JP2023062743A - Glass laminates and side glass for vehicles - Google Patents

Abstract

To provide a glass laminate having a coated glass plate with an inscription and a member with an adhesive layer, and having good visibility of the inscription and good adhesion of the member with the adhesive layer.SOLUTION: A glass laminate (1) includes a glass plate (10) having an inscription on one surface (SI) comprising a rough surface area with a larger surface roughness than the other portion; an engraved coated glass plate (2) having a coating film (20) formed over the engraving on the surface (SI) of the glass plate (10); and a member (3) with an adhesive layer affixed on the surface of the coating film (20) side of the engraved coated glass plate (2). When the smallest virtual rectangle inscribed with the mark is defined as the mark forming area (10M), the ratio of the overlapping area of the mark forming area (10M) and the member (3) with adhesive layer to the area of the mark forming area (10M) is 0 to 40% in plan view.SELECTED DRAWING: Figure 1A

Description

TECHNICAL FIELD The present invention relates to a glass laminate and a vehicle side glass.

In applications such as window glass, imprints such as letters, numbers, symbols, marks, and combinations thereof may be formed on the surface of the glass plate. For example, in a window glass for a vehicle, there are cases in which the name of a vehicle manufacturer, the name of a glass manufacturer, a product number, a JIS mark, a combination of these, and the like are stamped on the edge of the surface of a glass plate.
The engraving can be formed by partially roughening the surface of the colorless and transparent glass plate according to the engraving pattern by sandblasting or the like. The imprint formed by this method consists of a rough surface portion having a larger surface roughness than other portions, and has a high haze value due to light scattering and appears whitish.

In the above applications, a coating film having functions such as ultraviolet shielding and infrared shielding may be formed on the surface of the glass plate on which the engraving is formed.
In the present specification, the glass plate having the engraving is also referred to as "engraved glass plate". A glass plate having a coating film is also called a “coated glass plate”. A glass plate having a stamp and a coating film is also called a “stamped coated glass plate”.
For example, Patent Document 1 discloses a coated glass plate with a mark, which includes a glass plate and a coating film provided on the first main surface of the glass plate, and in which marks are formed on the first main surface of the glass plate. (Claim 1, Fig. 1).

JP 2015-074582 A JP 2016-108523 A

In the above applications, an anti-fogging film may be provided on the surface of the glass plate. As an anti-fogging film, a film containing a water-absorbent resin is known (Section [Background Art] of Patent Document 2).
As a method of providing an anti-fogging film on a glass plate, a method of attaching an anti-fogging film with an adhesive layer having a laminated structure of anti-fogging film/base film/adhesive layer on the surface of the glass plate, and a glass plate. A release film having a laminated structure of release film/anti-fogging film/adhesive layer and an anti-fogging film with an adhesive layer are attached to the surface of the adhesive layer, and then the release film is peeled off.

The present inventors conducted various studies on the case where a member with a coating film and/or an adhesive layer is provided on a glass plate with a stamp, and found that the presence of the adhesive layer may reduce the visibility of the stamp. I found out. In addition, it was found that the adhesion of the adhesive layer-attached member to the glass plate may be reduced in the engraving-forming region because the engraving-forming region of the glass plate has unevenness on the surface.

The present invention has been made in view of the above circumstances, and provides a glass laminate having a coated glass plate with a stamp and a member with an adhesive layer, and having good visibility of the stamp and good adhesion of the member with the adhesive layer. aim.

The present invention provides the following glass laminate and vehicle side glass.
[1] A glass plate having, on one surface thereof, a mark made of a rough surface portion having a larger surface roughness than that of the other portion, and a coating film formed on the surface of the glass plate so as to cover the mark. a coated glass plate;
A glass laminate having a member with an adhesive layer attached to the coating film side surface of the coating glass plate,
When the imprint forming area is defined as the smallest imaginary rectangle that inscribes the imprint in plan view,
A glass laminate, wherein a ratio of an overlapping area of the stamp-forming region and the adhesive layer-attached member to the area of the stamp-forming region in plan view is 0 to 40%.
[2] A vehicle side glass comprising the glass laminate of [1].

