of the glass substrate, the coating containing a siloxane bond and one or more organic components selected from the group consisting of an organic group bonded to a Si atom and an organic compound, the glass laminate being attached to a window opening of a vehicle,
the coating is formed on the surface of the glass substrate in a region including the window opening in a state in which the glass laminate completely closes the window opening,
The coating has an upper edge along the upper edge of the glass substrate and a specific dimension region having a vertical dimension of more than 100 mm;
the coating has a specific thickness distribution in at least a part of the specific dimension region, in which the thickness of the coating in a region between the upper edge of the coating and a first imaginary line obtained by moving the upper edge of the coating parallel to the surface of the coating 20 mm downward is more than 0 μm and not more than 2.0 μm, and the thickness of the coating on a second imaginary line obtained by moving the upper edge of the coating parallel to the surface of the coating 100 mm downward and in a region below the second imaginary line is 2.0 to 3.0 μm.

[2] The glass laminate according to [1], wherein, in the specific film thickness distribution, a film thickness on the first imaginary line of the coating is 1.0 to 2.0 μm.
[3] The glass laminate according to [1] or [2], wherein, in the specific film thickness distribution, the film thickness of the coating on a third imaginary line obtained by moving the upper edge of the coating parallel to a surface of the coating 80 mm downward and in a region below the third imaginary line is 2.0 to 3.0 μm.
[4] The glass laminate according to any one of [1] to [3], wherein, in the specific film thickness distribution, a film thickness of the coating on a fourth imaginary line obtained by moving the upper side of the coating parallel to a surface of the coating 40 mm downward is 1.5 to 3.0 μm.

[5] The glass laminate according to any one of [1] to [4], wherein the coating comprises a cured product of a composition containing one or more hydrolyzable silicon compounds which have one or more hydrolyzable groups and may be partially hydrolyzed and condensed between the same or different species.
[6] The glass laminate according to any one of [1] to [5], wherein the coating contains one or more functional components selected from the group consisting of an ultraviolet shielding agent and an infrared shielding agent.
[7] The glass laminate according to any one of [1] to [6], which is for use in a vehicle side glass.
[8] The glass laminate according to [7], which is for a vehicle side glass that is attached to a window opening of a vehicle so as to be freely opened and closed.

[9] A step (S1) of preparing a liquid composition containing one or more hydrolyzable silicon compounds having hydrolyzable groups;
The glass substrate is disposed with the upper side of the glass substrate facing upward, and is disposed substantially vertically or at an inclination angle between substantially horizontal and substantially vertical with respect to the ground.
a step (S2) of relatively moving a liquid nozzle that ejects the liquid composition toward a portion of the surface of the glass substrate near the upper edge of the glass substrate along the upper edge of the glass substrate from one end side to the other end side of the upper edge of the glass substrate in a width direction of the glass substrate to flow the liquid composition onto the surface of the glass substrate to form a coating film, thereby obtaining a glass substrate with a coating film;
and (S3) heating the glass substrate with a coating film to harden the coating film.

[10] In step (S2),
The method for manufacturing a glass laminate according to [9], further comprising the steps of: blowing air from one or more air blowing nozzles positioned lower than the position of the liquid nozzle onto the liquid composition ejected from the liquid nozzle at a certain timing, simultaneously with or immediately after the liquid composition reaches the surface of the glass substrate, in synchronization with the relative movement of the liquid nozzle from one end side to the other end side of the upper edge of the glass substrate, to form the coating film in which at least the area between the upper edge of the coating film and the second virtual line is dried.
[11] The method for producing a glass laminate according to [10], wherein in the step (S2), an angle of a central axis of the air blowing nozzle with respect to the surface of the glass substrate is set to 10 to 60°.

[12] In step (S2),
The glass substrate is fixed, and the liquid nozzle is configured to move in a width direction of the glass substrate;
a plurality of the air blowing nozzles capable of blowing air in an overall range at least between the upper side of the coating film and the second virtual line are arranged in a line in a width direction of the glass substrate in front of the surface of the glass substrate;
The method for manufacturing a glass laminate according to [10] or [11], wherein an operation of blowing air from one or more air blowing nozzles is performed on the liquid composition ejected from the liquid nozzle onto the surface of the glass substrate at a certain timing, from one end side to the other end side of the upper edge of the glass substrate, in accordance with the movement of the liquid nozzle, simultaneously with or immediately after the liquid composition reaches the surface of the glass substrate.
[13] The method for producing a glass laminate according to any one of [10] to [12], wherein the air blowing nozzle is capable of adjusting an angle of a central axis of the air blowing nozzle with respect to the surface of the glass base material.

Effects of the Invention The present disclosure can provide a glass laminate for vehicle window glass, which has a coating that is inhibited from localized thickening near the upper edge and thickening in the lower portion, has a favorable film thickness distribution in the vertical direction, and has good crack resistance, and a manufacturing method thereof.
The present disclosure also makes it possible to provide a glass laminate for vehicle window glass, which contains a functional component, has a coating that is inhibited from localized thickening near the upper edge and thickening at the lower part, has a favorable film thickness distribution in the vertical direction, and has good crack resistance and can stably exhibit desired functions, and a method for manufacturing the same.

1 is an example of a schematic plan view of a glass laminate according to an embodiment of the present invention. FIG. 2 is a schematic cross-sectional view (cross-sectional view taken along line II-II) of the glass laminate of FIG. 1 . FIG. 2 is a schematic side view of an example of a coating device suitable for use in step (S2). FIG. 2 is a schematic top view of the coating device. 1 is a graph showing the film thickness distribution in the vertical direction on the vertical center axis of the coating obtained in Example (E1). 1 is a graph showing the film thickness distribution in the vertical direction on the vertical center axis of the coating obtained in Example (E1). 1 is a graph showing the film thickness distribution in the vertical direction on the vertical center axis of the coating obtained in Example (E2). 1 is a graph showing the film thickness distribution in the vertical direction on the vertical center axis of the coating obtained in Example (E2). 1 is a graph showing the film thickness distribution in the vertical direction on the vertical center axis of the coating obtained in Example (E101). 1 is a graph showing the film thickness distribution in the vertical direction on the vertical center axis of the coating obtained in Example (E101). 1 is a graph showing the film thickness distribution in the vertical direction on the vertical center axis of the coating obtained in Example (E102). 1 is a graph showing the film thickness distribution in the vertical direction on the vertical center axis of the coating obtained in Example (E102). 1 is a graph showing the film thickness distribution in the vertical direction on the vertical center axis of the coating obtained in Example (E103). 1 is a graph showing the film thickness distribution in the vertical direction on the vertical center axis of the coating obtained in Example (E103).

In this specification, unless otherwise specified, the "surface" of a plate-like member such as a glass plate refers to the main surface having the largest area, excluding the end faces (also called side faces) of the plate-like member.
In this specification, unless otherwise specified, the forward moving direction of the vehicle is defined as the forward direction, and the backward moving direction of the vehicle is defined as the rearward direction.
In this specification, unless otherwise specified, the terms "front/rear,""up/down,""left/right,""vertical/horizontal," and "inside/outside" of a glass laminate refer to the "front/rear,""up/down,""left/right,""vertical/horizontal," and "inside/outside" of the glass laminate when it is fitted into a vehicle (actual usage state).
In this specification, "approximately horizontal with respect to the ground" means a range of ±10° from the perfectly horizontal direction with respect to the ground, and "approximately vertical with respect to the ground" means a range of ±10° from the perfectly vertical direction with respect to the ground.

Generally, thin film structures are referred to as "films" and "sheets" depending on their thickness. In this specification, no clear distinction is made between the two. Therefore, in this specification, "film" may include "sheet."

In a composition containing one or more hydrolyzable silicon compounds, the one or more hydrolyzable silicon compounds may be partially hydrolyzed and condensed between the same or different types of compounds.
In this specification, the hydrolysis condensate of one or more hydrolyzable silicon compounds refers to an oligomer (polymer) produced by hydrolysis of at least a portion of the hydrolyzable groups contained in one or more hydrolyzable silicon compounds, followed by dehydration condensation.

In this specification, the term "functional group" is a term that comprehensively indicates a group having a reaction, as distinguished from a simple substituent.
In this specification, (meth)acrylic is a general term for acrylic and methacrylic, and the same applies to (meth)acrylic acid, (meth)acrylonitrile, (meth)acryloxy, and the like.

In this specification, unless otherwise specified, ultraviolet light is light in the wavelength range of 300 to 380 nm, infrared light is light in the wavelength range of 780 to 2500 nm, and visible light is light in the wavelength range of 380 to 780 nm.
In this specification, unless otherwise specified, the term "to" indicating a range of values is used to mean that the range includes the values before and after it as the lower and upper limits.
Hereinafter, an embodiment of the present invention will be described.

[Glass laminate]
The present disclosure relates to a glass laminate for a vehicle window glass that is attached to a window opening of a vehicle such as an automobile, has an upper edge, and is used in a standing state with the upper edge side facing upward. Examples of the vehicle window glass include a front glass, a side glass, and a rear glass. The glass laminate of the present disclosure is suitable for a vehicle side glass, and is particularly suitable for a vehicle side glass that is attached to a window opening of a vehicle such as an automobile so as to be freely opened and closed.

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 a schematic plan view of a glass laminate according to the present embodiment. Fig. 2 is a schematic cross-sectional view (cross-sectional view taken along line II-II) of the glass laminate according to the present embodiment. For ease of visual recognition, the scales of the components in each drawing are appropriately changed.

As shown in FIG. 2, the glass laminate 1 of this embodiment has a glass substrate 10 and a coating 20 formed on one surface 10S of the glass substrate 10. The surface 10S of the glass substrate 10 on which the coating 20 is formed is not particularly limited, and can be, for example, the surface of the glass substrate 10 facing the vehicle interior (also referred to as the vehicle interior surface). The surface 10S is also referred to as the coating formation surface.

In the example shown in Fig. 1, the glass laminate 1 is a side glass located beside the driver's seat or the passenger seat of an automobile. The glass laminate 1 can be attached to a window opening of the vehicle so as to be freely opened and closed.
In the illustrated example, the glass substrate 10 has an outer periphery made up of four sides, namely, an upper side 11, a lower side 12, a front side 13, and a rear side 14, and the lower side 12 has an uneven surface.
In this embodiment, one of the front side 13 and the rear side 14 is also referred to as the “first side”, and the other side is also referred to as the “second side”. The upper side 11 can be a line connecting the upper end of the first side and the upper end of the second side, and the lower side 12 can be a line connecting the lower end of the first side and the lower end of the second side.
The number of sides of the glass substrate 10 is not particularly limited and can be 0, 1 or 2.

The maximum vertical dimension of the surface 10S of the glass substrate 10 exceeds 100 mm, and in applications such as automobile side glass, it can be 101 mm or more, 103 mm or more, 105 mm or more, 110 mm or more, 120 mm or more, 150 mm or more, 200 mm or more, or 300 mm or more. The upper limit of the maximum vertical dimension of the surface 10S is, for example, 800 mm.
In this specification, unless otherwise specified, the vertical dimension of a glass substrate at any position in the width direction is the distance between the upper end point and the lower end point of the glass substrate on the vertical axis passing through that position.
The surface 10S of the glass substrate 10 can be a concave curved surface. When the surface 10S is a curved surface, the vertical dimension of the glass substrate 10 is the vertical dimension along the curved surface, and is the vertical dimension when the glass substrate 10 is uncompressed and spread out flat.

The coating 20 is formed on the surface 10S of the glass substrate 10 in an area including the window opening when the glass laminate 1 completely closes the window opening. The coating 20 may be formed on the entire surface of the surface 10S of the glass substrate 10, or may be formed on substantially the entire surface of the surface 10S of the glass substrate 10 except for at least a portion of the periphery of the surface 10S of the glass substrate 10 (for example, an area within 30 mm of the above-mentioned four sides).

