JP2023154400A - Coated glass plate, production method therefor, windshield bench glass for vehicle, and production method of vehicular window glass with window frame member - Google Patents

Abstract

To provide means for providing a coating on a shield pattern, and for preventing weakening of adhesion between the shield pattern and a window frame member.SOLUTION: A coated glass plate 20 comprises: a light transmissive region Tr on a region except for a peripheral region: and on the peripheral region, a region In which is adjacent to the region Tr and is close to the region Tr relatively, and a region Ex which is adjacent to the region Tn and is separated from the region Tr relatively. A shield pattern 21 covers surfaces of the region In and region Ex of a glass plate (25). The coating (22) covers a surface of the region Tr of the glass plate (25) and a surface of the region In of the shield pattern (21), and does not cover a surface of the region Ex of the shield pattern (21). The coating (22) has, in the region Tr, a thickness increase part (22A) which gradually becomes thicker as approaching to the region In, and has in the region In, a reduction decrease part (22B) which gradually becomes thinner as approaching to the region Ex.SELECTED DRAWING: Figure 4

Description

The present disclosure relates to a coated glass plate and a method for manufacturing the same, a front bench glass for an automobile, and a method for manufacturing a vehicle window glass with a window frame member.

Patent Document 1 discloses a method for manufacturing a glass substrate with a functional film, which includes a step of applying a film-forming liquid composition onto a glass substrate on which a frame-shaped black frame portion is formed (Claim 1). . In this method, when applying the film-forming liquid composition, a masking tape is applied onto the black frame to prevent the film-forming liquid composition from being applied onto the black frame.

Patent Document 2 discloses a method for manufacturing a vehicle window glass with a functional coating, which includes a step of supplying and flowing a coating liquid onto a glass plate on which a shielding layer is formed (Claim 1). In this method, the film-forming liquid composition is applied onto the shielding layer by not masking the shielding layer when the coating liquid is applied. By limiting the distance through which the coating liquid flows to 30 cm or less, peeling of the coating from the shielding layer is suppressed.

Japanese Patent Application Publication No. 2007-167814 International Publication No. 2015/107904

The present disclosure relates to a coated glass plate having a glass plate, a shielding pattern and a coating laminated on one surface of the glass plate, and a method for manufacturing the same. In this manufacturing method, a coating is formed on the surface of a glass plate with a shielding pattern, in which a shielding pattern is formed in the peripheral area of one surface of the glass plate, by a method including a pouring process. In addition, by performing spraying on the shielding pattern as well, a film is formed also on the shielding pattern.
The above-mentioned coated glass plate is suitable as a window glass or the like. When attaching the coated glass plate to a window frame member, generally at least a portion of the shielding pattern formed in the peripheral area of the coated glass plate is adhered to the window frame member via a sealant. At this time, the coating provided on the shielding pattern may weaken the adhesion between the shielding pattern and the window frame member.
An object of the present disclosure is to provide a means for providing a coating on a shielding pattern without weakening the adhesion between the shielding pattern and other members.

The present disclosure provides the following coated glass plate and method for manufacturing the same, a front bench glass for an automobile, and a method for manufacturing a vehicle window glass with a window frame member.
[1] A coated glass plate having a glass plate and a shielding pattern and a coating layered on one surface of the glass plate,
The coated glass plate has a translucent region Tr in a region other than a peripheral region in a plan view, and a region In adjacent to the region Tr and relatively close to the region Tr in the peripheral region; a region Ex adjacent to the region In and relatively far from the region Tr;
The shielding pattern covers the surface of the region In and the region Ex of the glass plate,
The coating covers the surface of the region Tr of the glass plate and the surface of the region In of the shielding pattern, but does not cover the surface of the region Ex of the shielding pattern,
The coating has an increasing thickness portion in the region Tr that becomes gradually thicker as it approaches the region In, and a decreasing thickness portion that gradually becomes thinner as it approaches the region Ex in the region In. Coated glass plate.

[2] The coated glass plate according to [1], wherein the coating further has an increasing thickness portion within the region In and on the region Ex side of the decreasing thickness portion, the thickness increasing as the thickness approaches the region Ex.
[3] The coated glass plate according to [1] or [2], wherein within the region In, the ratio of the thickness of the coating to the thickness of the shielding pattern is 0.02 to 0.8.
[4] In plan view, the coated glass plate includes a portion of the glass plate adjacent to the area Tr, on the opposite side of the area In and the area Ex with the area Tr in between, in the peripheral area. having a region Op on the surface in which the shielding pattern is laminated;
The coated glass plate according to any one of [1] to [3], wherein the coating further covers at least a part of the region Op of the shielding pattern.

[5] The coated glass plate according to any one of [1] to [4], wherein the surface roughness of the area In of the coated glass plate is smaller than the surface roughness of the area Ex of the coated glass plate.
[6] The arithmetic mean roughness Ra of the surface of the region Ex of the coated glass plate is 0.55 μm or more, and the arithmetic mean roughness Ra of the surface of the region In of the coated glass plate is 0.45 μm or less. , the coated glass plate of [5].

[7] The coated glass plate according to any one of [1] to [6], wherein the surface gloss of the area In of the coated glass plate is higher than the surface gloss of the area Ex of the coated glass plate.
[8] The surface of the area Ex of the coated glass plate has a glossiness of 9 or less as measured in accordance with JIS Z 8741, and the surface of the area In of the coated glass plate has a glossiness measured in accordance with JIS Z 8741. The coated glass plate of [7], which has a measured glossiness of 10 or more.

[9] The coated glass plate according to any one of [1] to [8], wherein the coating contains a siloxane compound.
[10] The glass plate according to any one of [1] to [9], wherein the coating contains one or more functional components selected from the group consisting of an ultraviolet shielding agent and an infrared shielding agent.
[11] The glass plate according to any one of [1] to [10], wherein the shielding pattern is present along the entire circumference of the glass plate.

[12] A vehicle window glass that is attached to a window frame member provided on a vehicle body from the outside of the vehicle body,
At least a part of the surface of the area Ex of the shielding pattern is an adhesive surface that is adhered to the window frame member,
The coated glass plate according to any one of [1] to [11], wherein at least a part of the surface of the region In of the coating is a non-adhesive surface that is not bonded to the window frame member.
[13] An automobile front bench glass comprising the coated glass plate according to any one of [1] to [12].

[14] A method for manufacturing a coated glass plate according to any one of [1] to [13], comprising:
Step S1 of preparing a glass plate with a shielding pattern in which the shielding pattern is laminated on the surface of the region In and the region Ex of the glass plate;
Step S2 of applying a film-forming liquid composition by pouring onto the surface of the glass plate with the shielding pattern on which the shielding pattern is laminated to form a coating film;
a step S3 of drying, curing, or drying and curing the coating film to form the coating film,
In the step S2, while the surface of the region Ex of the glass plate with the shielding pattern is masked, the film-forming liquid composition is applied to the surface of at least the region Tr and the region In of the glass plate with the shielding pattern. A method for manufacturing a coated glass plate, wherein the film-forming liquid composition is poured in a direction from the region Tr side to the region In side so that the material flows down.

[15] A method for manufacturing a vehicle window glass with a window frame member using the coated glass plate according to any one of [1] to [14],
a step S4 of attaching the coated glass plate to a window frame member provided on the vehicle body from the outside of the vehicle body;
In the step S4,
bonding at least a portion of the surface of the region Ex of the shielding pattern and the window frame member;
A method for manufacturing a vehicle window glass with a window frame member, wherein at least a part of the surface of the region In of the coating is not bonded to the window frame member.

According to the present disclosure, it is possible to provide a means for providing a coating on a shielding pattern without weakening the adhesion between the shielding pattern and other members.

A schematic perspective view showing how a liquid composition for film formation is poured onto a glass plate with a shielding pattern. Schematic perspective view showing the state of masking on a glass plate with a shielding pattern Schematic cross-sectional view of intermediate product of coated glass plate (III-III cross-sectional view) Schematic cross-sectional view of a vehicle window glass with a coated glass plate and a window frame member Cross-sectional SEM photograph of the coated glass plate obtained in Example 1 Cross-sectional SEM photograph of the coated glass plate obtained in Example 1 Oblique SEM photograph of the coated glass plate obtained in Example 1 Oblique SEM photograph of the coated glass plate obtained in Example 2 A schematic perspective view or a schematic front view showing how the liquid composition for film formation is poured onto a glass plate with a shielding pattern. A schematic side view of an automobile according to an embodiment of the present invention

In this specification, unless otherwise specified, "the surface of the glass plate" refers to the main surface with a large area, excluding the end surfaces (also referred to as side surfaces) of the glass plate.
In this specification, unless otherwise specified, the "front and rear", "top and bottom", "left and right", "vertical and horizontal", and "inside and out" of the glass plate refer to the state in which the glass plate is fitted into a vehicle, etc. (actual usage state). These are the "front and back", "top and bottom", "left and right", "vertical and horizontal", and "inside and outside" of the glass plate.

In this specification, unless otherwise specified, "flowing direction" and "flowing direction" refer to the direction in which the film-forming composition flows in step S2 (flowing step).
In this specification, unless otherwise specified, the "upstream side" refers to the upstream side in the downstream direction of the film-forming composition in step S2 (flowing step). Similarly, the "downstream side" is the downstream side in the flowing direction of the film-forming composition in step S2 (flowing step).