The glass laminate of the present invention has a coated glass plate with a stamp and a member with an adhesive layer, and in plan view, the ratio of the overlapping area of the stamp-forming region and the member with the adhesive layer to the area of the stamp-forming region is 0 to 40%. In the glass laminate of the present invention having such a structure, the overlapping area between the stamp forming region and the member with the adhesive layer is sufficiently reduced, so that the visibility of the stamp and the adhesion of the member with the adhesive layer are good.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic plan view of a glass laminate (vehicle side glass) according to one embodiment of the present invention; FIG. 4 is a schematic enlarged plan view showing an example of a stamp and a stamp forming region; BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic cross section of the glass laminated body (side glass for vehicles) of one Embodiment which concerns on this invention. 1 is a schematic cross-sectional view of a glass laminate (vehicle side glass) according to a first embodiment; FIG. FIG. 3 is a schematic cross-sectional view of a glass laminate (vehicle side glass) according to a second embodiment; FIG. 5 is a schematic plan view showing an example of a design change of the vehicle side glass; FIG. 11 is a schematic plan view showing another design modification example of the vehicle side glass; FIG. 11 is a schematic plan view showing another design modification example of the vehicle side glass; FIG. 4 is an enlarged cross-sectional image diagram of a marking forming region of the glass laminate when the marking, the coating film, and the adhesive layer are completely overlapped.

Generally, thin film structures are referred to as "films" and "sheets", etc., depending on thickness. We do not make a clear distinction between them here. Therefore, the "film" referred to in this specification may include the "sheet".
In this specification, unless otherwise specified, the "surface of the glass plate" refers to a major surface with a large area, excluding end faces (also referred to as side faces) of the glass plate.
In this specification, unless otherwise specified, in the vehicle side glass, the forward direction of the vehicle is defined as the forward direction, and the backward direction of the vehicle is defined as the rearward direction. In addition, unless otherwise specified, "front and rear", "up and down", "left and right", "vertical and horizontal", and "inside and outside" refer to "front and back" when the vehicle side glass is installed in the vehicle (actual usage state). They are "up and down", "left and right", "vertical and horizontal", and "inner and outer".
In this specification, unless otherwise specified, ultraviolet light is light in the wavelength range of 300-380 nm, and infrared light is light in the wavelength range of 780-2500 nm.
In this specification, unless otherwise specified, the numerical range "to" is used to include the numerical values before and after it as lower and upper limits.

[Glass laminate, vehicle side glass]
The present invention relates to a glass laminate, and its use is not particularly limited. The glass laminate of the present invention is suitable for vehicle window glass and the like. The present invention is particularly suitable for vehicle side glass and the like.
Embodiments of the present invention will be described below by taking an example of application to a side glass for a vehicle.

A structure of a glass laminate (vehicle side glass) according to one embodiment of the present invention will be described with reference to the drawings. FIG. 1A is a schematic overall plan view of the glass laminate of the present embodiment. FIG. 1B is a schematic enlarged plan view showing an example of a stamp and a stamp forming region. FIG. 2 is a schematic cross-sectional view (cross-sectional view taken along line II-II) of the glass laminate of this embodiment. 3A and 3B are schematic cross-sectional views (cross-sectional views taken along line II-II) of first and second aspects of the vehicle side glass of the present embodiment. In order to facilitate visual recognition, the scale of each component is appropriately changed from the actual scale.