The coating 20 has an upper edge 21 that is aligned with the upper edge 11 of the glass substrate 10. In the illustrated example, the coating 20 has an outer periphery consisting of four edges: an upper edge 21, a lower edge 22, a front side edge 23, and a rear side edge 24. To facilitate visualization, a portion of the outer periphery of the coating 20 that does not coincide with the outer periphery of the glass substrate 10 is shown by a dashed line. In the illustrated example, the upper edge 21 of the coating 20 is located at a position obtained by shifting the upper edge 11 of the glass substrate 10 parallel to the surface 10S of the glass substrate 10 downward by about 2 to 30 mm, the front side edge 23 of the coating 20 coincides with the front side edge 13 of the glass substrate 10, and the rear side edge 24 of the coating 20 coincides with the rear side edge 14 of the glass substrate 10.
The number of sides of the coating 20 is not particularly limited and can be the same as the number of sides of the glass substrate 10 .
The planar shape of the glass substrate 10 and the area in which the coating 20 is formed can be designed appropriately depending on the shape of the vehicle or the like to which it is to be attached.

The maximum vertical dimension of the coating 20 is designed according to the size of the surface 10S of the glass substrate 10. The maximum vertical dimension of the coating 20 is more than 100 mm, and for applications such as automobile side glass, it can be 101 mm or more, 103 mm or more, 105 mm or more, 110 mm or more, 120 mm or more, 150 mm or more, 200 mm or more, or 300 mm or more. The upper limit of the maximum vertical dimension of the coating 20 is the maximum vertical dimension of the surface 10S of the glass substrate 10.
In this specification, unless otherwise specified, the longitudinal dimension of the coating at any position in the width direction is the distance between the upper and lower end points of the coating on the longitudinal axis passing through that position.
The surface 20S of the coating 20 can be a concave curved surface, similar to the surface 10S of the glass substrate 10. When the surface 20S of the coating 20 is a curved surface, the vertical dimension of the coating 20 is the vertical dimension along the curved surface, similar to the vertical dimension of the surface 10S of the glass substrate 10, and is the vertical dimension when the coating 20 is spread out and flat without being compressed.

The coating 20 contains a siloxane bond (Si--O bond) and one or more organic components selected from the group consisting of organic groups and organic compounds bonded to Si atoms.
The coating 20 can be formed using a liquid composition (LC) for forming a coating. The coating 20 is preferably made of a cured product of the liquid composition (LC) containing one or more hydrolyzable silicon compounds (SC) that have one or more hydrolyzable groups and may be partially hydrolyzed and condensed between the same or different types of compounds.

The coating 20 can be a functional film that imparts a specific function to a desired region of the glass substrate 10. The functions include selective transmission, selective absorption, or selective reflection of light or radio waves in a specific wavelength range; reflection or absorption of heat rays; anti-reflection; low reflection; low radiation; electrical current; heating; water or oil repellency; scratch resistance; antifouling; antibacterial properties; decoration such as coloring; and combinations of these.
The coating 20 can be, for example, a functional film that includes one or more functional components such as an ultraviolet ray shielding agent and an infrared ray shielding agent.

The coating 20 has a specific dimension region having a vertical dimension of more than 100 mm, and in at least a portion of this specific dimension region, has the following specific film thickness distribution:
The thickness (T) of the coating 20 in the region between the upper edge 21 of the coating 20 and a first imaginary line IL1 obtained by moving the upper edge 21 of the coating 20 parallel to the surface 20S of the coating 20 20 mm downward is greater than 0 μm and not greater than 2.0 μm.
The film thickness (T) of the coating 20 on the second imaginary line IL2 and in the region below the second imaginary line IL2 obtained by moving the upper side 21 of the coating 20 parallel to the surface 20S of the coating 20 downward by 100 mm is 2.0 to 3.0 μm.

The ratio of the area having the above-mentioned specific film thickness distribution to the area of a specific dimension region having a vertical dimension of more than 100 mm is not particularly limited, but is preferably 50% or more, more preferably 80% or more, particularly preferably 90% or more, and most preferably 100%.

1 , in a plan view, the central axis between a vertical axis YL1 passing through the front end of the glass laminate 1 and a vertical axis YR1 passing through the rear end of the glass laminate 1 is defined as a vertical central axis YC of the glass laminate 1. Furthermore, the central axis between the vertical axis YL1 and the vertical central axis YC is defined as a vertical axis YL2, and the central axis between the vertical central axis YC and the vertical axis YR1 is defined as a vertical axis YR2. By these vertical axes, the glass laminate 1 can be evenly divided into four regions in the width direction.
Coating 20 may, for example, have a particular dimensional region that includes longitudinal central axis YC and have the particular thickness distribution described above along longitudinal central axis YC.
For example, the specific dimension region of the coating 20 includes the region from the longitudinal central axis YC to the longitudinal axis YR2, and within the range from the longitudinal central axis YC to the longitudinal axis YR2, the coating 20 can have the above-mentioned specific film thickness distribution.
For example, the specific dimension region of the coating 20 includes the region from the vertical axis YL2 to the vertical axis YR2, and within the range from the vertical axis YL2 to the vertical axis YR2, the coating 20 can have the above-mentioned specific film thickness distribution.

The coating 20 having the above-mentioned specific film thickness distribution in at least a portion of the specific dimension region suppresses localized thickening near the upper edge 21 and thickening in the lower portion, has a favorable film thickness distribution in the vertical direction, and has good crack resistance.
The coating 20 having the above-mentioned specific film thickness distribution in at least a portion of the specific dimensional region suppresses the generation of initial cracks at the time of completion of film formation, has good initial crack resistance, and further has good crack resistance in environmental tests such as weather resistance tests.
A locally thickened portion extending in the width direction along the upper side is visually recognized as a perspective distortion, which may cause a poor appearance. In the present embodiment, since local thickening near the upper side 21 is suppressed, the coating 20 does not have a perspective distortion caused by the locally thickened portion, and has a good appearance.
Glass laminate 1 having coating 20 with the specific film thickness distribution in at least a part of the specific dimensional region can be produced by the production method described below.

It is preferable that the coating 20 has durability that allows it to maintain good performance even after long-term use. One example of durability is abrasion resistance.
In applications as vehicle side glass, the glass laminate 1 can be raised and lowered to open and close the window. For information on the mechanism for raising and lowering the side glass, see JP 2020-172403 A. In such applications, the coating 20 preferably has abrasion resistance that causes little damage even when the surface is repeatedly rubbed.
The coating 20 having the above-mentioned specific film thickness distribution in at least a portion of the specific dimensional region has a sufficient film thickness in the lower portion, so that even if the window is repeatedly opened and closed, damage such as cracks, scratches, and peeling is suppressed, and the coating 20 has good abrasion resistance.

If the film thickness (T) of the coating 20 in the region on the second imaginary line IL2 and below the second imaginary line IL2 is 2.0 to 3.0 μm, the coating 20 can satisfactorily exhibit the desired functions, such as blocking ultraviolet and/or infrared rays, when used for vehicle window glass such as vehicle side glass.

Hereinafter, preferred aspects of the above-mentioned specific film thickness distribution will be described.
From the viewpoint of functional expression, it is preferable that the difference between the film thickness (T) on the first imaginary line IL1 and the film thickness (T) on the second imaginary line IL2 is small. From this viewpoint, the film thickness (T) of the coating 20 on the first imaginary line IL1 is preferably 1.0 to 2.0 μm, more preferably 1.2 to 2.0 μm, and particularly preferably 1.3 to 2.0 μm.
From the same viewpoint, the thickness (T) of the coating 20 on an imaginary line obtained by moving the upper edge 21 of the coating 20 parallel to the surface 20S of the coating 20 15 mm downward is preferably 1.0 to 2.0 μm, more preferably 1.2 to 2.0 μm, and particularly preferably 1.3 to 2.0 μm.
From the same viewpoint, the thickness (T) of the coating 20 on an imaginary line (not shown, see Figures 4A and 5A, etc.) obtained by shifting the upper edge 21 of the coating 20 parallel to the surface 20S of the coating 20 10 mm downward is preferably 1.0 to 2.0 µm.

The thickness of the coating 20 on the third imaginary line IL3 (not shown, see Figures 4A and 5A, etc.) obtained by moving the upper edge 21 of the coating 20 parallel to the surface 20S of the coating 20 downward by 80 mm and in the region below the third imaginary line IL3 is preferably 2.0 to 3.0 μm. In this configuration, the range of the thickness (T) of the coating 20 from 2.0 to 3.0 μm is wider, and the coating 20 can better exhibit the desired function, such as blocking ultraviolet and/or infrared rays.

It is more preferable that the thickness of the coating 20 on and below an imaginary line (not shown, see Figures 4A and 5A, etc.) obtained by moving the upper edge 21 of the coating 20 parallel to the surface 20S of the coating 20 70 mm downward is 2.0 to 3.0 μm. In this configuration, the range of the thickness (T) of the coating 20 from 2.0 to 3.0 μm is wider, and the coating 20 can better exhibit the desired function, such as blocking ultraviolet and/or infrared rays.

From the viewpoint of achieving good functional expression, it is preferable that the film thickness (T) of the coating 20 on a fourth imaginary line IL4 (not shown, see Figures 4A and 5A, etc.) obtained by moving the upper edge 21 of the coating 20 parallel to the surface 20S of the coating 20 40 mm downward is 1.5 to 3.0 μm. It is more preferable that the film thickness (T) on the fourth imaginary line IL4 is 1.5 to 2.5 μm.

(Glass substrate)
The glass substrate may include tempered glass, laminated glass in which a plurality of glass sheets are bonded together via an interlayer film, or organic glass, and is preferably tempered glass or laminated glass. In Fig. 1 and Fig. 2, the glass substrate is illustrated as being flat, but for vehicles, the glass substrate is processed into a shape having a curved surface.

The type of glass plate that is the material for the tempered glass and laminated glass is not particularly limited, and examples thereof include soda-lime glass, borosilicate glass, aluminosilicate glass, lithium silicate glass, quartz glass, sapphire glass, and alkali-free glass.
The tempered glass is obtained by subjecting the above-mentioned glass plate to a tempering process 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 preferable.
The thickness of the tempered glass is not particularly limited, and is preferably 2 to 6 mm.
The thickness of the laminated glass is not particularly limited, but is preferably 2 to 6 mm.

The glass substrate may have a curved shape such that the vehicle exterior side is convex when the glass substrate is attached to a vehicle. When the glass substrate is a laminated glass, both the glass sheet on the vehicle interior side and the glass sheet on the vehicle exterior side may have a curved shape such that the vehicle exterior side is convex. The glass substrate may have a single curved shape curved in only one of the left-right direction or the up-down direction, or may have a compound curved shape curved in both the left-right direction and the up-down direction. The radius of curvature of the glass substrate may be 2000 to 11000 mm. The radius of curvature of the glass substrate in the left-right direction and the up-down direction may be the same or different. Gravity forming, press forming, roller forming, etc. are used for bending the glass substrate.

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

Materials for the 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.

(Coating)
The coating contains a siloxane bond (Si--O bond) and one or more organic components selected from the group consisting of organic groups and organic compounds bonded to Si atoms.
The coating can be formed using a liquid composition (LC) for forming a coating. The coating is preferably made of a cured product of the liquid composition (LC) containing one or more hydrolyzable silicon compounds (SC) having one or more hydrolyzable groups and which may be partially hydrolyzed and condensed between the same or different species.