In this specification, "abbreviation" attached to a shape refers to a partially changed shape, such as a chamfered shape with rounded corners, a shape with a part of the shape missing, or a shape with an arbitrary small shape added to the shape. means the shape of the
In this specification, "substantially horizontal to the ground" means a complete horizontal range of ±10° relative to the ground, and "substantially perpendicular to the ground" refers to a complete horizontal direction relative to the ground. Means a range of ±10° in the vertical direction.
Generally, thin film structures are referred to as "films", "sheets", etc., depending on their thickness. In this specification, these are not clearly distinguished. Therefore, the term "film" as used herein 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 species or between different species.
As used herein, a hydrolyzed condensate of one or more hydrolyzable silicone compounds refers to a hydrolyzed condensate in which at least a portion of the hydrolyzable groups contained in the one or more hydrolyzable silicone compounds are hydrolyzed, and then dehydrated. It is an oligomer (multimer) produced by condensation.
In this specification, "functional group" is a term that comprehensively indicates a reactive group, which is distinguished from a mere substituent.
In this specification, (meth)acrylic is a general term for acrylic and methacryl, and the same applies to (meth)acrylic acid, (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, "~" indicating a numerical range is used to include the numerical values described before and after it as the lower limit and upper limit.
Embodiments of the present invention will be described below.

[Coated glass plate and its manufacturing method]
The coated glass plate of the present disclosure includes a glass plate, and a shielding pattern and a coating laminated on one surface of the glass plate.
A shielding pattern is formed in the peripheral area of the glass plate. The peripheral region is, for example, a region within 150 mm, within 120 mm, within 100 mm, or within 80 mm from the outer periphery. In the coated glass plate of the present disclosure, the region where the shielding pattern is formed is a light shielding region that can shield at least part of visible light. The region where the shielding pattern is not formed is a light-transmitting region that can transmit at least part of visible light.

The coated glass plate of the present disclosure has a translucent region Tr in a region excluding the peripheral region in a plan view, and a region In adjacent to the region Tr and relatively close to the region Tr in the peripheral region; It has a region Ex adjacent to In and relatively far from the region Tr.
The shielding pattern covers the surfaces of the region In and the region Ex of the glass plate. The coating covers the surface of the region Tr of the glass plate and the surface of the region In of the shielding pattern, but does not cover the surface of the region Ex of the shielding pattern.
The coated glass sheet of the present disclosure can have any shielding pattern and/or any coating on the other surface of the glass sheet, if desired. The coated glass plate of the present disclosure can optionally include one or more optional components other than the shielding pattern and the coating.

The method for manufacturing a coated glass plate of the present disclosure includes:
Step S1 of preparing a glass plate with a shielding pattern, which includes a glass plate and a shielding pattern laminated on one surface of the glass plate;
Step S2 of applying a film-forming liquid composition by pouring onto the surface of the glass plate with a shielding pattern on which the shielding pattern is laminated to form a coating film;
The method includes a step S3 of drying and curing the coating film, or drying and curing the coating film to form a coating film.
In step S2, while the surface of the region Ex of the glass plate is masked, the liquid composition for film formation flows down on the surface of at least the region Tr and the region In of the glass plate with the shielding pattern on the region Tr side. The film-forming liquid composition is poured in the direction from the region In toward the region In.

A coated glass plate according to an embodiment of the present invention and a method for manufacturing the same will be described with reference to the drawings. FIG. 1 is a schematic perspective view showing how a liquid composition for film formation is poured onto a glass plate with a shielding pattern. FIG. 2 is a schematic perspective view showing masking locations and a masking method on a glass plate with a shielding pattern. FIG. 3 is a schematic cross-sectional view (III-III cross-sectional view) of an intermediate product of a coated glass plate. FIG. 4 is a schematic cross-sectional view of a vehicle window glass with a covered glass plate and a window frame member. These are all schematic diagrams, and for ease of visual recognition, the scale of each component in each drawing is appropriately different from the actual one.

As shown in FIG. 4, the coated glass plate 20 of this embodiment includes a glass plate 25, and a shielding pattern 21 and a coating 22 laminated on one surface 26 of the glass plate 25.
The application of the coated glass plate 20 is not particularly limited, and it is suitable for window glass (windshield, front bench glass, side glass, rear glass, etc.) of vehicles such as automobiles. The window glass may be of an openable type or a non-openable type. In a vehicle window, the coating 22 can be formed on the surface 26 of the glass pane 25 in the area that includes the window opening with the glass pane 25 completely closing the window opening of the vehicle.

In one embodiment, the planar shape of the glass plate 25 is a substantially polygonal shape, such as a substantially rectangular shape, a substantially parallelogram, a substantially quadrangular shape such as a substantially trapezoid; a substantially triangular shape, or the like. In the example shown in FIG. 1, the glass plate 25 has an outer periphery consisting of four sides: an upper side 25A, a lower side 25B, a front side 25C, and a rear side 25D. The lower side 25B may be uneven. The number of sides of the glass plate 25 is not particularly limited, and can be 0, 1, or 2. The planar shape of the glass plate 25 and the formation area of the coating 22 can be designed as appropriate depending on the form of the vehicle or the like to which the glass plate 25 is attached.
When used as a vehicle window glass, the glass plate 25 is usually processed into a curved shape. The surface 26 of the glass plate 25 on which the coating 22 is formed is not particularly limited, and may be, for example, the surface of the glass plate 25 on the inside of the vehicle (also referred to as the interior surface of the vehicle). The surface 26 is also referred to as a coating surface.

As shown in FIGS. 1 and 2, the covered glass plate 20 has a region Ar (also referred to as a light shielding region) in which a shielding pattern 21 is formed in a peripheral region in a plan view. The coated glass plate 20 has a translucent region Tr in the region excluding the peripheral region. No shielding pattern is formed in the transparent region Tr. The region Ar can surround at least a portion of the region Tr. For example, the shielding pattern 21 can be provided along one or more sides of the substantially polygonal glass plate 25. In one embodiment, the region Ar exists along the entire circumference of the glass plate 25. The planar outline of the area Ar can match the planar outline of the glass plate 25.

The coated glass plate 20 of this embodiment can be manufactured as follows.
(Step S1)
As shown in FIGS. 1 and 2, a glass plate 25X with a shielding pattern is prepared, which includes a glass plate 25 and a shielding pattern 21 laminated on one surface 26 of the glass plate 25.
As a constituent material of the shielding pattern 21, ceramics or the like is preferable. The shielding pattern 21 can be formed by a known method, for example, by applying and firing a ceramic paste containing a pigment (preferably a black pigment) and a glass frit. The shielding pattern 21 may be a continuous film or may be a film divided into several parts. The shielding pattern 21 does not need to be a film. The shielding pattern 21 may be a semi-light-shielding pattern, for example, a gradation pattern in which the border with the translucent area is not clear. The shielding pattern 21 may be formed by scattering powder such as ceramics onto the surface 26 of the glass plate 25.
The thickness of the shielding pattern 21 is not particularly limited, and is, for example, 5 to 20 μm, preferably 8 to 15 μm.

(Step S2)
Next, as shown in FIGS. 1 and 3, the shielding patterned glass plate 25X is placed approximately perpendicularly to the ground, or approximately horizontally and approximately perpendicularly to the ground, with one side of the shielding patterned glass plate 25X facing upward. Place it at an angle of inclination between. This arrangement is also called standing. This arrangement state is also called an upright state.
In the coated glass plate 20 for front bench glass, as shown in FIG. 1, one side (specifically the front side or the rear side, in the illustrated example, the front side 25C side) is placed upward , the glass plate 25X with a shielding pattern can be placed vertically.
Standing can be carried out using a vacuum suction device.

The film-forming liquid composition 27 is applied by a flow coating method to the surface of the glass plate 25X with the shielding pattern in the above arrangement on which the shielding pattern 21 is laminated. Specifically, as shown in FIG. 1, while the nozzle 28 is discharging the film-forming liquid composition 27, the above-mentioned one side (in the illustrated example, the front By relatively moving along the side 25C), continuous flow can be performed. The environmental temperature in step S2 is not particularly limited, and may be a normal environmental temperature, for example, 10 to 30°C.

Generally, the surface 26 of the glass plate 25 and the surface of the shielding pattern 21 have hydroxyl groups. The film-forming liquid composition 27 can contain a silicon compound that reacts with the hydroxyl groups present on these surfaces. In one embodiment, the film-forming liquid composition 27 contains a substance that absorbs or reflects ultraviolet (UV) or infrared (IR) radiation. In one embodiment, the film-forming liquid composition 27 contains a substance that imparts water repellency or oil repellency to the film 22. In one embodiment, the film-forming liquid composition 27 contains a substance that imparts water absorption or hygroscopicity to the film 22.

The coating 22 may weaken the adhesion between the shielding pattern 21 and other components. Therefore, in this embodiment, the film-forming liquid composition 27 is applied to a part of the surface of the shielding pattern 21, and the film-forming liquid composition 27 is not applied to the other part. Masking is applied to areas where the film-forming liquid composition 27 is not applied.

As shown in FIGS. 2 and 3, in this embodiment, in plan view, a downstream region located downstream in step S2 of the region Ar (light-shielding region) is adjacent to the region Tr and is located relative to the region Tr. The area is divided into an area In that is relatively close to the area In, and an area Ex that is adjacent to the area In and relatively far from the area Tr. A shielding pattern 21 is laminated on the surface of both the region In and the region Ex of the glass plate 25.
The region Ar can include an upstream region located on the upstream side in step S2. This upstream region is also called region Op. The region Op can exist adjacent to the region Tr on the opposite side of the region In and the region Ex with the region Tr in between, in a plan view. A shielding pattern 21 is also laminated on the surface of the region Op of the glass plate 25.

As shown in FIG. 3, in step S2, with masking applied to the surface of the region Ex of the glass plate 25X with a shielding pattern, the surface of at least the region Tr and the region In of the glass plate 25X with a shielding pattern is used for film formation. The film-forming liquid composition 27 is poured in a direction from the region Tr side to the region In side so that the liquid composition 27 flows down.
When the area Ar includes the area Op, as shown in FIG. The film-forming liquid composition 27 may be poured in a direction from the region Tr side to the region In side so that the film-forming liquid composition 27 flows down. By starting the spraying from the region Op, the spraying can be performed satisfactorily over the entire surface of the region Tr, and damage to the coating 22 within the region Tr can be suppressed.