As shown in FIGS. 1A and 2, a glass laminate (vehicle side glass) 1 of this embodiment has a stamped coated glass plate 2 and a member 3 with an adhesive layer.
The stamped coated glass plate 2 is a glass plate having stamps on one surface (in this embodiment, the surface on the inside of the vehicle) SI, which is a rough surface portion having a larger surface roughness than the other portions. and a coating film 20 formed on the surface SI of the engraved glass plate 10 to cover the engraved marks.
The member 3 with an adhesive layer includes a film with an adhesive layer, a film with an adhesive layer, and the like, and is attached on the surface of the coating glass plate 2 with a stamp on the side of the coating film 20 .

In the present invention, the smallest imaginary rectangle that inscribes the marking in plan view is defined as the marking forming area. FIG. 1B shows a schematic enlarged plan view showing an example of a stamp and a stamp forming region. In FIGS. 1A and 1B, reference numeral 10L indicates a marking, and reference numeral 10M indicates a marking forming region. In addition, in FIG. 1A, the marking forming region 10M is illustrated large so as to be easily visible.
The engraving 10L can be formed by partially roughening the surface of the colorless and transparent glass plate according to the pattern of the engraving 10L by a method such as sandblasting, shotblasting, wet etching, or the like. The marking 10L formed by this method consists of a rough surface portion having a larger surface roughness than other portions, and has a high haze value due to light scattering, and appears whitish.
The engraving 10L is letters, numbers, symbols, marks, combinations thereof, or the like. In a vehicle window glass such as a vehicle side glass, the engraving 10L is a vehicle manufacturer's name, a glass manufacturer's name, a product number, a JIS mark, a combination thereof, or the like. In FIG. 1B, circles indicate letters, numbers, symbols, marks, and the like.

In the present embodiment, when the forward direction of the vehicle is defined as the forward direction and the reverse direction of the vehicle is defined as the rearward direction, the glass plate 10 with the engraving is on the front side in a plan view in a state fitted in the vehicle. It has a side 11 , a rear side 12 , an upper side 13 and a lower side 14 . The planar shape of the engraved glass plate 10 is appropriately designed according to the type of vehicle.
Each side of the engraved glass plate 10 may be any one of a straight line, a combination of a plurality of straight lines, a single curved line, and a combination of one or more straight lines and one or more curved lines. When the perimeter of the engraved glass plate 10 includes curved lines, the boundary between two sides adjacent to each other is not necessarily clear.

The coating film 20 is a film formed by a coating method including a step of coating a liquid composition for forming a coating film (also referred to as coating film composition) on a glass plate. The formation area includes the stamp formation area 10M. In this embodiment, the coating film 20 is formed covering substantially the entire surface of the glass plate 10 with a stamp.
The coating film 20 can contain one or more functional materials such as ultraviolet shielding agents and infrared shielding agents.
A method for forming the coating film 20 will be described later.

In this embodiment, the adhesive layer-attached member 3 such as the adhesive layer-attached film and the adhesive layer-attached film is smaller in size than the engraved glass plate 10 and the coating film 20, and can be designed in any shape.
In the present embodiment, when the forward direction of the vehicle is defined as the forward direction and the backward direction of the vehicle is defined as the rearward direction, the adhesive layer-attached member 3 is positioned on the front side in a plan view in a state fitted in the vehicle. It may have a side 31 , a rearward side 32 , a top side 33 and a bottom side 34 .
Each side of the adhesive layer-attached member 3 may be any of one straight line, a combination of multiple straight lines, one curved line, and a combination of one or more straight lines and one or more curved lines.
The adhesive layer-attached member 3 preferably has a chamfered shape.
When the outer periphery of the adhesive layer-attached member 3 includes a curved line, the boundary between two sides adjacent to each other is not necessarily clear.