In the coating, the organic group bonded to the Si atom can be derived from a hydrolyzable organic group that can be contained in the hydrolyzable silicon compound (SC) and/or a non-hydrolyzable organic group that can be contained in the hydrolyzable silicon compound (SC). The organic group bonded to the Si atom can include an alkyl group and an alkylene group.
Examples of organic compounds that can be contained in the coating include the flexibility-imparting component (FL) described below, the functional component (FU) described below, and components derived therefrom.

<Hydrolyzable Silicon Compounds (SC)>
One or more hydrolyzable silicon compounds (SC) can be cured by a hydrolysis condensation reaction to form a silicon oxide matrix. The term "silicon oxide matrix" as used herein refers to a polymer compound that is two-dimensionally or three-dimensionally polymerized by siloxane bonds represented by --Si--O--Si--.

The hydrolyzable silicon compound (SC) is a silicon compound having one or more hydrolyzable groups. The number of hydrolyzable groups bonded to one Si atom is 1 to 4, preferably 2 to 4, and more preferably 3 to 4. The hydrolyzable groups may be hydrolyzed to hydroxyl groups in the composition.

Examples of the hydrolyzable group include an alkoxy group (including a substituted alkoxy group such as an alkoxy-substituted alkoxy group), an alkenyloxy group, an acyl group, an acyloxy group, an oxime group, an amide group, an amino group, an iminoxy group, an aminoxy group, an alkyl-substituted amino group, an isocyanate group, and a halogen atom. Among them, organoxy groups such as an alkoxy group, an alkenyloxy group, an acyloxy group, an iminoxy group, and an aminoxy group are preferred, and an alkoxy group is particularly preferred. As the alkoxy group, an alkoxy group having 4 or less carbon atoms and an alkoxy-substituted alkoxy group having 4 or less carbon atoms (such as a 2-methoxyethoxy group) are preferred, and a methoxy group and an ethoxy group are particularly preferred. As the halogen atom, a chlorine atom is preferred.
When a plurality of hydrolyzable groups are present in the hydrolyzable silicon compound (SC), the plurality of hydrolyzable groups may be the same or different, and it is preferable that the hydrolyzable groups are the same in terms of availability of the raw material.

The one or more hydrolyzable silicon compounds (SC) preferably contain one or more trifunctional hydrolyzable silicon compounds and/or one or more tetrafunctional hydrolyzable silicon compounds. A combination of one or more trifunctional hydrolyzable silicon compounds and one or more tetrafunctional hydrolyzable silicon compounds is preferred. The one or more hydrolyzable silicon compounds (SC) may contain one or more bifunctional hydrolyzable silicon compounds as required.

A tetrafunctional hydrolyzable silicon compound is a compound having a structure in which four hydrolyzable groups are bonded to one Si atom. A trifunctional hydrolyzable silicon compound is a compound having a structure in which three hydrolyzable groups are bonded to one Si atom. A bifunctional hydrolyzable silicon compound is a compound having a structure in which two hydrolyzable groups are bonded to one Si atom.
The hydrolyzable silicon compound (SC) may have two or more structures in one molecule in which one or more hydrolyzable groups are bonded to a Si atom.

The hydrolyzable silicon compound (SC) may have a functional group other than the hydrolyzable group. Examples of the functional group other than the hydrolyzable group include an epoxy group, a (meth)acryloxy group, a primary or secondary amino group, an oxetanyl group, a vinyl group, a styryl group, a ureido group, a mercapto group, an isocyanate group, and a cyano group.

Examples of tetrafunctional hydrolyzable silicon compounds include tetramethoxysilane (TMOS), tetraethoxysilane (TEOS), tetra-n-propoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, and tetra-tert-butoxysilane. Tetramethoxysilane (TMOS) and tetraethoxysilane (TEOS) are preferred.

Examples of trifunctional hydrolyzable silicon compounds that have no functional groups other than the hydrolyzable group include methyltrimethoxysilane, methyltriethoxysilane, methyltris(2-methoxyethoxy)silane, methyltriacetoxysilane, methyltripoxysilane, methyltriisopropenoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriacetoxysilane, and 1,6-bis(trimethoxysilyl)hexane.

Examples of trifunctional hydrolyzable silicon compounds having functional groups other than hydrolyzable groups include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyltris(2-methoxyethoxy)silane, vinyltriisopropenoxysilane, p-styryltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 5,6-epoxyhexyltrimethoxysilane, 9,10-epoxydecyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, Examples of such silane include ethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-ureidopropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, di-(3-methacryloxy)propyltriethoxysilane, 3-isocyanatepropyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 3-chloropropyltripropoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, and 2-cyanoethyltrimethoxysilane.

Bifunctional hydrolyzable silicon compounds include dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldi(2-methoxyethoxy)silane, dimethyldiacetoxysilane, dimethyldipropoxysilane, dimethyldiisopropenoxysilane, dimethyldibutoxysilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, vinylmethyldiacetoxysilane, vinylmethyldi(2-methoxyethoxy)silane, vinylmethyldiisopropenoxysilane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane, phenylmethyldiacetoxysilane, 3-chloropropylmethyldimeth Examples of such silane include silane, 3-chloropropylmethyldiethoxysilane, 3-chloropropylmethyldipropoxysilane, 3,3,3-trifluoropropylmethyldimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-acryloxypropylmethyldimethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropylmethyldiethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, and 2-cyanoethylmethyldimethoxysilane.

The amount of one or more tetrafunctional hydrolyzable silicon compounds, one or more trifunctional hydrolyzable silicon compounds, and one or more difunctional hydrolyzable silicon compounds in the liquid composition (LC) is not particularly limited.
The total amount of the one or more tetrafunctional hydrolyzable silicon compounds and the one or more trifunctional hydrolyzable silicon compounds is preferably 100 to 70 parts by mass, more preferably 100 to 80 parts by mass, and particularly preferably 100 to 90 parts by mass, per 100 parts by mass of the total amount of the one or more hydrolyzable silicon compounds (SC).
The amount of one or more bifunctional hydrolyzable silicon compounds (the total amount when multiple types are used) is preferably 0 to 30 parts by mass, more preferably 0 to 20 parts by mass, and particularly preferably 0 to 10 parts by mass, based on 100 parts by mass of the total amount of one or more hydrolyzable silicon compounds (SC).

The amount of one or more tetrafunctional hydrolyzable silicon compounds (total amount if multiple types) is preferably 30 to 100 parts by mass, more preferably 30 to 95 parts by mass, particularly preferably 40 to 90 parts by mass, and most preferably 50 to 85 parts by mass, and the amount of one or more trifunctional hydrolyzable silicon compounds (total amount if multiple types) is preferably 70 to 0 parts by mass, more preferably 70 to 5 parts by mass, particularly preferably 60 to 10 parts by mass, and most preferably 50 to 15 parts by mass, relative to 100 parts by mass of the total amount of the tetrafunctional hydrolyzable silicon compounds and the trifunctional hydrolyzable silicon compounds.

Although details will be described later, the liquid composition (LC) can contain, as the benzophenone-based UV absorber, a silylated benzophenone-based UV absorber which is a reaction product of a hydroxyl-containing benzophenone-based compound and an epoxy-containing hydrolyzable silicon compound. This silylated benzophenone-based UV absorber is contained in the hydrolyzable silicon compound (SC) and can form a silicon oxide matrix, similar to the above-mentioned bifunctional, trifunctional or tetrafunctional hydrolyzable silicon compounds.

The curing temperature of the hydrolyzable silicon compound (SC) is not particularly limited, and is a temperature that exceeds the upper limit of the normal storage temperature, preferably 80°C or higher. The upper limit of the curing temperature is not particularly limited, and from an economical viewpoint, is preferably 230°C. The curing temperature of the hydrolyzable silicon compound (SC) is preferably 150 to 230°C, more preferably 170 to 230°C.

The liquid composition (LC) may contain one or more optional components other than the hydrolyzable silicon compound (SC) as necessary.

<Silicon oxide particles (SP)>
The liquid composition (LC) may contain silicon oxide fine particles (SP) that are bound to and included in the silicon oxide matrix in the coating, if necessary. When the liquid composition (LC) contains silicon oxide fine particles (SP), the abrasion resistance of the coating may be improved.
The silicon oxide fine particles (SP) can be blended in the liquid composition (LC) in the form of colloidal silica in which the silicon oxide fine particles (SP) are dispersed in water and/or an organic solvent.
The average particle size of the silicon oxide fine particles (SP) measured by the BET method is not particularly limited, and is preferably 1 to 100 nm, more preferably 5 to 40 nm, from the viewpoint of improving the transparency and abrasion resistance of the coating. If the average particle size is 100 nm or less, diffuse reflection of light on the particle surface and the resulting decrease in transparency of the coating can be suppressed.

One or more hydrolyzable silicon compounds (SC) and the silicon oxide fine particles (SP) used as needed are components that form the silicon oxide matrix in the coating, and in this specification, these are collectively referred to as the matrix component (S).

Here, the content of the hydrolyzable silicon compound (SC) in the liquid composition (LC) is shown as the _SiO2 content when the Si atoms contained in the hydrolyzable silicon compound (SC) are converted into _SiO2 .
The content of one or more matrix components (S) in the total solid content of the liquid composition (LC) (when multiple types are used, the total amount) is preferably 10 to 90 mass%, more preferably 20 to 60 mass%, in terms of _SiO2 content.
From the viewpoints of the coatability of the liquid composition (LC) and the suppression of cracking of the coating, the content of one or more hydrolyzable silicon compounds (SC) in the total solid content of the liquid composition (LC) (when multiple types are used, the total amount) is preferably 10 to 90 mass%, more preferably 20 to 60 mass%, in terms of _SiO2 content.
The amount of the silicon oxide fine particles (SP) relative to the total amount of the matrix component (S) is not particularly limited, and from the viewpoint of suppressing the formation of cracks in the coating film and the decrease in transparency of the coating film due to aggregation of the silicon oxide fine particles (SP), it is preferably 0 to 50 mass %, more preferably 0 to 30 mass %.

<Flexibility-imparting component (FL)>
The liquid composition (LC) may optionally contain one or more flexibility-imparting components (FL) that improve the film-forming properties of the film and suppress cracking of the film.
Regardless of the type of one or more hydrolyzable silicon compounds (SC), the flexibility imparting component (FL) is effective. For example, when one or more hydrolyzable silicon compounds (SC) are composed only of tetrafunctional hydrolyzable silicon compounds, the resulting silicon oxide matrix may not have sufficient flexibility. In such a case, the flexibility imparting component (FL) can be used to impart appropriate flexibility to the silicon oxide matrix, forming a coating that is excellent in both mechanical strength and crack resistance.

Examples of the flexibility-imparting component (FL) include organic resins such as silicone resins, acrylic resins, polyester resins, polyurethane resins, epoxy resins, phenolic resins, and hydrophilic organic resins containing polyoxyalkylene groups; curable organic compounds such as monomers, oligomers, and prepolymers that become organic resins when heated or irradiated with active energy rays; and non-curable organic compounds other than resins such as glycerin. Known organic resins, curable organic compounds, and non-curable organic compounds can be used.

The organic resin is preferably a curable resin that is cured by heating or irradiation with active energy rays, such as ultraviolet rays and electron beams.
Thermosetting resins and thermosetting compounds such as monomers, oligomers, or prepolymers that become organic resins by heating can be cured simultaneously when one or more hydrolyzable silicon compounds (SC) are cured by heating.
Active energy ray-curable resins and active energy ray-curable compounds such as monomers, oligomers, and prepolymers that become organic resins upon irradiation with active energy rays can be cured by heating one or more hydrolyzable silicon compounds (SC) and then curing them by irradiation with active energy rays.
The curable resins and curable compounds may undergo a cross-linking reaction with one or more hydrolyzable silicon compounds (SC) upon curing.