Masking can be performed by a known method using a masking member such as a jig and a masking tape; or a masking means such as a masking agent.
A template-type jig 30 is shown in FIGS. 2 and 3. FIG. The material of the jig 30 is not particularly limited, and examples include metal, resin, and combinations thereof. The thickness of the jig 30 is not particularly limited, and is preferably 1 to 10 mm.
Masking can be performed by bringing the jig 30 into contact with the surface of the region Ex of the glass plate 25X with the shielding pattern. The surfaces of the region Tr and the region In of the glass plate 25</b>X with the shielding pattern are exposed in the blank portion of the jig 30 . Masking may be applied to the entire surface of the outer peripheral portion of the glass plate 25X with a shielding pattern, including the area Ex of the area Ar. Masking may be performed by pasting masking tape or applying a masking agent.

The surface of the region Ex of the shielding pattern 21 is masked, whereas the surface of the region In of the shielding pattern 21 is exposed to the film-forming liquid composition 27. In this step, a coating film 22W is formed on the surface of the glass plate 25X with a shielding pattern in a non-masking area within a flow area of the film-forming liquid composition 27.

As shown in FIG. 3, the film-forming liquid composition 27 reaches the masked region Ex via the boundary between the region Tr and the region In. The film-forming liquid composition 27 that has reached the region Ex may generate bubbles by colliding with the jig 30. This bubble may remain on the downstream end of coating 22. If the downstream end of the coating 22 has bubbles, the appearance of this end will be noticeable. The bubbles help make the boundary between the region In and the region Ex easier to see.

The end of the jig 30 on the inner peripheral side (region In side) may have a wave shape. The wave shape at the end of the jig may be copied onto the end of the film 22 by the film-forming liquid composition 27 hitting the end of the wave shape. The undulation of the downstream end of the coating 22 in the form of waves makes the appearance of this end noticeable. The wave shape helps to make the boundary between the region In and the region Ex easier to see. When masking tape is used instead of the jig 30, the end of the masking tape on the inner peripheral side (region In side) may be pasted in a wave shape.

(Standing process)
After the formation of the coating film 22W is completed, the obtained glass plate with the coating film may be held in an upright position for about 10 to 20 seconds, if necessary. This time is also called "standing time."

(Step S3)
Next, the coating film 22W is dried and cured, or dried and cured to form the coating film 22. In this way, the coated glass plate 20 shown in FIG. 4 is manufactured.
The masking means such as the jig 30 is removed from the shielding patterned glass plate 25X after step S2, the standing step, or step S3.

As shown in FIG. 4, the coated glass plate 20 includes a glass plate 25, and a shielding pattern 21 and a coating 22 laminated on one surface 26 of the glass plate 25. As shown in FIG. In plan view, the coated glass plate 20 has a translucent region Tr in the region excluding the peripheral region, and in the peripheral region, a region In adjacent to the region Tr and relatively close to the region Tr, and a region In in the peripheral region. It has an adjacent region Ex that is relatively far from the region Tr. The shielding pattern 21 covers the surface of the region In and the region Ex of the glass plate 25, and the coating 22 covers the surface of the region Tr of the glass plate 25 and the surface of the region In of the shielding pattern 21, and covers the surface of the region In and the region Ex of the shielding pattern 21. Do not cover the surface.

As shown in FIGS. 3 and 4, the surface of the shielding pattern 21 generally has fine irregularities. As shown in FIG. 4, the unevenness on the surface of the region In of the shielding pattern 21 can be filled with the coating 22. Thereby, the surface of the area In of the covered glass plate 20 can be made smoother than the surface of the area Ex of the covered glass plate 20. In other words, the surface roughness of the area In of the covered glass plate 20 can be made smaller than the surface roughness of the area Ex of the covered glass plate 20. In other words, the surface of the area Ex of the coated glass plate 20 remains rougher than the surface of the area In of the coated glass plate 20.

As shown in FIG. 4, the film 22 formed by the above method including the continuous flow process can have a first thickened portion 22A in the region Tr that becomes gradually thicker as it approaches the region In.
Further, since the liquid composition 27 for forming a film that is poured has surface tension, the film 22 can have a reduced thickness portion 22B in the region In, which becomes gradually thinner as it approaches the region Ex.

The coating 22 formed by the above-described method of masking in the continuous flow process further has a second thickened portion 22C in the region In and on the region Ex side of the reduced thickness portion 22B, which becomes gradually thicker as it approaches the region Ex. can have. The downstream end of the second thickened portion 22C may be a rising surface 22D that rises substantially perpendicularly or obliquely to the surface of the shielding pattern 21. The rising surface 22D can be a curved surface such as a concave curved surface.
When a masking tape is used in the pouring process, the downstream end of the second thickened portion 22C of the coating 22 can have a steep shape, for example. A sharp shape can be revealed by removing the masking tape. Further, when a jig is used, the downstream end portion of the second increased thickness portion 22C of the coating 22 has a mountain-like shape, for example.

The presence of the second increased thickness portion 22C within the region In of the coating 22, preferably including the rising surface 22D, facilitates the positioning of the sealant when attaching the coated glass plate 20 to another member such as a window frame member. It can function as an alignment mark to facilitate alignment.
The presence of the second increased thickness portion 22C within the region In of the coating 22, preferably including the rising surface 22D, allows the sealing material to adhere to the coating 22 when attaching the coated glass plate 20 to another member such as a window frame member. It can act as a barrier to prevent further spread.
The presence of the second increased thickness portion 22C, preferably including the rising surface 22D, in the region In of the coating 22 makes it easier to attach the coated glass plate 20 to another member such as a window frame member. It can function as an alignment mark that facilitates positioning of the coated glass plate 20 with respect to other members.

The film 22 having the thickness distribution as described above is formed by the composition, solid content concentration, and viscosity of the film-forming liquid composition (LC); Adjusting one or more conditions such as the discharge amount and the moving speed of the nozzle 28; the arrangement angle of the glass plate 25X with the shielding pattern in step S2; the type, thickness, and surface properties of the masking means; the peeling strength and peeling timing of the masking means. This can be achieved by doing so.
The higher the solid content concentration of the film-forming liquid composition (LC), the greater the overall thickness of the film 22 tends to be.
The larger the coating amount of the film-forming liquid composition (LC) per unit time, the more likely it is that the overall thickness of the film 22 can be increased.
The overall thickness of the coating 22 can be adjusted by adjusting the arrangement angle of the shielding patterned glass plate 25X. The thickness of the coating 22 can be made thinner overall if the glass plate 25X with the shielding pattern is arranged almost perpendicularly to the ground, and the coating 22 can be made thinner as a whole if the glass plate 25X is arranged substantially horizontally to the ground. There is a tendency for the overall thickness to be increased.

The specific thickness distribution of the coating 22 is not particularly limited and is designed according to the function of the coating 22.
Coating 22 can include a siloxane compound. A siloxane compound is a compound having a siloxane bond (Si—O bond). The coating 22 can contain one or more functional components selected from the group consisting of ultraviolet screening agents and infrared screening agents.
When the coating 22 contains functional components such as an ultraviolet screening agent and an infrared screening agent, the preferable thickness of the coating 22 is as follows.

The thickness of the region Tr of the coating 22 is preferably 1 to 10 μm. When the thickness of the region Tr of the coating 22 is 1 μm or more, the coating 22 can satisfactorily exhibit desired functions such as ultraviolet shielding and infrared shielding. If the thickness of the region Tr of the coating 22 is 10 μm or less, the thickness of the coating 22 is not too thick, and cracks (also referred to as cracks or initial cracks) of the coating 22 are unlikely to occur at the time of completion of step S3. The upper limit is more preferably 8 μm, still more preferably 7 μm, particularly preferably 6 μm, and most preferably 5 μm. The lower limit is more preferably 1.5 μm, particularly preferably 2.0 μm, and most preferably 2.5 μm.

The thickness of the region In of the coating 22 is preferably 0.1 to 10 μm. The upper limit is more preferably 8 μm, still more preferably 7 μm, particularly preferably 6 μm, and most preferably 5 μm. The lower limit is more preferably 1 μm, particularly preferably 2 μm, and most preferably 3 μm.
The height of the rising surface 22D of the coating 22 from the surface of the shielding pattern 21 (the maximum height of the second increased thickness portion 22C) is not particularly limited, and is 3 to 20 times the minimum thickness of the region In of the coating 22. The thickness is preferably 10 to 120 μm, for example.

In FIG. 4, reference numeral WG indicates a vehicle window glass with a window frame member, and reference numeral 35 indicates a window frame member provided on the body of a vehicle such as an automobile.
When the covered glass plate 20 is for a vehicle window glass that is attached to a window frame member 35 provided on a vehicle body from the outside of the vehicle body, at least a part of the surface of the area Ex of the shielding pattern 21 is bonded to the window frame member 35. At least a portion of the surface of the region In of the coating 22 can be a non-adhesive surface that is not adhered to the window frame member 35.

The method for manufacturing a vehicle window glass with a window frame member according to the present disclosure includes a step S4 of attaching the covering glass plate 20 to the window frame member 35 provided on the vehicle body from the outside of the vehicle body.
In step S4, at least a portion (preferably the whole) of the surface of the region Ex of the shielding pattern 21 and the window frame member 35 are bonded, and at least a portion (preferably the whole) of the surface of the region In of the coating 22 is bonded. It does not adhere to the window frame member 35. In this way, at least a portion (preferably the entire surface) of the area Ex of the shielding pattern 21 is covered by the window frame member 35, while at least a portion (preferably the entire surface) of the surface of the area In of the coating 22 is It is exposed toward the inside of the vehicle body inside the window frame member 35.
As shown in FIG. 4, the surface of the region Ex of the shielding pattern 21 and the window frame member 35 can be bonded by a known method using a sealing material 34 such as an adhesive or an adhesive tape.