As shown in FIGS. 3A and 3B, the adhesive layer-attached member 3 can include an adhesive layer 30 and a functional film 50 .
Examples of the functional film 50 include an anti-fogging film, a scratch-resistant film, an anti-fouling film, and the like.
As a method of providing the functional film 50 on the glass plate 10 with a stamp, a method 1 of sticking a film with an adhesive layer having a laminated structure of functional film/base film/adhesive layer on the surface of the glass plate, and a glass plate. A release film having a laminate structure of release film/functional film/adhesive layer and a functional film with an adhesive layer are attached to the surface of the adhesive layer, and then the release film is peeled off.
By the method 1 described above, it is possible to provide the glass laminate (vehicle side glass) 1X of the first embodiment, to which the adhesive layer-attached film 3X including the adhesive layer 30, the base film 40, and the functional film 50 shown in FIG. 3A is attached. .
A glass laminate of the second embodiment (vehicle side glass) in which a film 3Y with an adhesive layer including an adhesive layer 30 and a functional film 50 is attached to the surface of a glass plate 10 with a stamp shown in FIG. 3B by the method 2 above. ) 1Y.
A method for forming the functional film 50 will be described later.

The present inventors conducted various studies on the case where a member with a coating film and/or an adhesive layer is provided on a glass plate with an engraving, and found that the visibility of the engraving may be lowered.
(Case 1)
When only the coating film is provided on the surface unevenness of the stamp-forming region of the glass plate with a stamp, the coating film of the stamp-forming region can be formed to have surface unevenness along the surface unevenness of the stamp-forming region of the glass plate. (See coating film 20 in FIG. 5). In this case, since surface irregularities of the coating film exist on the outermost surface of the engraving formation region of the glass laminate, and light scattering occurs on the surface irregularities, the visibility of the engraving can be ensured.

(Case 2)
Even if the adhesive layer is directly provided on the surface unevenness of the engraving forming region of the glass plate with engraving, it is difficult for the adhesive layer to completely fill the concave portions of the surface of the engraving forming region of the glass plate. In this case, an air layer remains between the surface unevenness of the marking forming region of the glass plate and the adhesive layer, and light scattering occurs on the surface unevenness of the marking forming region of the glass plate, so that the visibility of the marking can be ensured.

(Case 3)
FIG. 5 shows an enlarged cross-sectional image diagram of the marking forming region of the glass laminate when the marking, the coating film, and the adhesive layer are completely overlapped. In the figure, reference numeral 10A schematically indicates a convex portion of the stamp, which is shown enlarged here for easy viewing.
When the coating film 20 is provided on the surface unevenness of the engraving forming region 10M of the engraving glass plate 10 and the adhesive layer 30 is provided thereon, as schematically shown in FIG. There is a possibility that it will enter the recesses of the surface unevenness of the coating film 20 formed with the described surface unevenness and further cover the coating film 20 . In this case, there is a possibility that the engraving formation region 10M of the glass laminate will have less surface irregularities in contact with the air, light scattering on the surface irregularities will be reduced, and the visibility of the engraving will be reduced.

The present inventors have also found that the adhesion of the adhesive layer-attached member to the glass plate is reduced in the engraving-formed region of the engraving-formed glass plate because the engraving-formed region has surface irregularities. It has been found that the adhesive layer-attached member may peel off from the glass plate in the engraving formation region under environments such as a high-temperature environment, a high-humidity environment, and a high-temperature and high-humidity environment.

The present inventors found the ratio of the overlapping area (Sb) between the marking forming region 10M and the adhesive layer-attached member 3 to the area (Sa) of the marking forming region 10M, the visibility of the marking 10L, and the adhesive layer-attached member 3. A study was conducted on the relationship with the adhesion to the glass plate. As a result, by optimizing the ratio of the overlapping area (Sb) between the stamp forming region 10M and the adhesive layer-attached member 3, the visibility of the stamp 10L and the adhesion of the adhesive layer-attached member 3 to the glass plate can be improved. I found
In order to improve the visibility of the marking 10L and the adhesion of the member 3 with the adhesive layer, it was found that the ratio of the overlapping area (Sa) between the marking forming region 10M and the member 3 with the adhesive layer is preferably small. .