The content of the flexibility-imparting component (FL) in the liquid composition (LC) is not particularly limited, and is preferably 0 to 100 parts by mass, more preferably 0.1 to 100 parts by mass, and particularly preferably 1.0 to 50 parts by mass, relative to 100 parts by mass of the total amount of one or more hydrolyzable silicon compounds (SC).

<Functional Ingredients (FU)>
The liquid composition (LC) may contain one or more functional components (FU) as required. The functions of the functional components (FU) include selective transmission, selective absorption, or selective reflection of light or radio waves in a specific wavelength range; reflection or absorption of heat rays; anti-reflection; low reflection; low radiation; electricity supply; heating; water or oil repellency; scratch resistance; antifouling; antibacterial properties; decoration such as coloring; and combinations thereof.
The coating may, for example, contain an ultraviolet ray shielding agent and/or an infrared ray shielding agent as a functional component (FU).

As the ultraviolet shielding agent, a known agent can be used, and it may be of an ultraviolet absorbing type or an ultraviolet reflective type. 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 are preferred.

Benzophenone-based UV absorbers include silylated benzophenone-based UV absorbers, which are reaction products of hydroxyl-containing benzophenone-based compounds and epoxy-containing hydrolyzable silicon compounds. These silylated benzophenone-based UV absorbers are contained in hydrolyzable silicon compounds (SC) and can form a silicon oxide matrix. By using a silylated benzophenone-based UV absorber as a UV shielding agent, the UV absorber can be fixed to the silicon oxide matrix, and bleeding out of the UV absorber can be suppressed. For details of silylated benzophenone-based UV absorbers, see International Publication No. WO 2011/142463.

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

As the infrared shielding particles, metal compound particles containing cesium-doped tungsten oxide (CWO (registered trademark)) and/or lanthanum hexaboride (LaB ₆ ) are particularly preferred. When using these metal compound particles, the value obtained by dividing the absorbance of the coating for light with a wavelength of 800 to 1500 nm by the mass of the infrared shielding particles contained per m ² of the coating can be made relatively large, for example, 1.5 or more. In this case, the content of the infrared shielding particles in the coating can be reduced. This reduces the absolute number of particles present in the vicinity of the interface of the coating with the glass substrate, improving the adhesion between the glass substrate and the coating and improving the abrasion resistance.

When the liquid composition (LC) contains infrared shielding particles, it is preferable to use a dispersion liquid containing infrared shielding particles, an organic solvent as a dispersion medium, and, if necessary, a dispersant, as the raw material for the infrared shielding particles.

<Catalyst>
The liquid composition (LC) may optionally contain one or more catalysts.
When a catalyst is contained in the raw material of the components of the liquid composition (LC), the one or more catalysts include the catalyst in the raw material.
Examples of the catalyst include acid catalysts and alkali catalysts. Examples of the acid catalyst include inorganic acids such as nitric acid, hydrochloric acid, sulfuric acid, and phosphoric acid; carboxylic acids such as formic acid, acetic acid, propionic acid, glycolic acid, oxalic acid, malonic acid, succinic acid, maleic acid, phthalic acid, citric acid, malic acid, and glutaric acid; and sulfonic acids such as methanesulfonic acid and p-toluenesulfonic acid. Examples of the alkali catalyst include sodium hydroxide, potassium hydroxide, and ammonia. The catalyst is preferably an acid catalyst. The catalyst can be used in the form of an aqueous solution.
The content of the catalyst in the liquid composition (LC) is not particularly limited. The content of the one or more catalysts (the total amount in the case of a plurality of types) is preferably 0.01 to 10 parts by mass relative to 100 parts by mass of the total amount of the one or more hydrolyzable silicon compounds (SC).

<Water>
The liquid composition (LC) may contain water as necessary.
When water is contained in the raw materials that are components of the liquid composition (LC), the water includes the water in the raw materials.
In the coating formation step, the hydrolysis and condensation reaction of one or more hydrolyzable silicon compounds (SC) can be carried out using moisture in the atmosphere, so the liquid composition (LC) does not need to contain water.
The amount of water in the liquid composition (LC) is not particularly limited as long as it is an amount sufficient to hydrolyze and condense one or more hydrolyzable silicon compounds (SC). Specifically, the amount of water is preferably 1 to 20 equivalents, more preferably 4 to 18 equivalents, in terms of molar ratio relative to the _SiO2 equivalent of one or more hydrolyzable silicon compounds (SC).

<Organic Solvent>
The liquid composition (LC) may contain one or more organic solvents as a solvent and/or dispersion medium, if necessary.
In the case where an organic solvent is contained in the raw materials constituting the liquid composition (LC), the one or more organic solvents include the organic solvent in the raw materials.

Organic solvents include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and acetylacetone; ethers such as tetrahydrofuran, 1,4-dioxane, 1,2-dimethoxyethane, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, and diisopropyl ether; esters such as ethyl acetate, butyl acetate, isobutyl acetate, and methoxyethyl acetate; alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-methoxyethanol, 4-methyl-2-pentanol, 2-butoxyethanol, 1-methoxy-2-propanol, and 2-ethoxyethanol, and diacetone alcohol; hydrocarbons such as n-hexane, n-heptane, isoctane, benzene, toluene, and xylene; and acetonitrile and nitromethane.

Among the above, from the viewpoints of solubility in the liquid composition (LC) and coatability of the liquid composition (LC), alcohols having a boiling point of 60 to 160° C. are preferred, and specifically, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 1-methoxy-2-propanol, 2-ethoxyethanol, 4-methyl-2-pentanol, 2-butoxyethanol, and the like are preferred.
As the organic solvent, one or more types of alcohol may be used in combination with one or more types of organic solvent other than the alcohol that is miscible with water and the alcohol.

The total amount of liquid media, such as water and organic solvents, contained in the liquid composition (LC) is not particularly limited, and can be adjusted so that the liquid composition (LC) has a preferred solids concentration. The solids concentration of the liquid composition (LC) is preferably 3.5 to 50 mass%, more preferably 9 to 30 mass%. The "solids concentration" is the total concentration of non-volatile components excluding liquid media, such as water and organic solvents.

<Dispersant>
The liquid composition (LC) may contain, as necessary, one or more dispersants for dispersing inorganic fine particles such as infrared shielding particles.
When a dispersant is contained in the raw material of the component of the liquid composition (LC), the one or more dispersants include the dispersant in the raw material.
As the dispersant, a known dispersant can be used.

<Chelating Agent>
The liquid composition (LC) may optionally contain one or more chelating agents.
When the liquid composition (LC) contains infrared shielding particles and an ultraviolet shielding agent, one or more chelating agents capable of forming a complex with the infrared shielding particles can be used. The chelating agent is coordinated to the surface of the infrared shielding particles, and can suppress the ultraviolet shielding agent from chelating to the infrared shielding particles.
When a chelating agent is contained in the raw material of the components of the liquid composition (LC), one or more types of chelating agent include a dispersing agent in the raw material.

As the chelating agent, a known one can be used.
The chelating agent preferably has a low visible light absorption rate. The chelating agent is appropriately selected depending on the type of liquid medium, such as water and organic solvents. The liquid medium may contain water and/or alcohol, and the chelating agent is preferably soluble in these polar solvents. Such chelating agents include carboxylic acids such as maleic acid and (meth)acrylic acid; and (co)polymers thereof (e.g., polymaleic acid and polyacrylic acid).

<Other additives>
The liquid composition (LC) may contain one or more additives other than those described above, as necessary. Examples of the additives other than those described above include a surface conditioner, a defoamer, a viscosity adjuster, an adhesion imparting agent, a light stabilizer, an antioxidant, a dye, a pigment, and a filler.

[Method of manufacturing glass laminate]
The method for producing the glass laminate 1 is not particularly limited.
In one embodiment, a method for producing the glass laminate 1 includes the steps of:
A step (S1) of preparing a liquid composition (LC) containing one or more hydrolyzable silicon compounds (SC) having a hydrolyzable group;
A step (S2) of applying a liquid composition (LC) to one surface (film-forming surface) 10S of the glass substrate 10 to form a coating film to obtain a glass substrate with a coating film;
and a step (S3) of heating the glass substrate with the coating film to cure the coating film.

(Step (S1))
In step (S1), a liquid composition (LC) is prepared that contains one or more hydrolyzable silicon compounds (SC) and, if necessary, one or more optional components. The preferred composition of the liquid composition (LC) has been described above, so a detailed description is omitted here.
The liquid composition (LC) can be prepared by uniformly mixing one or more materials including one or more hydrolyzable silicon compounds (SC) by a known method. When the liquid composition (LC) is composed of a plurality of materials, the materials may be mixed together or in portions, and the mixing procedure is not particularly limited.
The environmental temperature in step (S1) is not particularly limited, and may be a normal environmental temperature, for example, 10 to 30°C.

(Step (S2))
In step (S2), the glass substrate 10 is arranged with the upper side 11 of the glass substrate 10 facing upward, substantially vertically or at an inclination angle between substantially horizontal and substantially vertical with respect to the ground. This arrangement is also called standing. This arrangement is also called an upright state. In this arrangement, a liquid composition (LC) is applied onto the surface 10S of the glass substrate 10 to form a coating film, thereby obtaining a glass substrate with a coating film.
In the application of the glass to vehicle side glass, the glass substrate is usually processed into a shape having a curved surface. The coating film can be formed, for example, on the vehicle inner surface (usually a concave curved surface) of the glass substrate.
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 (S2) is not particularly limited, and may be a normal environmental temperature, for example, 10 to 30°C.

As a coating method, a flow coating method is preferred. In the flow coating method, a liquid nozzle that ejects a liquid composition (LC) toward a portion near the upper edge 11 of the surface 10S of the glass substrate 10 is moved relatively in the width direction of the glass substrate 10 along the upper edge 11 of the glass substrate 10 from one end side of the upper edge 11 to the other end side of the upper edge 11, so that the liquid composition (LC) is poured onto the surface 10S of the glass substrate 10 to form a coating film.

It is preferable to move the liquid nozzle in the width direction of the glass substrate 10 along the upper edge 11 of the glass substrate 10 from one end side to the other end side of the upper edge 11 of the glass substrate 10 while the glass substrate 10 is fixed approximately vertically or at an inclination angle between approximately horizontal and approximately vertical to the ground by a known technique such as vacuum suction. The method of moving a liquid nozzle smaller than the glass substrate 10 while the glass substrate 10 having a large area is fixed is simple and low-cost.

In step (S2), it is preferable to perform an operation of blowing air from one or more blowing nozzles to the liquid composition (LC) discharged from the liquid nozzle onto the surface 10S of the glass substrate 10 at a certain timing, simultaneously with or immediately after the liquid composition (LC) reaches the surface 10S of the glass substrate 10, in accordance with the relative movement of the liquid nozzle from one end side to the other end side of the upper edge 11 of the glass substrate 10, thereby forming a coating film in which at least the area between the upper edge of the coating film and the second imaginary line IL2 (an imaginary line obtained by moving the upper edge 21 of the coating film 20 parallel to the surface 20S of the coating film 20 downward by 100 mm) is dried. The upper edge of the coating film is the upper edge of the coating film 20 before hardening shown in FIG. 1.

For example, step (S2) can be carried out using a coating device 2 as shown in Figures 3A and 3B. Figure 3A is a schematic side view, and Figure 3B is a schematic top view. The same components as those in Figures 1 and 2 are given the same reference symbols, and their explanations will be omitted.
The coating device 2 has a liquid nozzle 31 that ejects a liquid composition (LC) toward a portion of the surface 10S of the glass substrate 10 in the vicinity of the upper side 11 .
The liquid nozzle 31 is disposed so that the discharge port 31M of the liquid nozzle 31 faces a portion near the upper side 11 of the surface 10S of the glass substrate 10.
On the surface 10S of the glass substrate 10, the portion in the vicinity of the upper side 11 can be, for example, a region between the upper side 11 and an imaginary line obtained by shifting the upper side 11 parallel to the surface 10S downward by 30 mm.