As shown in FIG. 4, at least a portion (preferably the entirety) of the region In of the shielding pattern 21 is observed from the inside of the vehicle body. The region In of the shielding pattern 21 is covered with a smooth film 22 continuous from the translucent region Tr. Therefore, the shielded region In can exhibit the same gloss as the translucent region Tr. The luster can be expressed by the degree of gloss.
On the other hand, the surface of the region Ex of the shielding pattern 21 is not covered with the film 22. However, at least a portion (preferably the entire surface) of the region Ex of the shielding pattern 21 is blocked by the window frame member 35 and cannot be observed from the inside of the vehicle body. Therefore, the exposure of the surface of the region Ex of the shielding pattern 21 does not affect the aesthetic appearance of the inner surface of the vehicle body of the covered glass plate 20. The same applies to the area Op.

As described above, the surface roughness of the area In of the covered glass plate 20 is smaller than the surface roughness of the area Ex of the covered glass plate 20.
In this specification, unless otherwise specified, surface roughness is an arithmetic mean roughness Ra measured in accordance with JIS B 0601-1994.

The sealing material 34 can adhere well to the relatively rough surface of the region Ex of the shielding pattern 21 . On the other hand, the relatively smooth surface of the coating 22 is not bonded to the window frame member 35. As described above, the presence of the coating 22 prevents the bond between the surface of the region Ex of the shielding pattern 21 and the window frame member 35 from being weakened. The same applies to the area Op.
In the present disclosure, since masking is performed only on a part of the outer circumference side of the surface of the shielding pattern 21, there is no need to strictly perform masking alignment. Masking is performed only on a part of the outer peripheral side of the surface of the shielding pattern 21, and by making the film 22 exist on the surface of both the region Tr and the region In of the covered glass plate 20, the masking extends to the region Tr. The film 22 can be satisfactorily formed over the entire region Tr, and defects in the film 22 within the region Tr can be suppressed. These effects are advantageous in terms of process ease, quality stability, and productivity improvement.

The dimension of the region In in the flow direction of the film-forming liquid composition (LC) in step S2 (the distance between the region Tr and the region Ex) is defined as H _In . The dimension of the region Ex in the flow direction of the film-forming liquid composition (LC) in step S2 is defined as H _Ex .
The sum of H _In and H _Ex (H _In +H _Ex ) is preferably 20 to 150 mm, more preferably 50 to 100 mm.
The ratio of H _In to the sum of H _In and H _Ex (H _In /(H _In +H _Ex )) is preferably 0.2 to 0.6, more preferably 0.3 to 0.5.
The ratio of H _Ex to the sum of H _In and H _Ex (H _Ex /(H _In +H _Ex )) is preferably 0.4 to 0.8, more preferably 0.5 to 0.7.
By designing as described above, a sufficient bonding area between the surface of the region Ex of the shielding pattern 21 and the window frame member 35 is ensured, and the covered glass plate 20 can be bonded well to the window frame member 35.

From the viewpoint of adhesiveness between the surface of the region Ex of the shielding pattern 21 and the window frame member 35, the arithmetic mean roughness Ra (Ex) of the surface of the region Ex of the covered glass plate 20 is preferably 0.55 μm or more, more preferably is 0.6 μm or more. The upper limit value of Ra(Ex) is, for example, 1.0 μm, 0.9 μm, or 0.8 μm.
From the viewpoint of good appearance of the region In of the coated glass plate 20, the arithmetic mean roughness Ra (In) of the surface of the region In of the coated glass plate 20 is preferably 0.45 μm or less, more preferably 0.4 μm or less, Particularly preferably, it is 0.38 μm or less. The lower limit of Ra(In) is not particularly limited, and is, for example, 0.01 μm, 0.02 μm, 0.03 μm, or 0.04 μm.
In this specification, unless otherwise specified, the surface of the area In of the coated glass plate is the surface on the side where the shielding pattern and coating are formed in the area In of the coated glass plate, and the surface of the area Ex of the coated glass plate is the surface of the area In of the coated glass plate where the coating is formed. This is the surface of the area Ex of the glass plate on the side where the shielding pattern is formed.

It is preferable that the difference between the glossiness of the surface on the inside of the vehicle and the glossiness of the surface on the outside of the vehicle of the coated glass plate 20 is smaller. The gloss level on the outside of the vehicle is, for example, 90 to 95.
The surface of the area In of the covered glass plate 20 can have a higher gloss than the surface of the area Ex of the covered glass plate 20.
The glossiness Gr(Ex) of the surface of the region Ex of the coated glass plate 20 can be, for example, 9 or less, 7 or less, or 5 or less.
The glossiness Gr (In) of the surface of the region In of the coated glass plate 20 is preferably 10 or more, more preferably 15 or more, even more preferably 20 or more, even more preferably 25 or more, particularly preferably 30 or more, and most preferably It is 35 or more. The upper limit of Gr(In) is, for example, 95.
In this specification, unless otherwise specified, gloss is a value measured using a gloss meter in accordance with JIS Z 8741-1997 "Specular gloss - measurement method".

As described above, the thickness of the shielding pattern 21 is, for example, 10 to 20 μm.
In the region In of the coated glass plate 20, the ratio (C _T /S T ) of the thickness (C _{T )} of the coating 22 to the thickness (S _T ) of the shielding pattern 21 is preferably 0.02 to 0.8. be.
If C _T /S _T is greater than or equal to the above lower limit, the surface of the region In of the shielding pattern 21 is well covered with the film 22, and the surface of the region In of the coated glass plate 20 has a sufficient arithmetic mean roughness Ra. Can be small and have high gloss. Further, if C _T /S _T is equal to or less than the above upper limit value, the thickness of the coating 22 will not become too thick, and cracks (initial cracks) in the coating 22 will not easily occur at the time of completion of step S3. The lower limit of C _T /S _T is more preferably 0.03, still more preferably 0.05, particularly preferably 0.1, and most preferably 0.2. When C _T /S _T is 0.2 or less, optical distortion of the region In of the shielding pattern 21 is suppressed, so that its appearance is less likely to be impaired. The upper limit of C _T /S _T is more preferably 0.7, particularly preferably 0.6, and most preferably 0.5.

(Glass plate)
The glass plate 25 can be tempered glass, laminated glass made by bonding a plurality of glass plates with an interlayer interposed therebetween, or organic glass. For applications such as vehicle window glass, the glass plate is preferably tempered glass or laminated glass.

The type of glass plate that is the material for tempered glass and laminated glass is not particularly limited, and examples include soda lime glass, borosilicate glass, aluminosilicate glass, lithium silicate glass, quartz glass, sapphire glass, and alkali-free glass.
Tempered glass is obtained by subjecting a glass plate as described above to a strengthening process using a known method such as an ion exchange method or an air-cooling strengthening method. As the tempered glass, air-cooled tempered glass is preferable.
The thickness of the tempered glass is not particularly limited and is designed depending on the application. For vehicle window glass applications, the thickness is preferably 2 to 6 mm. The thickness of the laminated glass is not particularly limited and is designed depending on the application. For vehicle window glass applications, the thickness is preferably 2 to 6 mm.

In applications such as vehicle window glass, a glass plate is processed into a shape having a curved surface.
The glass plate may have a curved shape so that the outside of the vehicle is convex when attached to the vehicle. When the glass plate is laminated glass, the glass plate on the inside of the vehicle and the glass plate on the outside of the vehicle may both have a curved shape such that the outside of the vehicle is convex. The glass plate may have a single curved shape that is curved in only one direction, ie, the left-right direction or the up-down direction, or may have a double-curved shape that is curved in the left-right direction and the up-down direction. The radius of curvature of the glass plate may be between 2000 and 11000 mm. The glass plate may have the same radius of curvature in the left-right direction and the up-down direction, or may not have the same radius of curvature. Gravity forming, press forming, roller forming, etc. are used for bending the glass plate.

The interlayer film of laminated glass is made of a resin film. The constituent resin is not particularly limited as long as it can bond a plurality of glass plates well. The interlayer film may include, for example, 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. preferable.
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 film of the laminated glass may be a single layer film or a laminated film.

Examples of organic glass materials include engineering plastics such as polycarbonate (PC); acrylic resins such as polyethylene terephthalate (PET): polymethyl methacrylate (PMMA); polyvinyl chloride; polystyrene (PS); combinations thereof, etc. Engineering plastics such as polycarbonate (PC) are preferred.

(film)
Coating 22 can include a siloxane compound.
The coating 22 can be formed using a coating composition (LC). The coating 22 preferably contains 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. Consists of a cured film-forming liquid composition (LC).

<Hydrolyzable silicon compound (SC)>
One or more hydrolyzable silicon compounds (SC) can be cured to form a silicon oxide matrix by a hydrolytic condensation reaction. The "silicon oxide matrix" referred to in this specification is a polymer compound whose molecular weight is increased two-dimensionally or three-dimensionally by siloxane bonds represented by -Si-O-Si-.

Hydrolyzable silicon compounds (SC) are silicon compounds that have one or more hydrolyzable groups. The number of hydrolyzable groups bonded to one Si atom is 1 to 4, preferably 2 to 4, more preferably 3 to 4. The hydrolyzable group may be hydrolyzed into a hydroxyl group in the composition.