In the present embodiment, in the glass laminate (vehicle side glass) 1, the overlapping area (Sb) of the stamp forming region 10M and the adhesive layer-attached member 3 with respect to the area (Sa) of the stamp forming region 10M in plan view. The proportion is 0-40%, preferably 0-30%, more preferably 0-20%, particularly preferably 0-10%, most preferably 0%.
The fact that the ratio of the overlapping area (Sb) between the marking forming region 10M and the member 3 with the adhesive layer to the area (Sa) of the marking forming region 10M is 0% means that the marking forming region 10M and the member 3 with the adhesive layer do not overlap at all, or the adhesive layer-attached member 3 does not exist at all on the stamp forming region 10M.
The area (Sa) of the imprint forming region 10M is not particularly limited, and is preferably 600-3000 mm ² , more preferably 800-1500 mm ² .

4A to 4C are schematic plan views showing design modifications of the positional relationship between the engraved glass plate 10 and the member 3 with an adhesive layer. These figures are simplified diagrams (image diagrams) corresponding to FIG. 1A.
As shown in FIG. 4C, the adhesive layer-attached member 3 may have a shape in which one corner is cut out from a square or a similar shape so as not to overlap the marking forming region 10M.
The examples shown in FIGS. 4A and 4C are examples in which the ratio of the overlapping area (Sb) between the marking forming region 10M and the member 3 with the adhesive layer to the area (Sa) of the marking forming region 10M is 0%.
As shown in FIGS. 1A, 4A, and 4B, from the viewpoint of appearance, etc., the front side 11 of the engraved glass plate 10 and the front side 31 of the member 3 with the adhesive layer are substantially parallel. , and the rear side 12 of the glass plate 10 with a stamp and the rear side 32 of the adhesive layer-attached member 3 are preferably substantially parallel to each other.
In this specification, "two sides are substantially parallel" is defined as two sides being completely parallel or an intersection angle of extension lines of two sides being 30° or less. If the sides are not straight lines, an approximate straight line is obtained to obtain the crossing angle.

From the viewpoint of visibility and ease of formation of the marking 10L, the arithmetic mean surface roughness (Ra) of the marking 10L is preferably 1.0 to 5.0 μm, more preferably 2.0 to 5.0 μm, particularly preferably 2.0 to 3.0 μm.
The arithmetic mean surface roughness (Ra) of the engraved non-forming region of the engraved glass plate 10 is usually less than 1.0 μm, for example, 0.01 to 0.7 μm.
As used herein, "surface roughness (Ra)" is the arithmetic mean roughness determined according to JIS B 0601 (2013).

The haze value of the marking 10L is preferably 20% to 90%, more preferably 30% to 80%, and particularly preferably 50% to 80%, from the viewpoint of visibility and ease of formation of the marking 10L.
The haze value of the non-engraved region of the engraved glass plate 10 is usually less than 1%, for example 0.01 to 0.7%.
The average haze value of the engraving forming region 10M of the engraving glass plate 10 is the average value obtained by dividing the engraving forming region 10M into 1 cm squares and measuring the haze value for each divided region. This average haze value is preferably 4 to 30%, more preferably 5 to 25%, particularly preferably 7 to 20%.
The "haze value" can be measured by the method described in the section [Examples] below.

The thickness of the coating film 20 can be appropriately designed according to the type of functional material and the required functions. 2 to 5 μm.
The thickness of the adhesive layer 30 included in the adhesive layer-attached member 3 can be appropriately designed, and is preferably 10 to 200 μm, more preferably 10 to 100 μm, particularly preferably 10 to 50 μm from the viewpoint of adhesiveness, cost, and the like.

The ratio of the area of the adhesive layer-attached member 3 to the area of the glass plate 10 with the engraving can be appropriately designed. When the ratio of the area of the member 3 with the adhesive layer to the area of the glass plate 10 with the engraving is large, the function expression region of the functional film 50 becomes wide. It can grow. In the present invention, as described above, in order to improve the visibility of the marking 10L and the adhesion of the member 3 with the adhesive layer, it is preferable to reduce the overlap between the marking 10L and the member 3 with the adhesive layer.
From the viewpoint of manifesting the function of the functional film 50 and reducing the overlap between the marking 10L and the member 3 with the adhesive layer, the ratio of the area of the member 3 with the adhesive layer to the area of the glass plate 10 with the marking in plan view. is preferably 30 to 90%, more preferably 40 to 90%, particularly preferably 60 to 90%.