A liquid composition (LC) is supplied to the liquid nozzle 31 by known means and method. The liquid nozzle 31 is configured to be movable in the width direction along the upper side 11 of the glass substrate 10 from one end side to the other end side of the upper side 11 of the glass substrate 10 by known moving means. The liquid nozzle 31 can continuously eject the liquid composition (LC).
The diameter of the discharge port 31M of the liquid nozzle 31 is not particularly limited, and is preferably, for example, 2 to 6 mmφ. The discharge amount of the liquid composition (LC) from the liquid nozzle 31 is not particularly limited, and is preferably, for example, 10 to 15 g/s.

It is preferable that the height position of the center of the discharge port 31M of the liquid nozzle 31 during the movement of the liquid nozzle 31 in the width direction is set to a position about 2 to 30 mm lower than the upper side 11 of the glass substrate 10.
During the movement in the width direction, the horizontal distance of the center of the discharge port 31M of the liquid nozzle 31 from the surface 10S of the glass substrate 10 may be within a range in which the liquid composition (LC) discharged from the liquid nozzle 31 can reach the surface 10S of the glass substrate 10, and is preferably, for example, about 0.1 to 5 mm.

The coating device 2 has one or more air blowing units 50 including an air blowing nozzle 51. In the drawing, the air blown out from the air blowing nozzle 51 is diagrammatically indicated by two broken lines and the symbol W.
One or more blowing units 50 including a blowing nozzle 51 are disposed in front of the surface 10S of the glass substrate 10.
As shown in Fig. 3B, a plurality of air blowing nozzles 51 capable of blowing air over at least the entire range between the upper edge of the coating film and a second imaginary line IL2 (an imaginary line obtained by moving the upper edge 21 of the coating film 20 parallel to the surface 20S of the coating film 20 downward by 100 mm) are preferably arranged in a line in the width direction of the glass substrate 10 in front of the surface 10S of the glass substrate 10. The plurality of air blowing nozzles 51 are preferably arranged at equal intervals. In the figure, reference symbol 51P indicates the arrangement pitch of the plurality of air blowing nozzles 51.

The diameter of the outlet 51M of the air blowing nozzle 51 is not particularly limited, and is preferably, for example, about 2 to 6 mmφ. The width WA of the area where air can be blown from one air blowing nozzle 51 on the surface 10S of the glass substrate 10 is preferably, for example, 100 mm or more.
It is preferable to design the number of air blowing nozzles 51 and the arrangement pitch 51P so that air from one of the air blowing nozzles 51 always reaches the liquid composition (LC) that has reached the surface 10S of the glass substrate 10 simultaneously with or immediately after the liquid composition reaches the surface 10S of the glass substrate 10, in accordance with the movement of the liquid nozzle 31 in the width direction from one end side to the other end side of the upper side 11 of the glass substrate 10.
In addition, the area on the surface 10S of the glass substrate 10 where air can be blown from any one air blowing nozzle 51 and the area on the surface 10S of the glass substrate 10 where air can be blown from the air blowing nozzle 51 adjacent to that air blowing nozzle 51 may partially overlap.

A compressor or the like can be connected to the blower unit 50 to blow air or other wind from the blower nozzle 51. The blower unit 50 can preferably include a wind speed adjustment means such as an electromagnetic valve and an electropneumatic regulator. The blowing of air from the blower nozzle 51 can be turned on and off and the wind speed can be adjusted using the wind speed adjustment means such as an electromagnetic valve and an electropneumatic regulator. The blower nozzle 51 is preferably configured so that the angle θ of the central axis 51A of the blower nozzle 51 relative to the surface 10S of the glass substrate 10 can be adjusted.

The air blowing nozzle 51 is preferably disposed at a position lower than the position of the liquid nozzle 31 .
It is preferable that, simultaneously with or immediately after the liquid composition (LC) reaches the surface 10S of the glass substrate 10 from the liquid nozzle 31 at a certain timing, air is blown from one or more air blowing nozzles 51 arranged at a position lower than the position of the liquid nozzle 31 from one end side to the other end side of the upper edge 11 of the glass substrate 10 in accordance with the relative movement of the liquid nozzle 31, to form a coating film in which at least the area between the upper edge of the coating film and a second virtual line IL2 (a virtual line obtained by moving the upper edge 21 of the coating film 20 parallel to the surface 20S of the coating film 20 downward by 100 mm) is dried.

The liquid composition (LC) is ejected from the liquid nozzle 31 onto the surface 10S of the glass substrate 10 at a certain timing, and simultaneously with or immediately after the liquid composition (LC) reaches the surface 10S of the glass substrate 10, air can be blown from one air blowing nozzle 51 closest to the liquid nozzle 31 from one end side to the other end side of the upper edge 11 of the glass substrate 10 in accordance with the relative movement of the liquid nozzle 31.
In this case, the timing for starting blowing air from the air blowing nozzle 51 closest to the liquid nozzle 31 may be either before the liquid nozzle 31 arrives within the blowing area where air can be blown from this air blowing nozzle 51 (e.g., 2 to 10 seconds before the arrival timing), simultaneously with the arrival, or immediately after the arrival (e.g., within 3 seconds after the arrival timing).
When the timing for starting blowing air is set before the liquid nozzle 31 arrives within the blowing area where air can be blown from the blowing nozzle 51, air can be reliably blown onto the liquid composition (LC) ejected onto the surface 10S of the glass substrate 10 at the same time as the liquid composition (LC) reaches the surface 10S of the glass substrate 10.
In this specification, unless otherwise specified, "immediately" is defined as within 3 seconds.

By forming the coating film in the above-described manner, localized thickening near the upper side of the coating film and thickening in the lower part of the coating film can be suppressed.
By forming the coating film by the above-mentioned method, it is easy to form a coating 20 having a specific film thickness distribution in which, in at least a part of a specific dimension region having a vertical dimension of more than 100 mm, the film thickness (T) of the coating 20 in the region between the upper edge 21 of the coating 20 and a first imaginary line IL1 obtained by moving the upper edge 21 of the coating 20 parallel to the surface 20S of the coating 20 20 mm downward is more than 0 μm and not more than 2.0 μm, and the film thickness (T) of the coating 20 in the region on the second imaginary line IL2 obtained by moving the upper edge 21 of the coating 20 parallel to the surface 20S of the coating 20 100 mm downward and below the second imaginary line IL2 is 2.0 to 3.0 μm.
As a result, it is easy to form a coating 20 that has a favorable film thickness distribution in the vertical direction, has good crack resistance, and can satisfactorily exhibit the desired functions, such as blocking ultraviolet and/or infrared rays.

In addition, in Patent Document 1 listed in the [Background Art] section, the air blowing unit (5) is arranged in contact with the side or upper part of the injection part (2), or arranged above and away from the injection part (2) (FIGS. 5A, 7, and 8). In Patent Document 1, in order to prevent the coating liquid from flowing around to the opposite side of the coating surface of the glass plate, the air blowing system (5) is arranged at the same height as the injection part (2) or above the injection part (2), and there is no description of a method of arranging the air blowing system (5) below the injection part (2).

As explained in the section "Problems to be Solved by the Invention," the coating obtained by the method described in Patent Document 1 has a large up-down peak within 1 mm from the coating line, has a local thick part with a thickness of more than 2.5 μm, and has a thickness variation of about 0.9 μm or more (FIGS. 12 and 13 of Patent Document 1). In particular, compared to Examples 2 to 4 in which air was blown from the front, Example 1 in which air was blown from above has a larger thickness variation. The coating obtained by the method described in Patent Document 1 also has a thin thickness of less than 2 μm within a range of 3 mm or more from the coating line, and the thickness tends to gradually decrease as the distance from the coating line increases.
In the local thick film part that protrudes locally near the coating line, residual stress is large and cracks may occur. In the local thick film part that extends in the width direction along the coating line, it is visually recognized as perspective distortion and may deteriorate the appearance. In the range of 3 mm or more away from the coating line, the film thickness is thin and the desired function such as blocking ultraviolet and/or infrared rays may not be fully realized.

Patent Document 1 states that "when the functional liquid is ejected while blowing air from above (Example 1), the functional liquid dries out at an early stage, resulting in a film thickness difference of approximately 2 μm in the region within 1 mm of the coating line L, particularly in the region below the position where the film thickness first reaches its maximum value below the coating line L" (paragraph 0101).
It is believed that when air is blown from the front or from above, the upper edge vicinity dries too quickly, making it easy for localized thick film portions to form near the upper edge.

In this specification, the angle θ of the central axis 51A of the air blowing nozzle 51 located directly below the surface 10S of the vertically standing glass substrate 10 is defined as 0°, the angle θ of the central axis 51A of the air blowing nozzle 51 located in front of the surface 10S is defined as 90°, and the angle θ of the central axis 51A of the air blowing nozzle 51 located directly above the surface 10S is defined as 180°.
When the surface 10S is a curved surface, in a side view such as that shown in FIG. 3A , a tangent line (not shown) passing through the intersection point between the central axis 51A of the air blowing nozzle 51 and the surface 10S is drawn to the surface 10S of the glass substrate 10, and the angle between the central axis 51A and the obtained tangent line is defined as the "angle θ of the central axis 51A of the air blowing nozzle 51 with respect to the surface 10S of the glass substrate 10."

In this embodiment, it is preferable to arrange the air blowing nozzle 51 at a position lower than the position of the liquid nozzle 31, and blow air from below onto the liquid composition (LC) ejected from the liquid nozzle 31 onto the surface 10S of the glass substrate 10 at a certain timing.
It is believed that blowing air from below allows the drying near the upper edge to proceed at an appropriate speed, and suppresses the formation of a local thick film portion near the upper edge of the coating film. It is also believed that blowing air at least in the range between the upper edge of the coating film and the second imaginary line IL2 makes it easier to form a coating 20 with a film thickness (T) of 2.0 to 3.0 μm on the second imaginary line IL2 and in the region below the second imaginary line IL2 in at least a part of a specific dimension region with a vertical dimension of more than 100 mm.

In step (S2), the set angle θ of the central axis 51A of the air blowing nozzle 51 with respect to the surface 10S of the glass substrate 10 is preferably more than 0° and less than 90°. The lower limit is more preferably 5°, even more preferably 10°, particularly preferably 15°, and most preferably 20°. The upper limit is more preferably 80°, even more preferably 70°, even more preferably 60°, particularly preferably 50°, and most preferably 40°.
When the angle θ is 10 to 50° (preferably 10 to 40°, more preferably 20 to 40°), it is easy to design the arrangement of the liquid nozzle 31 and the air blowing nozzle 51 relative to the glass substrate 10, and it is easy to control the flow of the liquid composition (LC) and the air blowing relative to the surface of the glass substrate 10. As a result, it is possible to effectively prevent problems such as the liquid composition (LC) being applied to the air blowing nozzle 51. In addition, it is easy to stably form a coating 20 that is prevented from locally thickening near the upper side and from thickening at the lower part, has a favorable film thickness distribution in the vertical direction, and has good crack resistance and appearance such as good appearance near the upper side.