Hydrolyzable groups include alkoxy groups (including substituted alkoxy groups such as alkoxy-substituted alkoxy groups), alkenyloxy groups, acyl groups, acyloxy groups, oxime groups, amide groups, amino groups, iminoxy groups, aminoxy groups, and alkyl-substituted groups. Examples include an amino group, an isocyanate group, and a halogen atom. Among these, organooxy 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 methoxy and ethoxy groups are particularly preferred. As the halogen atom, a chlorine atom or the like is preferable.
When a plurality of hydrolyzable groups are present in the hydrolyzable silicon compound (SC), the plurality of hydrolyzable groups may be the same or non-identical, and it is preferable that the plurality of hydrolyzable groups be the same from the viewpoint of easy availability of raw materials.

The one or more hydrolyzable silicon compounds (SC) preferably include one or more trifunctional hydrolyzable silicon compounds and/or one or more tetrafunctional hydrolyzable silicon compounds. A combination of one or more trifunctional hydrolyzable silicone compounds and one or more tetrafunctional hydrolyzable silicone compounds is preferred. The one or more hydrolyzable silicon compounds (SC) can optionally include one or more difunctional hydrolyzable silicon compounds.

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 which one or more hydrolyzable groups are bonded to a Si atom in one molecule.

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

Examples of the tetrafunctional hydrolyzable silicon compound include tetramethoxysilane (TMOS), tetraethoxysilane (TEOS), tetra n-propoxysilane, tetra n-butoxysilane, tetra sec-butoxysilane, and tetra tert-butoxysilane. can be mentioned. Tetramethoxysilane (TMOS), tetraethoxysilane (TEOS), and the like are preferred.

Trifunctional hydrolyzable silicon compounds that do not have functional groups other than hydrolyzable groups include methyltrimethoxysilane, methyltriethoxysilane, methyltris(2-methoxyethoxy)silane, methyltriacetoxysilane, and methyltripropoxy. Silane, methyltriisopropenoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriacetoxysilane, and 1,6-bis(trimethoxysilyl) Examples include hexane.

Examples of trifunctional hydrolyzable silicon compounds having functional groups other than hydrolyzable groups include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyltris(2-methoxyethoxy)silane, and vinyltriisopropenoxy. Silane, 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-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-ureidopropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane Roxypropyltriethoxysilane, 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.

Difunctional hydrolyzable silicone compounds include dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldi(2-methoxyethoxy)silane, dimethyldiacetoxysilane, dimethyldipropoxysilane, dimethyldiisopropenoxysilane, and dimethyldibutoxysilane. , vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, vinylmethyldiacetoxysilane, vinylmethyldi(2-methoxyethoxy)silane, vinylmethyldiisopropenoxysilane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane, phenylmethyldiacetoxy Silane, 3-chloropropylmethyldimethoxysilane, 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, 2-cyanoethylmethyldimethoxysilane, and the like.

One or more tetrafunctional hydrolyzable silicone compounds, one or more trifunctional hydrolyzable silicone compounds, and one or more difunctional hydrolyzable silicone in the film-forming liquid composition (LC) The amount of the compound is not particularly limited.
The total amount of one or more tetrafunctional hydrolyzable silicon compounds and one or more trifunctional hydrolyzable silicon compounds is based on 100 parts by mass of the one or more hydrolyzable silicon compounds (SC). The amount is preferably 100 to 70 parts by weight, more preferably 100 to 80 parts by weight, particularly preferably 100 to 90 parts by weight.
The amount of one or more bifunctional hydrolyzable silicon compounds (in the case of multiple types, the total amount) is preferably 0 with respect to 100 parts by mass of the total amount of one or more hydrolyzable silicon compounds (SC). ~30 parts by weight, more preferably 0 to 20 parts by weight, particularly preferably 0 to 10 parts by weight.

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

Although the details will be described later, the film-forming liquid composition (LC) is a benzophenone-based ultraviolet absorber based on silylated benzophenone, which is a reaction product of a hydroxyl group-containing benzophenone compound and an epoxy group-containing hydrolyzable silicone compound. It can contain a UV absorber. This silylated benzophenone ultraviolet absorber is included in the hydrolyzable silicon compound (SC) and can form a silicon oxide matrix like the above bifunctional, trifunctional, or tetrafunctional hydrolyzable silicon compound. .

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

The film-forming liquid composition (LC) may contain one or more optional components other than the hydrolyzable silicon compound (SC), if necessary.

<Silicon oxide fine particles (SP)>
The film-forming liquid composition (LC) can optionally contain silicon oxide fine particles (SP) that are included in the film by bonding to the silicon oxide matrix. When the film-forming liquid composition (LC) contains silicon oxide fine particles (SP), the wear resistance of the film may be improved.
The silicon oxide fine particles (SP) can be blended into the film-forming 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 silicon oxide fine particles (SP) measured by the BET method is not particularly limited, and from the viewpoint of improving the transparency and abrasion resistance of the coating, it is preferably 1 to 100 nm, more preferably 5 to 40 nm. . When 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 silicon oxide fine particles (SP) used as necessary are components that form the silicon oxide matrix in the coating, and herein they are collectively referred to as , also called matrix component (S).

Here, the content of the hydrolyzable silicon compound (SC) in the liquid composition for film formation (LC) is SiO ₂ when Si atoms contained in the hydrolysable silicon compound (SC) are converted to SiO ₂ Shown in content.
The content (in the case of multiple types, the total amount) of one or more matrix components (S) in the total solid content of the liquid composition for film formation (LC) is preferably 10 to 90% as SiO ₂ content. % by weight, more preferably 20-60% by weight.
From the viewpoint of coating properties of the liquid composition for film formation (LC) and suppression of initial cracks in the film, one or more hydrolyzable silicon compounds (SC) are added to the total solid content of the liquid composition for film formation (LC). ) content (in the case of multiple types, the total amount) is preferably 10 to 90% by mass, more preferably 20 to 60% by mass as SiO ₂ content.
The amount of silicon oxide fine particles (SP) relative to the total amount of matrix component (S) is not particularly limited, and from the viewpoint of suppressing initial crack formation in the film and reduction in transparency of the film due to aggregation of silicon oxide fine particles (SP), etc. , preferably 0 to 50% by weight, more preferably 0 to 30% by weight.

<Functional ingredient (FU)>
The film-forming liquid composition (LC) can contain one or more functional components (FU), if necessary. The functions of the functional component (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; antireflection; low reflection; low radiation; energization; heating Water repellency or oil repellency; Water absorption or moisture absorption; Scratch resistance; Antifouling; Antibacterial; Decoration such as coloring; Combinations of these. The coating can, for example, contain an ultraviolet screening agent and/or an infrared screening agent as a functional component (FU).

As the ultraviolet shielding agent, any known one can be used, and it may be of the ultraviolet absorbing type or the ultraviolet reflecting type. One or more UV absorbers selected from the group consisting of benzophenone UV absorbers, benzotriazole UV absorbers, benzodithiol UV absorbers, azomethine UV absorbers, indole UV absorbers, and triazine UV absorbers Agents are preferred.

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

Any known infrared shielding agent can be used, and may be of an infrared absorbing type or an infrared reflecting type. As the infrared shielding agent, infrared shielding particles are preferred. As the infrared shielding particles, metal compound particles containing one or more metal compounds are preferred. For example, indium tin oxide (ITO), antimony-doped tin oxide (ATO), cesium-doped tungsten oxide (CWO®), fluorine-doped tin oxide (FTO), lanthanum hexaboride (LaB ₆ ), and pentoxide. Metal compound particles containing one or more metal compounds selected from the group consisting of vanadium (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 relatively large, for example, 1.5 or more. . In this case, the content of infrared shielding particles in the coating can be reduced. This reduces the absolute number of particles present in the vicinity of the interface between the coating and the glass plate, improving the adhesion between the glass plate and the coating and improving wear resistance.

When the film-forming liquid composition (LC) contains infrared-shielding particles, a dispersion containing the infrared-shielding particles, an organic solvent as a dispersion medium, and, if necessary, a dispersant may be used as a raw material for the infrared-shielding particles. preferable.

<Flexibility imparting component (FL)>
The film-forming liquid composition (LC) may contain one or more flexibility-imparting components (FL) that improve the film formability of the film and suppress initial cracks of the film, if necessary. .
The flexibility imparting component (FL) is effective regardless of the type of one or more hydrolyzable silicon compounds (SC). For example, when the one or more hydrolyzable silicon compounds (SC) consist only of tetrafunctional hydrolyzable silicon compounds, the resulting silicon oxide matrix may not have sufficient flexibility. In such a case, by using the flexibility imparting component (FL), it is possible to impart appropriate flexibility to the silicon oxide matrix and form a film that is excellent in both mechanical strength and initial crack resistance.

Flexibility-imparting components (FL) include organic resins such as silicone resins, acrylic resins, polyester resins, polyurethane resins, epoxy resins, phenol resins, and hydrophilic organic resins containing polyoxyalkylene groups; heating or active energy rays; Examples include curable organic compounds such as monomers, oligomers, or prepolymers that become organic resins upon irradiation; non-curable organic compounds other than resins such as glycerin, and the like. 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. Examples of active energy rays include ultraviolet rays and electron beams.
Thermosetting resins and thermosetting compounds such as monomers, oligomers, or prepolymers that become organic resins when heated are cured simultaneously when one or more hydrolyzable silicone compounds (SC) are cured by heating. can.
Active energy ray curable resins and active energy ray curable compounds such as monomers, oligomers, or prepolymers that become organic resins by irradiation with active energy rays are prepared by heating one or more hydrolyzable silicon compounds (SC). After being cured, it can be cured by irradiation with active energy rays.
The curable resin and curable compound may undergo a crosslinking reaction with one or more hydrolyzable silicon compounds (SC) during curing.