The location where the marking 10L is formed is not particularly limited, and an inconspicuous location is preferable. The engraving 10L is preferably formed at the edge of the glass plate 10 with engraving. The area where the adhesive layer-attached member 3 is attached is designed so that the overlap between the stamp 10L and the adhesive layer-attached member 3 is reduced according to the location where the stamp 10L is formed.
The adhesive layer-attached member 3 can be provided in a relatively wide range including the center of the glass plate 10 with a stamp or the central portion. Depending on the shape of the engraved glass plate 10, the "center" cannot be clearly defined. In this case, a similar shape is drawn in which the area is as small as possible by shrinking the same distance inward from the outer periphery, and the region of this similar shape is defined as the central portion.
As shown in FIG. 1A, in the engraved glass plate 10, there is a non-existing region 71 of the adhesive layer-attached member 3 at the front side end portion including the front side edge 11 of the glass plate and the vicinity thereof. good too. A non-existing region 72 of the adhesive layer-attached member 3 may be present at the rear side end including the rear side 12 of the glass plate and its vicinity. A non-existing area 73 of the member 3 with the adhesive layer may be present in the upper end portion including the upper side 13 of the glass plate and its vicinity. There may be a non-existence region 74 of the member 3 with the adhesive layer in the lower end portion including the lower edge 14 of the glass plate and its vicinity.
In this specification, unless otherwise specified, the "portion near a certain side" is a range within 100 mm from a certain side.

In applications such as a vehicle side glass, as shown in FIG. 1A, the engraving 10L can be formed on the rear side end including the rear side 12 of the glass plate 10 with the engraving and the vicinity thereof. It is preferably formed at the lower end of the rear side end of the plate 10 .
In this case, the adhesive layer-attached member is arranged so that the adhesive layer-attached member 3 does not exist region 72 at least at the rear side end including the rear side edge 12 of the engraved glass plate 10 and its vicinity. 3 application areas can be designed.

Since the engraving region 10M of the engraving glass plate 10 has surface irregularities, the adhesive layer-attached member 3 has a corner portion with an angle of less than 90° (also referred to as an acute angle) that overlaps or is close to the engraving forming region 10M. In particular, if the corner has an angle (acute angle) of less than 90° that overlaps with the stamp forming region 10M, the corner is relatively peeled off in a high-temperature environment, a high-humidity environment, or a high-temperature and high-humidity environment. may be easier.
Therefore, it is preferable that the adhesive layer-attached member 3 does not have a corner portion with an angle (acute angle) of less than 90° that overlaps or is close to the marking forming region 10M, and particularly an angle of less than 90° (acute angle) that overlaps with the marking forming region 10M. It is preferred not to have sharp corners.
In this specification, unless otherwise specified, "the imprint forming area is close to the corner" is defined as the shortest distance between the imprint forming area and the corner being 100 mm or less.

In FIGS. 1A and 4A to 4C, reference numeral 3C denotes a corner portion overlapping or adjacent to the marking forming region 10M of the member 3 with the adhesive layer.
In the example shown in FIG. 1A, the angle θ of the corner 3C adjacent to the marking forming region 10M of the adhesive layer-attached member 3 is greater than 90°. In the example shown in FIGS. 4A and 4B, the angle θ of the corner 3C adjacent to the marking forming region 10M of the adhesive layer-attached member 3 is 90°. In the example shown in FIG. 4C, the angle θ of the corner 3C adjacent to the marking forming region 10M of the adhesive layer-attached member 3 is less than 90°.
When the adhesive layer-attached member 3 has a corner portion 3C that overlaps or is adjacent to the imprint forming region 10M, the angle θ is preferably 90° or more, more preferably 100°, as shown in FIGS. ° or more, particularly preferably 110° or more, most preferably 120° or more.