When air is not blown onto the liquid composition (LC) discharged from the liquid nozzle 31 onto the surface 10S of the glass substrate 10, the maximum film thickness, minimum film thickness and film thickness distribution of the coating 20 can generally be adjusted by adjusting one or more conditions such as the composition, solids concentration, viscosity and coating amount of the liquid composition (LC) and the arrangement angle of the glass substrate 10 in step (S2).
The higher the solids concentration and viscosity of the liquid composition (LC), the greater the maximum film thickness of the coating 20 tends to be.
The greater the amount of the liquid composition (LC) applied, the greater the maximum film thickness of the coating 20 tends to be.
The film thickness (T) of the lower part of the coating 20 can be adjusted by adjusting the arrangement angle of the glass substrate 10. In a flow coating method in which a liquid composition (LC) is poured from above the glass substrate 10, the film thickness (T) of the lower part tends to be thinner when the glass substrate 10 is arranged approximately vertically to the ground, and the film thickness (T) of the lower part of the coating 20 tends to be thicker when the glass substrate 10 is arranged approximately horizontally to the ground.

The composition, solid content concentration, viscosity, and coating amount of the liquid composition (LC), as well as conditions other than air blowing, such as the arrangement angle of the glass substrate 10 in step (S2), and the air blowing conditions may be designed collectively.
The solid content concentration of the liquid composition (LC) is not particularly limited, and is preferably 7 to 15% by mass, more preferably 8 to 11% by mass.
The viscosity of the liquid composition (LC) at the environmental temperature during the step (S2) is not particularly limited, and is preferably 0.8 to 2.3 mPa·s, more preferably 1.0 to 2.0 mPa·s, and particularly preferably 1.0 to 1.5 mPa·s.

(Standing process)
After the formation of the coating film is completed, the obtained glass substrate with the coating film may be held in an upright position for about 10 to 20 seconds.

(Drying process)
Between steps (S2) and (S3), a drying step may be carried out, if necessary, to dry the entire coating film under conditions in which the curing reaction does not proceed. The drying method is not particularly limited, and examples thereof include heat drying at about 40 to 60°C, drying under reduced pressure, and heat drying under reduced pressure at about 40 to 60°C.

(Step (S3))
In step (S3), the glass substrate with the coating film is heated to cure the coating film. The heating is performed under temperature conditions that cure one or more hydrolyzable silicon compounds (SC). Step (S3) can be performed in a single stage of only main baking or in multiple stages of pre-baking and main baking.
The firing temperature is not particularly limited. When the glass substrate is a 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 substrate is a laminated glass, the firing temperature is preferably 80 to 110° C., more preferably 90 to 110° C. The heating time can be appropriately designed depending on the composition of the liquid composition (LC), the heating temperature, and the like.

The orientation of the coated glass substrate in the drying step and step (S3) is not particularly limited. In the drying step and step (S3), the coated glass substrate may be disposed substantially horizontally with respect to the ground so that the coated side faces upward, or, as in step (S2), the coated glass substrate may be disposed substantially vertically with the upper side facing upward, or at an inclination angle between substantially horizontal and substantially vertical with respect to the ground. The substantially horizontal arrangement with respect to the ground is also called flat placement.
When the liquid composition (LC) contains a thermosetting resin and/or a thermosetting compound, the thermosetting resin and/or the thermosetting compound can be cured together with one or more hydrolyzable silicon compounds (SC) in this step (S3).
After this step (S3), the coating 20 is formed.

(Step (S4))
When the liquid composition (LC) contains an active energy ray curable resin and/or an active energy ray curable compound, after the step (S3), a step (S4) can be carried out in which the coating is irradiated with active energy rays to cure the active energy ray curable resin and/or the active energy ray curable compound. Examples of active energy rays include ultraviolet rays and electron beams.
In this manner, the glass laminate 1 is obtained.

As described above, the present disclosure can provide a glass laminate for vehicle window glass, which has a coating that is suppressed from localized thickening near the upper edge and thickening in the lower portion, has a favorable film thickness distribution in the vertical direction, and has good crack resistance, and a manufacturing method thereof.
The coating may contain a functional component having a function such as blocking ultraviolet and/or infrared rays.
Effects of the present disclosure: It is possible to provide a glass laminate for vehicle window glass, which contains a functional component, has a coating that suppresses localized film thickening near the upper edge and film thickening at the lower part, has a favorable film thickness distribution in the vertical direction, has good crack resistance, and is able to stably exhibit desired functions, and a method for manufacturing the same.

The present invention will be described below based on examples, but the present invention is not limited to these. Examples (E1) to (E5) are examples, and examples (E101) to (E104) are comparative examples.

[Evaluation items and evaluation methods]
The evaluation items and evaluation methods are as follows.
(Viscosity of Liquid Composition (LC))
The viscosity of the liquid composition (LC) was measured at room temperature during the coating process using a viscometer ("RE85L" manufactured by Toki Sangyo Co., Ltd.).

(Film thickness distribution)
The thickness distribution in the vertical direction of the coating of the obtained glass laminate was measured using a laser microscope (Keyence Corporation, "VK-X100").
1, in a plan view, the central axis between a vertical axis YL1 passing through the front end of the glass laminate 1 and a vertical axis YR1 passing through the rear end of the glass laminate 1 was defined as a vertical central axis YC of the glass laminate 1. Furthermore, the central axis between the vertical axis YL1 and the vertical central axis YC was defined as a vertical axis YL2, and the central axis between the vertical central axis YC and the vertical axis YR1 was defined as a vertical axis YR2. The glass laminate 1 was divided into four equal regions in the width direction by these vertical axes.
The thickness (T) of the coating 20 was measured at approximately 2 mm intervals (specifically, 2.1 to 2.3 mm) from the top to the bottom of the coating 20 along the vertical axis YL2, the vertical center axis YC, or the vertical axis YR2. Correlation data was obtained between the distance (D) [mm] from the top end of the coating 20 and the thickness (T) [μm] of the coating 20. Note that the distance (D) [mm] from the top end of the coating 20 is the distance from the top end along the surface (concave curved surface) of the coating 20, and is the distance from the top end when the coating 20 is spread out and flat without being compressed.

(Crack resistance in weather resistance tests)
A test piece measuring 65 mm long x 35 mm wide and centered at a distance (D) of 300 mm from the upper end of the coating on the longitudinal central axis YC was cut out from the glass laminate.
A weather resistance test was carried out on this test piece using a weather resistance tester ("Super Xenon Weather Meter SX75" manufactured by Suga Test Instruments Co., Ltd.) The test piece was left in an environment of illuminance of 150 W/ ^m2 , black panel temperature of 83°C, and relative humidity of 50%, and the time (Tc) until cracks appeared on the surface of the coating was measured using an optical microscope.
The ratio of Tc of each example to Tc of Example (E1) (= Tc (each example)/Tc (E1)) was determined. This ratio is defined as the "Tc ratio." The Tc ratio of Example (E1) was 1, and a larger Tc ratio indicates higher crack resistance in the weather resistance test of the coating.

(Wear resistance)
A test piece measuring 100 mm in length and 100 mm in width was cut out from the glass laminate and centered at a position 50 mm away (D) from the upper end of the coating on the longitudinal central axis YC.
The coating surface of the test piece was subjected to an abrasion test at 500 revolutions using a Taber abrasion tester and a CS-10F abrasion wheel in accordance with JIS-R3212 (1998). The haze difference (ΔHz) of the test piece before and after the test was measured in accordance with the above JIS standard.
The ratio of ΔHz of each example to ΔHz of Example (E1) (= ΔHz (each example) / ΔHz (E1)) was determined. This ratio is defined as the "ΔHz ratio." The ΔHz ratio of Example (E1) was 1, and the smaller the ΔHz ratio, the less damage such as scratches and peeling of the coating, and the higher the abrasion resistance of the coating.

(UV transmittance of glass laminate (optical function))
To evaluate the optical function of the coating, the ultraviolet ray transmittance was evaluated.
The average thickness of the coating was measured at positions where the distance (D) from the top end on the vertical center axis YC of the coating of the glass laminate was 20 mm, 40 mm, 60 mm, 80 mm, and 100 mm. The ultraviolet transmittance (Tuv [%]) of the glass laminate was measured at the position where the actual thickness was this average thickness. The transmission spectrum of the glass laminate in the wavelength range of 300 to 380 nm was measured using a spectrophotometer (Hitachi, Ltd.'s "U-4100"), and the ultraviolet transmittance (Tuv [%]) was calculated in accordance with ISO 9050 (2003).
The ratio of Tuv of each example to Tuv of Example (E1) (= Tuv (each example)/Tuv (E1)) was determined. This ratio is defined as the "Tuv ratio." The Tuv ratio of Example (E1) is 1, and the smaller the Tuv ratio, the higher the ultraviolet shielding ability of the coating.

(Appearance near the top)
The appearance of the coating near the upper edge of the glass laminate was visually observed under sunlight and evaluated according to the following criteria.
Good (◯): No perspective distortion was observed near the upper edge, regardless of the angle of incidence of sunlight.
Fair (△): Depending on the angle of incidence of sunlight, perspective distortion was sometimes not observed near the top edge and sometimes was observed.
Poor (x): Perspective distortion was observed near the upper edge, regardless of the angle of incidence of sunlight.

[material]
The materials used in each example are as follows:
<Glass substrate>
(G1) A tempered glass (manufactured by AGC) was prepared for use as a side window next to the driver's seat of an automobile, as shown in Fig. 1. This glass had dimensions of 932 mm length × 513 mm width × 3.1 mm thickness, and the radius of curvature of the inner surface (concave curved surface) in the vertical direction was 1300 mm, and the radius of curvature in the horizontal direction was 34000 mm.

<Tetrafunctional hydrolyzable silicon compound (tetrafunctional silane)>
TEOS: tetraethoxysilane.

<Trifunctional Hydrolyzable Silicon Compound (Trifunctional Silane)>
KBM-403: 3-glycidoxypropyltrimethoxysilane, "KBM-403" manufactured by Shin-Etsu Chemical Co., Ltd.

<Ultraviolet ray absorber (ultraviolet ray shielding agent)>
THBP: Dihydroxybenzophenone-based ultraviolet absorber, 2,2',4,4'-tetrahydroxybenzophenone, "Uvinul (registered trademark) 3050" manufactured by BASF.
Si-THBP solution (63% by mass): 49.2 g of the above THBP, 123.2 g of 3-glycidoxypropyltrimethoxysilane (KBM-403), 0.8 g of benzyltriethylammonium chloride (manufactured by Junsei Chemical Co., Ltd.) as a curing catalyst, and 100 g of butyl acetate (manufactured by Junsei Chemical Co., Ltd.) were heated to 60° C. with stirring to dissolve, and then heated to 120° C. and reacted for 4 hours to obtain a silylated ultraviolet absorber (Si-THBP) solution with a solid content concentration of 63% by mass. This silylated ultraviolet absorber (Si-THBP) is a functional component and a trifunctional hydrolyzable silicon compound.

<Infrared absorbing agent (infrared shielding agent)>
ITO dispersion: 20% by mass indium tin oxide (ITO) dispersion. 11.9 g of ITO fine particles (average primary particle size 20 nm, average dispersed particle size 55 nm) manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd., 3.0 g of a dispersant (DISPERBYK-190 manufactured by BYK Japan Co., Ltd.), and 24.2 g of the mixed solvent (AP-1) described below were dispersed using a ball mill for 48 hours. The mixed solvent (AP-1) was further added to dilute the ITO concentration to 20% by mass, to obtain an ITO dispersion.

<Flexibility-imparting component>
EX-614B solution: sorbitol polyglycidyl ether (a thermosetting polyfunctional epoxy compound, "Denacol EX-614B" manufactured by Nagase ChemteX Corporation), 50 mass % methanol solution.

<Chelating Agent>
PMA-50W: Polymaleic acid aqueous solution, solid content 40 to 48% by mass, NOF Corporation "Nonpol PMA-50W".
Maleic acid: Purity 99.0% by mass.

<Surface conditioner>
BYK307 dispersion: Silicone surface conditioner (BYK307 manufactured by BYK-Chemie Japan KK), 12 mass% dispersion in methanol.