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

<Catalyst>
The film-forming liquid composition (LC) can contain one or more catalysts, if necessary.
When a catalyst is included in the raw materials for the constituent components of the film-forming liquid composition (LC), the one or more types of catalysts include the catalyst in the raw materials.
Examples of the catalyst include acid catalysts and alkali catalysts. Acid catalysts include inorganic acids such as nitric acid, hydrochloric acid, sulfuric acid and phosphoric acid; 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. As the catalyst, an acid catalyst is preferred. The catalyst can be used in the form of an aqueous solution.
The content of the catalyst in the film-forming liquid composition (LC) is not particularly limited. The content of one or more catalysts (in the case of multiple types, the total amount) is preferably 0.01 to 10 parts by mass, relative to the total amount of one or more hydrolyzable silicon compounds (SC) of 100 parts by mass. It is.

<Water>
The film-forming liquid composition (LC) can contain water, if necessary. When water is included in the raw materials for the constituent components of the film-forming liquid composition (LC), the water includes the water in the raw materials.
In the film forming process, the hydrolytic condensation reaction of one or more hydrolyzable silicon compounds (SC) can be carried out using moisture in the atmosphere, so the film forming liquid composition (LC) does not contain water. Good too.
The amount of water in the film-forming liquid composition (LC) is not particularly limited as long as it is sufficient to hydrolyze and condense one or more hydrolyzable silicon compounds (SC). Specifically, the amount is preferably 1 to 20 equivalents in molar ratio, more preferably 4 to 18 equivalents, based on the SiO ₂ equivalent amount of one or more hydrolyzable silicon compounds (SC).

<Organic solvent>
The film-forming liquid composition (LC) can contain one or more organic solvents as a solvent and/or a dispersion medium, if necessary. When organic solvents are included in the raw materials for the constituent components of the film-forming liquid composition (LC), the one or more organic solvents include the organic solvents in the raw materials.

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

Among the above, alcohols with a boiling point of 80 to 160°C are preferred from the viewpoint of solubility in the liquid composition for film formation (LC) and coatability of the liquid composition for film formation (LC), and specific Includes 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 alcohols and one or more other organic solvents other than the alcohols that are miscible with water and alcohol may be used in combination.

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

<Dispersant>
The film-forming liquid composition (LC) may contain one or more dispersants for dispersing inorganic fine particles such as infrared shielding particles, if necessary. When a dispersant is included in the raw materials for the constituent components of the film-forming liquid composition (LC), the one or more types of dispersants include the dispersant in the raw materials.
As the dispersant, known ones can be used.

<Chelating agent>
The film-forming liquid composition (LC) can contain one or more chelating agents, if necessary.
When the film-forming liquid composition (LC) contains infrared-shielding particles and an ultraviolet-shielding agent, one or more chelating agents that can form a complex with the infrared-shielding particles can be used. The chelating agent can be coordinated to the surface of the infrared-shielding particles to suppress the chelate bonding of the ultraviolet-shielding agent to the infrared-shielding particles.The chelating agent is included in the raw materials of the constituent components of the liquid composition for film formation (LC). In this case, the one or more chelating agents include dispersants in the feedstock.

As the chelating agent, known ones can be used. It is preferable that the chelating agent has a low absorption rate of visible light. The chelating agent is appropriately selected depending on the type of liquid medium such as water and organic solvent. The liquid medium can include water and/or alcohol, and chelating agents soluble in these polar solvents are preferred. Examples of such chelating agents include carboxylic acids such as maleic acid and (meth)acrylic acid; and (co)polymers thereof (eg, polymaleic acid and polyacrylic acid).

<Other additives>
The film-forming liquid composition (LC) may contain one or more additives other than those mentioned above, if necessary. Examples of additives other than those mentioned above include surface conditioners, antifoaming agents, viscosity modifiers, adhesion agents, light stabilizers, antioxidants, dyes, pigments, and fillers.

In step S3, the coating film 22W can be dried under conditions that do not allow the curing reaction to proceed. The drying method is not particularly limited, and examples include heat drying at about 40 to 60°C, vacuum drying, and vacuum drying at about 40 to 60°C.
In step S3, the coating film 22W can be cured by heating under temperature conditions at which one or more hydrolyzable silicon compounds (SC) are cured. The curing can be carried out in one stage of only main firing or in multiple stages of preliminary firing and main firing.
The main firing temperature is not particularly limited. When the glass plate is tempered glass, the temperature is preferably 80 to 230°C, more preferably 100 to 230°C, particularly preferably 150 to 230°C, and most preferably 180 to 210°C. When the glass plate is laminated glass, the 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 film-forming liquid composition (LC), the heating temperature, and the like.

The orientation of the glass plate with the coating film in step S3 is not particularly limited. The coated glass plate may be arranged approximately horizontally so that the coated film side is on the upper side.
When the liquid composition for film formation (LC) contains a thermosetting resin and/or a thermosetting compound, the thermosetting resin and/or the thermosetting compound is treated with one or more hydrolyzable compounds in step S3. Can be cured together with silicon compounds (SC).

When the film-forming liquid composition (LC) contains an active energy ray-curable resin and/or an active energy ray-curable compound, after step S3, the film is irradiated with active energy rays to form the active energy ray-curable resin. and/or a step of curing the active energy ray-curable compound. Examples of active energy rays include ultraviolet rays and electron beams.

[Front bench glass]
The automobile front bench glass of the present disclosure includes the coated glass plate of the present disclosure described above. The front bench glass is also called the front side glass.
FIG. 10 is a schematic side view of an automobile according to an embodiment of the present invention. 101 is a windshield, 102 is a front bench glass (front side glass), 103 is a front door glass (side glass), 104 is a rear door glass (side glass), 105 is a rear side glass (side glass), and 106 is a rear glass. show.
The front bench glass 102 may include the above-described coated glass plate 20 having a glass plate 25 , a shielding pattern 21 and a coating 22 . In addition, in FIG. 10, the covering glass plate 20 is shown in a perspective view.

Examples of dimensions for the coated glass plate 20 for front bench glass are as follows.
The dimension (H _Tr ) of the region Tr in the flow direction of the film-forming liquid composition (LC) in step S2 (the distance between the region Op and the region In) is, for example, 30 to 150 mm.
The dimension (H _In ) of the region In in the flow direction of the film-forming liquid composition (LC) in step S2 (the distance between the region Tr and the region Ex) is, for example, 20 to 80 mm.
The dimension (H _Ex ) of the region Ex in the flow direction of the film-forming liquid composition (LC) in step S2 is, for example, 20 to 100 mm.

The sum of H _In and H _Ex (H _In +H _Ex ) is preferably 20 to 150 mm, more preferably 50 to 100 mm.
The ratio of H _In to the sum of H _In and H _Ex (H _In /(H _In +H _Ex )) is preferably 0.2 to 0.6, more preferably 0.3 to 0.5.
The ratio of H _Ex to the sum of H _In and H _Ex (H _Ex /(H _In +H _Ex )) is preferably 0.4 to 0.8, more preferably 0.5 to 0.7.
By designing as described above, a sufficient bonding area between the surface of the region Ex of the shielding pattern 21 and the window frame member 35 is ensured, and the covered glass plate 20 can be bonded well to the window frame member 35.

As described above, according to the present disclosure, it is possible to provide a coated glass plate that does not weaken the adhesion between the shielding pattern and other members while providing a coating on the shielding pattern, and a method for manufacturing the same.

[Application]
The coated glass sheet of the present disclosure can be used for any purpose, and is suitable for window glass for transportation equipment such as automobiles, trains, ships, and aircraft; window glass for buildings, etc.
The coated glass plate of the present disclosure is suitable for window glass (windshield, front bench glass, side glass, rear glass, etc.) of vehicles such as automobiles.

The present invention will be described below based on Examples, but the present invention is not limited thereto. Examples 1 to 4 and 11 to 17 are examples. Unless otherwise specified, room temperature is 20-25°C.

[Evaluation items and evaluation methods]
The evaluation items and evaluation methods are as follows.
(Viscosity of liquid composition for film formation (LC))
Using a viscometer (“RE85L” manufactured by Toki Sangyo Co., Ltd.), the viscosity of the film-forming liquid composition (LC) at room temperature during step S2 was measured.

(Shielding pattern and coating thickness)
The shielding pattern and the thickness of the coating were measured by cross-sectional observation using a scanning electron microscope (SEM).

(Arithmetic mean roughness Ra)
Using a surface roughness meter ("SURFCOM NEX 001 DX-12" manufactured by Tokyo Seimitsu Co., Ltd.), the arithmetic mean roughness Ra of the surface of the coated glass plate was measured in accordance with JIS B 0601-1994.

(Glossiness)
Using a gloss meter (“IG-331” manufactured by Horiba, Ltd.), the gloss of the surface of the coated glass plate was measured at a measurement angle of 60° in accordance with JIS Z 8741-1997 “Specular gloss - measurement method”. was measured.

(Initial crack resistance)
The surface of the coating on the coated glass plate was observed using an optical microscope ("BX53M" manufactured by OLYMPUS) at a magnification of 50 times. The presence or absence of initial cracks and partial peeling was confirmed. The evaluation criteria are as follows.
Good (A): No initial cracks are observed.
Fair (B): Slight initial cracks were observed, but no partial peeling was observed.
Poor (C): Initial cracking and partial peeling were observed.

[material]
The materials used in each example are as follows.
<Glass plate (G)>
As schematically shown in FIG. 9, two glass plates (GA) and (GB) having different dimensions in the flowing direction in step S2 were prepared.
(GA) Tempered glass for automobile front bench glass (manufactured by AGC), the top side (25A) and bottom side (25B) are 202 mm, the front side (25C) and the rear side (25D) are 688 mm, A curved glass plate having a thickness of 3.1 mm and having a substantially parallelogram shape in plan view (inner surface (concave surface) vertical radius of curvature = 2000 to 8000 mm, horizontal radius of curvature = 300 to 800 mm).

(GB) Tempered glass for automobile front bench glass (manufactured by AGC), the top side (25A) and bottom side (25B) are 170 mm, the front side (25C) and the rear side (25D) are 699 mm, A curved glass plate having a thickness of 3.1 mm and having a substantially parallelogram shape in plan view (inner surface (concave surface) vertical radius of curvature = 4000 to 6000 mm, horizontal radius of curvature = 500 to 600 mm).

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

<Ultraviolet absorber (ultraviolet shielding agent)>
THBP: dihydroxybenzophenone 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), and 0.8 g of benzyltriethylammonium chloride (manufactured by Junsei Kagaku Co., Ltd.) as a curing catalyst. , and 100 g of butyl acetate (manufactured by Junsei Kagaku Co., Ltd.) were dissolved by raising the temperature to 60°C with stirring, and by heating at 120°C and reacting for 4 hours, a silylated ultraviolet absorber with a solid content concentration of 63% by mass was obtained. (Si-THBP) solution was obtained. This silylated ultraviolet absorber (Si-THBP) is a functional component and a trifunctional hydrolyzable silicon compound.

<Infrared absorber (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 Quantum Kasei Co., Ltd., 3.0 g of dispersant (“DISPERBYK-190” manufactured by BYK Chemie Japan Co., Ltd.), and the mixed solvent described below ( 24.2 g of AP-1) was subjected to dispersion treatment for 48 hours using a ball mill.Additionally, a mixed solvent (AP-1) was added to dilute the ITO concentration to 20% by mass to obtain an ITO dispersion. I got it.

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

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

<Surface conditioning agent>
BYK307 dispersion liquid: Silicone surface conditioner (“BYK307” manufactured by Big Chemie Japan), 12% by mass methanol dispersion liquid.

<Organic solvent>
MEK: Methyl ethyl ketone, purity 99.9% by mass.
Methanol: purity 99.5% by mass.

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

[Production Example 1] (Preparation of liquid composition for film formation (LC1))
In a round bottom flask, add 12.4g of TEOS, 11.6g of Si-THBP solution (63% by mass), 1.9g of EX-614B solution (50% by mass), 1.7g of PMA-50W, and maleic acid. 1.0g, 0.5g of BYK307 dispersion (12% by mass), 8.6g of methanol, 38.0g of MEK, 9.5g of acetic acid aqueous solution (90% by mass), and 12.8g of pure water. , and stirred and mixed at 50° C. for 2 hours. Finally, 6.80 g of ITO dispersion (20% by mass) was added and mixed with stirring. As described above, a liquid composition for film formation (LC1) having a solid content concentration of 12.2% by mass was obtained.

[Example 1 to Example 3] (Manufacture of coated glass plate)
The upper and middle diagrams of FIG. 9 are schematic perspective views showing how the liquid composition for film formation is poured over the glass plate with the shielding pattern. In FIG. 9, the same components as in FIG. 1 are given the same reference numerals, and their explanations will be omitted.
As shown in the upper and middle diagrams of FIG. 9, the glass plate (G) is a glass plate (GA) with different heights of the region Tr in the flow direction of the film-forming liquid composition (LC) (Examples 1 and 2). ) and a glass plate (GB) (Example 3) were prepared. The glass plate (GA) has a higher height of the region Tr in the flow direction of the film-forming liquid composition (LC1) than the glass plate (GB).

(Step S1)
A commercially available shielding pattern containing black pigment and glass frit is applied to the peripheral area (area within 80 mm from the outer periphery) of one surface (vehicle inner surface, concave curved surface) of the glass plate (GA) or (GB) by screen printing. A ceramic paste for formation (BP1) was applied, dried and fired to form a shielding pattern (21). In this way, a glass plate with a shielding pattern (25X) as shown in FIG. 9 was obtained. Hereinafter, unless otherwise specified, the surface of the shielding patterned glass plate is a concave curved surface.

(Step S2)
Next, as shown in FIGS. 2 and 3, masking was performed on the outer periphery (area within 15 mm from the outer periphery) of the peripheral area of the glass plate with the shielding pattern. In Examples 1 and 3, a template-shaped jig (made of resin, 3 mm thick) was brought into contact with the outer periphery of the peripheral region of the glass plate with the shielding pattern. In Example 2, masking tape (0.5 mm thick) was attached to the outer periphery of the peripheral area of the glass plate with the shielding pattern. In both examples, the masking area includes the area Ex and the outer periphery of the area Op, but does not include the area In.

Next, using a vacuum suction device, place the masked glass plate with the shielding pattern on the ground with one side (front side 25C side) facing upward, as shown in Figures 1 and 3. It was held in a vertical position. The room temperature at the time of step S2 was 22°C. The viscosity of the film-forming liquid composition (LC1) at room temperature during step S2 was 1.2 mPa·s. The temperature of the glass plate with the shielding pattern (also referred to as glass temperature) was the same as room temperature.
In this state, the film-forming liquid composition (LC1) was poured onto the surface (inner surface of the car, concave curved surface) of the glass plate with the shielding pattern by a flow coating method.

A liquid nozzle was arranged near the one side of the surface of the glass plate with a shielding pattern so that the discharge openings of the liquid nozzle faced each other. The diameter of the discharge port of the liquid nozzle was 3 mmφ.
During 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 above-mentioned one side of the glass plate with the shielding pattern.
During movement of the liquid nozzle in the width direction, the horizontal separation distance of the center of the discharge port of the liquid nozzle from the surface of the glass plate with the shielding pattern was set to 3 mm±3 mm.

While continuously discharging the liquid composition for film formation (LC1) from the liquid nozzle, the liquid nozzle is applied along the one side of the glass plate with the shielding pattern to one end of the one side of the glass plate with the shielding pattern. It was moved in the width direction of the glass plate with the shielding pattern from one side to the other end.
The moving speed of the liquid nozzle was 40 mm/s, and the discharge amount (also referred to as liquid discharge amount) of the film-forming liquid composition (LC1) from the liquid nozzle was 11 g/s. The amount of liquid discharged was adjusted by the moving speed.

As described above, while the surface of the region Ex of the glass plate with a shielding pattern is masked, the surfaces of at least a part of the region Op, the region Tr, and the region In of the glass plate with a shielding pattern are masked. A coating film (22W) was formed by pouring the liquid composition for film formation (LC1) in the direction from the region Tr side to the region In side so that the liquid composition for film formation (LC1) flowed down. .
The dimension (H _Tr ) of the region Tr in the flow direction of the liquid composition for film formation (LC1) on the glass plate (GA) was 36 to 100 mm.
The dimension (H _Tr ) of the region Tr in the flow direction of the liquid composition for film formation (LC1) on the glass plate (GB) was 30 to 70 mm.

(Standing process)
After the formation of the coating film was completed, the obtained glass plate with the coating film was held in an upright state for 15 seconds. This time is called "standing time."
After this step, the masking was removed.

(Step S3)
Next, the glass plate with the coating film was baked at 180° C. for 20 minutes in an air atmosphere to harden the coating film. In this step, the glass plate with the coating film was placed approximately horizontally with respect to the ground (laying flat) so that the coating film side was on the upper side. As described above, a coating (22) was formed to obtain a coated glass plate (20). The obtained coated glass plate was observed using a scanning electron microscope (SEM).

[SEM observation results of the coated glass plate obtained in Example 1]
In Example 1, a glass plate (GA) was used, and masking was performed using a jig in step S2. As shown in FIG. 4, it was confirmed that the coating of the coated glass plate obtained in Example 1 had a tendency to become gradually thicker within the region Tr as it approached the region In. That is, it was confirmed that the coating of the coated glass plate obtained in Example 1 had a first increased thickness portion (22A) within region Tr that gradually became thicker as it approached region In.

FIG. 5 is a cross-sectional SEM photograph in the running direction at a point approximately 1 cm upstream from the boundary between the region In and the region Ex within the region In of the coated glass plate obtained in Example 1.
In the region In, it was confirmed that a shielding pattern (Shield) and a coating (Coating) were sequentially laminated on the glass plate (Glass). In the figure, the upper side is the upstream side of the continuous flow, and the lower side is the downstream side of the continuous flow. Masking was performed using a jig further downstream of the area shown in the photo.

FIG. 6 is a further enlarged photograph of points L01 to L06 in FIG.
The thickness of the coating decreases in the order of L02, L03, L04, L05, and L06, and the coating has a decreasing thickness part (22B) on the upstream side in the region In, which becomes gradually thinner as it approaches the region Ex. was confirmed. The thickness of the coatings L03 to L06 was approximately 0.5 to 1.2 μm.

FIG. 7 is a perspective SEM photograph of the downstream end of the coating of the coated glass plate obtained in Example 1. Swelling of the coating was observed at the downstream end of the coating (near the boundary between region In and region Ex). The downstream end of the coating included a second thickened portion (22C), and the downstream end was a raised surface (22D) that rose obliquely with respect to the surface of the shield pattern (Shield). .

[SEM observation results of the coated glass plate obtained in Example 2]
In Example 2, a glass plate (GA) was used, and masking with tape was performed in step S2. As in Example 1, it was confirmed that the coating of the coated glass plate obtained in Example 2 had a tendency to become gradually thicker within region Tr as it approached region In, as shown in FIG. That is, it was confirmed that the coating of the coated glass plate obtained in Example 2 had a first increased thickness portion (22A) within region Tr that gradually became thicker as it approached region In.
Similar to Example 1, it was confirmed that the coating of the coated glass plate obtained in Example 2 had a reduced thickness portion (22B) on the upstream side within region In, which became gradually thinner as it approached region Ex.