<Organic Solvent>
AP-1: a mixed solvent of ethanol:2-propanol:methanol=85.5:13.4:1.1 (mass ratio), "Solmix (registered trademark) AP-1" manufactured by Japan Alcohol Sales Co., Ltd.
MEK: methyl ethyl ketone, purity 99.9% by mass.
Methanol: purity 99.5% by mass.

<Acid catalyst>
Acetic acid aqueous solution: 90% by weight.

[Production Example (PE1)] (Preparation of Liquid Composition (LC1))
In a round-bottom flask, 12.4 g of TEOS, 11.6 g of Si-THBP solution (63% by mass), 1.9 g of EX-614B solution (50% by mass), 1.7 g of PMA-50W, 1.0 g of maleic acid, 0.5 g of BYK307 dispersion (12% by mass), 18.9 g of methanol, 62.0 g of MEK, 9.5 g of aqueous acetic acid solution (90% by mass), and 12.8 g of pure water were added and stirred and mixed at 50 ° C. for 2 hours. Finally, 6.80 g of ITO dispersion (20% by mass) was added and stirred and mixed. In this way, a liquid composition (LC1) with a solid content concentration of 9.2% by mass was obtained. The blending composition and solid content concentration are shown in Table 1.

[Production Examples (PE2) to (PE4)] (Preparation of Liquid Compositions (LC2) to (LC4))
Liquid compositions (LC2) to (LC4) were obtained in the same manner as in Production Example 1, except that the blending compositions were changed to those shown in Table 1. The blending compositions and solid content concentrations are shown in Table 1.

[Examples (E1) to (E5)] (Production of glass laminate)
(Step (S1))
As the liquid composition (LC), liquid compositions (LC1) and (LC2) were prepared.

(Step (S2)) (Coating step)
Next, the glass substrate (G1) was held upright and approximately vertical to the ground with the upper side facing upward using a vacuum suction device. The room temperature during the coating process was 22 to 24°C. The viscosity of the liquid composition (LC) at room temperature during the coating process was 1.2 to 1.3 mPa·s. The temperature of the glass substrate (G1) (also referred to as the glass temperature) was set to the same temperature as room temperature or 35°C.
In this state, the liquid composition (LC) was poured onto one surface (vehicle inner surface, concave curved surface) of the glass substrate (G1) by a flow coating method using a coating device as shown in Figures 3A and 3B. Hereinafter, unless otherwise specified, the surface of the glass substrate (G1) is a concave curved surface.

The liquid nozzle was disposed so that the discharge port of the liquid nozzle faced the vicinity of the upper side of the surface of the glass substrate (G1). The diameter of the discharge port of the liquid nozzle was 3 mmφ.
During the movement of the liquid nozzle in the width direction, the height position of the center of the discharge port of the liquid nozzle was set at a position 15 mm±5 mm lower than the upper side of the glass substrate (G1).
During the movement of the liquid nozzle in the width direction, the horizontal distance of the center of the discharge port of the liquid nozzle from the surface of the glass substrate (G1) was set to 3 mm±3 mm.

While continuously ejecting the liquid composition (LC) from the liquid nozzle, the liquid nozzle was moved along the upper edge of the glass substrate (G1) in the width direction of the glass substrate (G1) from the rear end side to the front end side of the upper edge of the glass substrate (G1).
The moving speed of the liquid nozzle was set to 40 to 60 mm/s, and the discharge amount of the liquid composition (LC) from the liquid nozzle (also referred to as the liquid discharge amount) was set to 11 to 12 g/s. The liquid discharge amount was adjusted by the moving speed.

A number of air blowing units including air blowing nozzles were placed in front of the surface of the glass substrate (G1). A compressor was connected to the air blowing unit, and the air blowing unit was configured to blow air from the air blowing nozzle. The air blowing unit included an electromagnetic valve and an electropneumatic regulator, and was configured so that the air blowing from the air blowing nozzle could be turned on and off and the wind speed could be adjusted. The air blowing nozzle was configured so that the angle θ of the central axis of the air blowing nozzle relative to the surface of the glass substrate (G1) (also referred to as the air blowing nozzle angle θ) could be adjusted.

As shown in Fig. 3B, a plurality of air blowing nozzles capable of blowing air over at least the entire range between the upper side of the coating film and a second virtual line (a virtual line shifted 100 mm downward along the surface of the coating film) were arranged in a line in the width direction of the glass substrate (G1) in front of the surface of the glass substrate (G1). The plurality of air blowing nozzles were arranged at equal intervals.
The diameter of the outlet of the air blowing nozzle was 4 mm. The width of the area on the surface of the glass substrate (G1) through which air could be blown from one air blowing nozzle was 50 mm or more.

The number and arrangement pitch of the air blowing nozzles were designed so that the liquid composition (LC) that had reached the surface of the glass substrate (G1) was always blown air from any one of the air blowing nozzles at the same time as or immediately after the liquid composition (LC) reached the surface of the glass substrate (G1) in accordance with the movement of the liquid nozzle in the width direction from the rear end side to the front end side of the upper side of the glass substrate (G1). Specifically, the number of the air blowing nozzles was 10, and the arrangement pitch was 100 mm.
The air blowing nozzle was disposed at a position lower than (i.e., below) the position of the liquid nozzle. The angle θ of the central axis of the air blowing nozzle with respect to the surface of the glass substrate (G1) was set to 20°.

The liquid composition (LC) was discharged from the liquid nozzle onto the surface of the glass substrate (G1) at a certain timing, and simultaneously with or immediately after the liquid composition (LC) reached the surface of the glass substrate (G1), air was blown from the air blowing nozzle closest to the liquid nozzle in accordance with the relative movement of the liquid nozzle from the rear end side to the front end side of the upper edge of the glass substrate (G1).

In Example (E1), the timing for starting air blowing from the air blowing nozzle closest to the liquid nozzle is set to be before the liquid nozzle arrives within the area where air can be blown from this air blowing nozzle. This ensures that air is blown toward the liquid composition (LC) ejected onto the surface of the glass substrate (G1) at the same time that the liquid composition (LC) reaches the surface of the glass substrate (G1). The timing for starting air blowing in this example is referred to as "before the liquid nozzle arrives."

In example (E2), the timing for starting blowing air from the blowing nozzle closest to the liquid nozzle was set to immediately (2 to 3 seconds later) after the liquid nozzle arrived within the area where air can be blown from the blowing nozzle. In this example, air was blown from the blowing nozzle closest to the liquid nozzle immediately (2 to 3 seconds later) after the liquid composition (LC) was discharged from the liquid nozzle onto the surface of the glass substrate (G1) at a certain timing and the liquid composition (LC) reached the surface of the glass substrate (G1). The timing for starting blowing air in this example is referred to as "immediately after the arrival of the liquid nozzle."

In Examples (E3) and (E4), air was blown in the same manner as in Example (E2), except that the angle θ of the central axis of the air blowing nozzle with respect to the surface of the glass substrate (G1) was changed.
In Example (E5), air was blown in the same manner as in Example (E1), except that the angle θ of the central axis of the air blowing nozzle with respect to the surface of the glass substrate (G1) was changed.

Using an anemometer (ISA-80 manufactured by SIBATASCIENTIFICTECHNOLOGY), the wind speed on the surface of the glass substrate (G1) was measured at several positions along the vertical center axis YC. Specifically, measurements were taken at the top end of the glass substrate (G1) and at positions 50 mm, 100 mm, or 150 mm below the top end of the glass substrate (G1) along the surface of the glass substrate (G1). The wind speed measurement results are shown in Table 2-1.

The time for blowing air onto the liquid composition (LC) that had reached the surface of the glass substrate (G1) at an arbitrary timing was set to 15 to 17 seconds.
The liquid composition (LC) that reached the surface of the glass substrate (G1) at any given time flowed downward and was dried by blowing air.
In this manner, a glass substrate with a coating film was obtained.

(Standing process)
After the formation of the coating film was completed, the obtained glass substrate with the coating film was held in an upright position for 13 to 17 seconds. This time is called the "standing time."

(Step (S3)) (Curing step)
Next, the glass substrate with the coating film was heated and baked in an air atmosphere at 180° C. or 200° C. for 20 to 30 minutes.
In examples (E1) and (E5), the glass substrate with the coating film was placed (laid flat) substantially horizontally with respect to the ground with the coating film side facing up. In examples (E2) to (E4), the glass substrate with the coating film was placed (laid up) substantially vertically with respect to the ground with the upper side facing up, as in step (S2).
The coating films were cured as described above to obtain glass laminates (GL1) to (GL5), which were then evaluated. The main production conditions are shown in Table 2-1.

[Examples (E101) to (E104)]
In each of Examples (E101) to (E104), glass laminates (GL101) to (GL104) were obtained and evaluated in the same manner as in Example (E1) or (E2), except that some conditions were changed.
In examples (E101) and (E102), no air was blown from the blower unit in step (S2).
In Example (E103), in step (S2), as in Examples (E1) and (E2), as shown in FIG. 3B, a plurality of blowing units were arranged in a line in the width direction of the glass substrate (G1) to blow air, but the blowing nozzle was arranged at a position higher than the position of the liquid nozzle (i.e., above). In this example, the angle θ of the central axis of the blowing nozzle with respect to the surface of the glass substrate (G1) was set to 120°. The blowing range in this example was narrower than the blowing range in Examples (E1) and (E2), and was relatively close to the upper side of the coating film.
In Example (E104), air was blown in the same manner as in Example (E1), except that the angle θ of the central axis of the air blowing nozzle with respect to the surface of the glass substrate (G1) was changed.
The main production conditions are shown in Table 3-1. In addition, in each example of Tables 2-1 and 3-1, conditions not shown in the table were common conditions.

[Summary of results]
In each of Examples (E1) to (E5) and (E101) to (E104), the thickness distribution in the up-down direction of the coating of the obtained glass laminate was measured along the vertical center axis YC, and a graph (also called a D-T curve) showing the relationship between the distance (D) [mm] from the top end of the coating and the thickness (T) [μm] of the coating was obtained. The distance (D) of the first imaginary line IL1 from the top end of the coating is 20 mm. The distance (D) of the second imaginary line IL2 from the top end of the coating is 100 mm. The distance (D) of the third imaginary line IL3 from the top end of the coating is 80 mm. The distance (D) of the fourth imaginary line IL4 from the top end of the coating is 40 mm.

The film thickness distribution in the vertical direction on the vertical center axis YC of the coating obtained in Example (E1) is shown in Figures 4A and 4B. The film thickness distribution in the vertical direction on the vertical center axis YC of the coating obtained in Example (E2) is shown in Figures 5A and 5B. The film thickness distribution in the vertical direction on the vertical center axis YC of the coating obtained in Example (E101) is shown in Figures 6A and 6B. The film thickness distribution in the vertical direction on the vertical center axis YC of the coating obtained in Example (E102) is shown in Figures 7A and 7B. The film thickness distribution in the vertical direction on the vertical center axis YC of the coating obtained in Example (E103) is shown in Figures 8A and 8B.
For each example, film thickness (T) data at major distances (D) along the longitudinal central axis YC of the coating are shown in Tables 2-2 and 3-2.
Other evaluation results of the coating for each example are shown in Tables 2-2 and 3-2.

In Examples (E1) to (E5), air was blown from below during the coating process, and a coating film was formed in which at least the area between the upper edge of the coating film and the second virtual line was dried. In all of the coatings obtained in these examples, localized thickening near the upper edge and thickening at the bottom were suppressed, and the film thickness distribution in the vertical direction was favorable.
The film thickness distribution in the vertical direction on the longitudinal central axis YC of the films obtained in these examples was as follows.
The thickness (T) of the coating in the region where the distance (D) from the top end of the coating was 0 to 20 mm was more than 0 μm and 2.0 μm or less.
In the region where the distance (D) from the top end of the coating was 0 to 100 mm, there were no locally prominent large peaks, and the DT curve was generally parabolic and gentle.
The film thickness (T) of the film in the region at a distance (D) of 100 mm or more from the top end of the film was 2.0 to 3.0 μm.
The film thickness (T) on the first imaginary line IL1 of the coating was 1.0 to 2.0 μm.
The thickness (T) of the coating in the region where the distance (D) from the top end of the coating was 80 mm or more was 2.0 to 3.0 μm.
The film thickness (T) on the fourth imaginary line IL4 of the coating was 1.5 to 3.0 μm.