FIG. 8 is a cross-sectional SEM photograph of the downstream end of the coating of the coated glass plate obtained in Example 2. It can be seen that while the surface of the coating is smooth, the surface of the shield pattern is rougher. Swelling of the coating was observed at the downstream end of the coating (near the boundary between region In and region Ex). The downstream end of the coating includes a second thickened portion (22C), and the downstream end thereof is a raised surface (22D) that rises substantially perpendicularly to the surface of the shield pattern (Shield). Ta.

[Arithmetic mean roughness Ra and glossiness of coated glass plates obtained in Examples 1 and 3]
In Example 1, a glass plate (GA) was used, and masking was performed using a jig in step S2. In Example 3, a glass plate (GB) was used, and masking was performed using a jig in step S2. The arithmetic mean roughness Ra and glossiness were measured for the shielding pattern and the area In and Ex of the surface on the coating side of the coated glass plates obtained in these examples, respectively. The evaluation results are shown in Table 1.

[Example 4]
The lower diagram in FIG. 9 is a schematic front view showing how the liquid composition for film formation is poured onto the glass plate with the shielding pattern.
As shown in the lower diagram of FIG. 9, a rectangular glass plate (TP) (200 mm long, 100 mm wide, and 5 mm thick) in plan view was prepared as a test piece. A planar shielding pattern (21) (10 mm long, 50 mm wide, 8 μm thick) as shown in FIG. 9 was formed on the lower end of one surface by the same method as in step S1 of Example 1. A glass plate (25X) with a shielding pattern was obtained. This glass plate with a shielding pattern is also called a test piece without a coating.
Next, the obtained glass plate with a shielding pattern was subjected to the same steps as steps S2 and S3 of Example 1, except that masking was not performed, to coat almost the entire surface of the glass plate with a shielding pattern. A coated glass plate was obtained. This coated glass plate is also called a coated test piece.
The arithmetic mean roughness Ra and gloss of the surface of the shielding pattern formation area were measured for the test piece without a coating and the test piece with a coating, respectively. The evaluation results are shown in Table 1.

As shown in Table 1, in both Examples 1 and 3, the arithmetic mean roughness Ra (In) of the region In where the film is present on the surface is the arithmetic mean roughness Ra (Ex ) was confirmed to be smaller than The arithmetic mean roughness Ra (Ex) of the surface of the area Ex of the coated glass plates obtained in these examples was all 0.55 μm or more. The arithmetic mean roughness Ra (In) of the area In of the coated glass plates obtained in these examples were all 0.45 μm or less and 0.40 μm or less.
Similar results were obtained for Example 4 using the test piece.

As shown in Table 1, in both Examples 1 and 3, the glossiness Gr (In) of the region In where the film is present on the surface is higher than the glossiness Gr (Ex) of the region Ex where the shielding pattern is exposed. This was confirmed. The glossiness Gr(Ex) of the surface of the region Ex of the coated glass plate obtained in these examples was all 9 or less, 7 or less, and 5 or less. The glossiness Gr(In) of the region In of the coated glass plates obtained in these examples were all 10 or more, 20 or more, 25 or more, and 30 or more.
Similar results were obtained for Example 4 using the test piece.

[Examples 11 to 17]
A 3.5 mm thick unreinforced glass plate (“VFL” manufactured by AGC, green color) having a square shape of 300 mm×300 mm was prepared. In the same manner as Step S1 of Example 1, a commercially available ceramic paste for forming a shielding pattern (BP1) containing a black pigment and a glass frit was coated on one surface of this glass plate by a screen printing method. , dried and fired to form a shielding pattern (21). In this way, a glass plate (25X) with a shielding pattern was obtained. The planar shape of the shielding pattern was a 50 mm x 50 mm square cut out from a 200 mm x 200 mm square. The center and diagonal of the outer shape (200 mm x 200 mm square) and inner shape (50 mm x 50 mm square) of the shielding pattern were aligned with the center and diagonal of the glass plate. The thickness of the shielding pattern was 15 μm.
On the shielding pattern of the obtained glass plate with a shielding pattern, a liquid composition for film formation (LC1) was applied by spin coating to form a coating film (22W). Thereafter, a step similar to step S3 of Example 1 was carried out to cure the coating film and form a coating (22). In the manner described above, a coated glass plate (20) was obtained. In Examples 11 to 17, the thickness of the coating was changed by changing the rotation speed of the spin coater.
SEM cross-sectional observation of the coated glass plate obtained in each example was carried out to determine the ratio (C _T /S _{T ) of the coating thickness (C T )} to the thickness of the shielding pattern (S _T ). In addition, the surface gloss and initial crack resistance of the coating were evaluated. The evaluation results are shown in Table 2.

As _{shown in} Table 2 _, when the ratio ( _C A coated glass plate was obtained in which the glass plate had a hardness of 10 or more, an evaluation of initial crack resistance of “A” or “B”, a high surface gloss, and good initial crack resistance.
In particular, when C _T /S _T is within the range of 0.05 to 0.5, the surface gloss is 30 or more, the initial crack resistance evaluation is "A", and the surface gloss is high; A coated glass plate with excellent initial crack resistance was obtained.

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

20: Covered glass plate, 21: Shielding pattern, 22: Coating, 22A: First increased thickness portion, 22B: Reduced thickness portion, 22C: Second increased thickness portion, 22D: Rising surface, 22W: Coating coating film, 25: glass plate, 25X: glass plate with shielding pattern, 26: surface of glass plate, 27: liquid composition for film formation, 28: nozzle, 30: jig, 34: sealing material, 35: window frame Member, 102: Front bench glass, WG: Vehicle window glass with window frame member, Ar: region, Ex: region, In: region, Op: region, Tr: region.

Claims (15)

A coated glass plate comprising a glass plate and a shielding pattern and a coating laminated on one surface of the glass plate,
The coated glass plate has a translucent region Tr in a region other than a peripheral region in a plan view, and a region In adjacent to the region Tr and relatively close to the region Tr in the peripheral region; a region Ex adjacent to the region In and relatively far from the region Tr;
The shielding pattern covers the surface of the region In and the region Ex of the glass plate,
The coating covers the surface of the region Tr of the glass plate and the surface of the region In of the shielding pattern, but does not cover the surface of the region Ex of the shielding pattern,
The coating has an increasing thickness portion in the region Tr that becomes gradually thicker as it approaches the region In, and a decreasing thickness portion that gradually becomes thinner as it approaches the region Ex in the region In. Coated glass plate. The coated glass plate according to claim 1, wherein the coating further has an increasing thickness portion within the region In and on the region Ex side of the decreasing thickness portion, the thickness increasing as the thickness approaches the region Ex. The coated glass plate according to claim 1 or 2, wherein within the region In, the ratio of the thickness of the coating to the thickness of the shielding pattern is 0.02 to 0.8. The coated glass plate includes, in a plan view, a layer on the surface of the glass plate in the peripheral area, on the opposite side of the area In and the area Ex with the area Tr in between, and adjacent to the area Tr. has a region Op in which the shielding pattern is laminated;
The coated glass plate according to claim 1 or 2, wherein the coating further covers at least a portion of the region Op of the shielding pattern. The coated glass plate according to claim 1 or 2, wherein the surface roughness of the area In of the coated glass plate is smaller than the surface roughness of the area Ex of the coated glass plate. The arithmetic mean roughness Ra of the surface of the region Ex of the coated glass plate is 0.55 μm or more, and the arithmetic mean roughness Ra of the surface of the region In of the coated glass plate is 0.45 μm or less. 5. The coated glass plate according to 5. The coated glass plate according to claim 1 or 2, wherein the surface gloss of the region In of the coated glass plate is higher than the surface gloss of the region Ex of the coated glass plate. The surface of the area Ex of the coated glass plate has a glossiness of 9 or less as measured in accordance with JIS Z 8741, and the surface of the area In of the coated glass plate is measured in accordance with JIS Z 8741. The coated glass plate according to claim 7, having a glossiness of 10 or more. The coated glass plate according to claim 1 or 2, wherein the coating contains a siloxane compound. The glass plate 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 plate according to claim 1 or 2, wherein the shielding pattern exists along the entire circumference of the glass plate. For vehicle window glass that is attached to a window frame member provided on a vehicle body from the outside of the vehicle body,
At least a part of the surface of the area Ex of the shielding pattern is an adhesive surface that is adhered to the window frame member,
The coated glass plate according to claim 1 or 2, wherein at least a part of the surface of the region In of the coating is a non-adhesive surface that is not bonded to the window frame member. An automobile front bench glass comprising the coated glass plate according to claim 1 or 2. A method for manufacturing a coated glass plate according to claim 1 or 2, comprising:
Step S1 of preparing a glass plate with a shielding pattern in which the shielding pattern is laminated on the surface of the region In and the region Ex of the glass plate;
Step S2 of applying a film-forming liquid composition by pouring onto the surface of the glass plate with the shielding pattern on which the shielding pattern is laminated to form a coating film;
a step S3 of drying, curing, or drying and curing the coating film to form the coating film,
In the step S2, while the surface of the region Ex of the glass plate with the shielding pattern is masked, the film-forming liquid composition is applied to the surface of at least the region Tr and the region In of the glass plate with the shielding pattern. A method for manufacturing a coated glass plate, wherein the film-forming liquid composition is poured in a direction from the region Tr side to the region In side so that the material flows down. A method for manufacturing a vehicle window glass with a window frame member using the coated glass plate according to claim 1 or 2,
a step S4 of attaching the coated glass plate to a window frame member provided on the vehicle body from the outside of the vehicle body;
In the step S4,
bonding at least a portion of the surface of the region Ex of the shielding pattern and the window frame member;
A method for manufacturing a vehicle window glass with a window frame member, wherein at least a part of the surface of the region In of the coating is not bonded to the window frame member.

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