In Example (E1), for the coating of the obtained glass laminate, the film thickness distribution in the up-down direction of the coating was measured along the vertical axis YL2 and the vertical axis YR2, respectively, and a graph showing the relationship between the distance (D) [mm] from the upper end of the coating and the film thickness (T) [μm] of the coating was obtained (not shown).
The thickness distributions along the longitudinal axis YL2 and the longitudinal axis YR2 of the coating obtained in Example (E1) were as follows, as was the thickness distribution along the central longitudinal axis YC:
The thickness (T) of the coating in the region where the distance (D) from the top end of the coating was 0 to 20 mm was more than 0 μm and 2.0 μm or less.
The film thickness (T) of the film in the region at a distance (D) of 100 mm or more from the top end of the film was 2.0 to 3.0 μm.
The film thickness (T) on the first imaginary line IL1 of the coating was 1.0 to 2.0 μm.
The thickness (T) of the coating in the region where the distance (D) from the top end of the coating was 80 mm or more was 2.0 to 3.0 μm.
The film thickness (T) on the fourth imaginary line IL4 of the coating was 1.5 to 3.0 μm.
The coating obtained in Example (E1) had the specific thickness distribution defined in the present disclosure at least within the range of the vertical axis YL2 to the vertical axis YR2. The ratio of the area having the specific thickness distribution defined in the present disclosure to the area of the specific dimension region having a vertical dimension of more than 100 mm was 50% or more.

In Example (E2), for the coating of the obtained glass laminate, the film thickness distribution in the up-down direction of the coating was measured along the vertical axis YL2 and the vertical axis YR2, respectively, and a graph showing the relationship between the distance (D) [mm] from the upper end of the coating and the film thickness (T) [μm] of the coating was obtained (not shown).
The thickness distribution along the longitudinal axis YL2 and the longitudinal axis YR2 of the coating obtained in Example (E2) was as follows, as was the thickness distribution along the central longitudinal axis YC:
The thickness (T) of the coating in the region where the distance (D) from the top end of the coating was 0 to 20 mm was more than 0 μm and 2.0 μm or less.
The film thickness (T) of the film in the region at a distance (D) of 100 mm or more from the top end of the film was 2.0 to 3.0 μm.
The film thickness (T) on the first imaginary line IL1 of the coating was 1.0 to 2.0 μm.
The thickness (T) of the coating in the region where the distance (D) from the top end of the coating was 80 mm or more was 2.0 to 3.0 μm.
The film thickness (T) on the fourth imaginary line IL4 of the coating was 1.5 to 3.0 μm.
The coating obtained in Example (E2) had the specific thickness distribution defined in the present disclosure at least within the range of the vertical axis YL2 to the vertical axis YR2. The ratio of the area having the specific thickness distribution defined in the present disclosure to the area of the specific dimension region having a vertical dimension of more than 100 mm was 50% or more.

In the examples (E3) to (E5), the same results as in the examples (E1) and (E2) were obtained.
The coatings obtained in Examples (E1) to (E5) all had good crack resistance, abrasion resistance, ultraviolet shielding performance (optical function) in the weather resistance test, and good appearance near the upper edge.
The coatings obtained in Examples (E1) to (E5) in which the angle θ of the central axis of the air blowing nozzle relative to the surface of the glass substrate was 10 to 50°, and particularly in Examples (E1) to (E4) in which the angle θ was 10 to 40°, had good appearance near the upper edge. Under the condition of an angle θ of 10 to 50° (preferably 10 to 40°, more preferably 20 to 40°), it was easy to design the arrangement of the liquid nozzle and the air blowing nozzle relative to the glass substrate, and it was easy to control the flow of the liquid composition (LC) and the air blowing relative to the surface of the glass substrate. As a result, it was possible to effectively suppress inconveniences such as the liquid composition (LC) being applied to the air blowing nozzle. In addition, localized thickening near the upper edge and thickening at the lower part were suppressed, and the film thickness distribution in the vertical direction was favorable, and it was easy to stably form a coating having good crack resistance and appearance near the upper edge.

In Example (E101), the solid content concentration of the liquid composition (LC) used was relatively low, and the resulting coating had a thin overall thickness. In this example, since no air was blown during the coating process, the resulting coating tended to become thicker from top to bottom. The thickness distribution of the resulting coating in the vertical direction on the vertical center axis YC was as follows.
The film thickness (T) of the coating in the region at a distance (D) of 100 to 300 mm from the top end of the coating was less than 2.0 μm.
The resulting coating had poor abrasion resistance and ultraviolet shielding performance (optical function).

In Example (E102), the solid content of the liquid composition (LC) used was relatively high, and the resulting coating had a thick overall thickness. In this example, since no air was blown during the coating process, the resulting coating had a tendency to become thicker from top to bottom, with the lower part being thicker. The thickness distribution of the resulting coating in the vertical direction on the vertical center axis YC was as follows.
The film thickness (T) of the coating in a region where the distance (D) from the top end of the coating was more than 100 mm was more than 3.0 μm.
The resulting coating had poor crack resistance in a weather resistance test.

In the example (E103), air was blown from above during the coating process, so that the drying near the upper edge proceeded too quickly, resulting in the formation of a localized thick film near the upper edge and a thick film at the bottom. The film thickness distribution in the vertical direction on the vertical center axis YC of the obtained coating was as follows.
In the region where the distance (D) from the top end of the coating was 0 to 40 mm, there were locally prominent peaks with large ups and downs, and the DT curve was an irregular, irregular curve.
Within a region at a distance (D) of 10 to 20 mm from the top end of the coating, there was a local thick portion where the coating thickness (T) exceeded 2.0 μm.
The film thickness (T) on the fourth imaginary line IL4 of the coating was less than 1.5 μm.
The film thickness (T) of the coating in a region at a distance (D) of 250 mm or more from the top end of the coating was more than 3.0 μm.
The resulting coating had poor crack resistance, poor abrasion resistance in a weather resistance test, and poor appearance near the top edge.

In Example (E104), the angle θ of the central axis of the air blowing nozzle relative to the surface of the glass substrate was 80°. In this example, the film thickness (T) of the coating in the area where the distance (D) from the top end of the coating was 100 mm or more was less than 2.0 μm. The appearance of the obtained coating near the top edge was poor.

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

1: glass laminate, 10: glass substrate, 10S: surface, 11: top edge, 13: front side edge, 14: rear side edge, 20: coating, 20S: surface, 21: top edge, 31: liquid nozzle, 51: air nozzle, 51A: central axis of air nozzle, IL1: first virtual line, IL2: second virtual line, IL3: third virtual line, IL4: fourth virtual line.

Claims (13)

A glass laminate for a vehicle window glass to be attached to a window opening of a vehicle, comprising: a glass substrate having an upper side; and a coating formed on one surface of the glass substrate, the coating containing a siloxane bond and one or more organic components selected from the group consisting of an organic group bonded to a Si atom and an organic compound, the glass laminate comprising:
the coating is formed on the surface of the glass substrate in a region that includes the window opening in a state in which the glass laminate completely closes the window opening,
The coating has an upper edge along the upper edge of the glass substrate and a specific dimension region having a vertical dimension of more than 100 mm;
In at least a part of the specific dimension region, the coating has a thickness greater than 0 μm and less than 2.0 μm in a region between the upper edge of the coating and a first imaginary line obtained by moving the upper edge of the coating parallel to a surface of the coating 20 mm downward;
a glass laminate, wherein the film thickness of the coating on a second imaginary line obtained by moving the upper side of the coating 100 mm downward in parallel along the surface of the coating and in a region below the second imaginary line has a specific film thickness distribution of 2.0 to 3.0 μm. The glass laminate according to claim 1, wherein the film thickness on the first imaginary line of the coating is 1.0 to 2.0 μm in the specific film thickness distribution. The glass laminate according to claim 1 or 2, wherein in the specific thickness distribution, the thickness of the coating on a third imaginary line obtained by moving the upper edge of the coating 80 mm downward parallel to the surface of the coating and in a region below the third imaginary line is 2.0 to 3.0 μm. The glass laminate according to claim 1 or 2, wherein in the specific film thickness distribution, the film thickness of the coating on a fourth imaginary line obtained by moving the upper edge of the coating parallel to the surface of the coating 40 mm downward is 1.5 to 3.0 μm. The glass laminate according to claim 1 or 2, wherein the coating is made of a cured product of a composition containing one or more hydrolyzable silicon compounds having one or more hydrolyzable groups and which may be partially hydrolyzed and condensed between the same or different species. The glass laminate according to claim 1 or 2, wherein the coating contains one or more functional components selected from the group consisting of an ultraviolet shielding agent and an infrared shielding agent. The glass laminate according to claim 1 or 2, which is for use in vehicle side glass. The glass laminate according to claim 7, which is for a vehicle side glass that is attached to a window opening of a vehicle so as to be freely opened and closed. A step (S1) of preparing a liquid composition containing one or more hydrolyzable silicon compounds having hydrolyzable groups;
The glass substrate is disposed with the upper side of the glass substrate facing upward, and is disposed substantially vertically or at an inclination angle between substantially horizontal and substantially vertical with respect to the ground.
a step (S2) of relatively moving a liquid nozzle that ejects the liquid composition toward a portion of the surface of the glass substrate near the upper edge of the glass substrate along the upper edge of the glass substrate from one end side to the other end side of the upper edge of the glass substrate in a width direction of the glass substrate to flow the liquid composition onto the surface of the glass substrate to form a coating film, thereby obtaining a glass substrate with a coating film;
The method for producing a glass laminate according to claim 1 or 2, further comprising a step (S3) of heating the glass substrate with a coating film to harden the coating film. In step (S2),
10. The method for producing a glass laminate according to claim 9, wherein an operation of blowing air from one or more air blowing nozzles arranged at a position lower than a position of the liquid nozzle is performed on the liquid composition ejected from the liquid nozzle onto the surface of the glass substrate at a certain timing, simultaneously with or immediately after the liquid composition reaches the surface of the glass substrate, from one end side to the other end side of the upper edge of the glass substrate in synchronization with the relative movement of the liquid nozzle, to form the coating film in which at least an area between an upper edge of the coating film and the second virtual line is dried. The method for manufacturing a glass laminate according to claim 10, wherein in step (S2), the angle of the central axis of the air blowing nozzle relative to the surface of the glass substrate is set to 10 to 60°. In step (S2),
The glass substrate is fixed, and the liquid nozzle is configured to move in a width direction of the glass substrate;
a plurality of the air blowing nozzles capable of blowing air in an overall range at least between the upper side of the coating film and the second virtual line are arranged in a line in a width direction of the glass substrate in front of the surface of the glass substrate;
11. The method for producing a glass laminate according to claim 10, wherein an operation of blowing air from one or more air blowing nozzles is performed on the liquid composition ejected from the liquid nozzle onto the surface of the glass substrate at a certain timing, from one end side to the other end side of the upper edge of the glass substrate in accordance with movement of the liquid nozzle, simultaneously with or immediately after the liquid composition reaches the surface of the glass substrate. The method for manufacturing a glass laminate according to claim 10, wherein the angle of the central axis of the air blowing nozzle relative to the surface of the glass substrate is adjustable.

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