As shown in FIG. 4B, when the adhesive layer-attached member 3 having sides with different lengths on the front side and the back side is superimposed on the stamp 10L, the longer side of the adhesive layer-attached member 3 is , and the inscription 10L. In the example shown in FIG. 4B, in the adhesive layer-attached member 3, the side edge 32 on the rear side is longer than the side edge 31 on the front side. In this case, as shown in the figure, it is preferable that the side edge 32 on the rear side overlaps the marking 10L.
Since the engraving formation region 10M of the engraving glass plate 10 has unevenness on the surface, there is a tendency that the adhesion of the member 3 with the adhesive layer to the glass plate decreases in the engraving formation region 10M. If the member 3 with the adhesive layer is superimposed on the marking 10L, by overlapping the longer side on the marking 10L, the length of the side existing on the marking with respect to the overall length of the side of the member 3 with the adhesive layer can be reduced, and peeling of the side edge of the adhesive layer-attached member 3 can be effectively suppressed.

(glass plate)
Examples of the glass plate constituting the glass plate 10 with the engraving include laminated glass in which a plurality of glass plates are laminated via an intermediate film, tempered glass, or organic glass, and laminated glass or tempered glass is preferable.

There are no particular restrictions on the type of glass plate that is the material for laminated glass and tempered glass, and examples thereof include soda lime glass, borosilicate glass, aluminosilicate glass, lithium silicate glass, quartz glass, sapphire glass, and alkali-free glass.
The tempered glass is obtained by tempering the above-described glass plate by a known method such as an ion exchange method or an air-cooling tempering method. Air-cooled tempered glass is preferable as the tempered glass.

The thickness of the laminated glass is not particularly limited, and is preferably 2 to 6 mm when used as a vehicle side glass.
When the laminated glass is composed of two glass plates, the thickness of the glass plate on the inside of the vehicle and the thickness of the glass plate on the outside of the vehicle may or may not be the same. The thickness of the glass plate inside the vehicle is preferably 0.3 to 2.3 mm. When the thickness of the glass plate on the inside of the vehicle is 0.3 mm or more, the handling property is good, and when it is 2.3 mm or less, the mass does not become too large. The thickness of the vehicle-exterior glass plate is preferably 1.0 to 3.0 mm. When the thickness of the glass plate on the outside of the vehicle is 1.0 mm or more, strength such as resistance to stepping stones is sufficient, and when it is 3.0 mm or less, the mass of the laminated glass does not become too large, and the fuel efficiency of the vehicle is improved. point is preferable. If both the thickness of the glass plate on the vehicle exterior side and the thickness of the glass plate on the vehicle interior side are 1.8 mm or less, both weight reduction and sound insulation of the laminated glass can be achieved, which is preferable.

The thickness of the tempered glass is not particularly limited, and is preferably 1.5 to 6 mm when used as a side glass for vehicles. If the tempered glass has a thickness of 1.5 mm or more, it is easy to obtain tempered glass that satisfies the crushing standards for surface compressive stress and internal tensile stress in contrast to this in the air-cooling tempering method.

The vehicle side glass may have a curved shape such that the outside of the vehicle is convex when attached to the vehicle. Gravity molding, press molding, roller molding, and the like are used for bending the vehicle side glass.

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

Laminated glass and tempered glass may have a light shielding layer in a predetermined area. The light-shielding layer can be formed by a known method. For example, a ceramic paste containing a black pigment and a glass frit is applied to a predetermined region on the surface of a glass plate or tempered glass, which is the material of laminated glass, and fired. , can be formed. The thickness of the light shielding layer is not particularly limited, and is, for example, 5 to 20 μm. The light-shielding layer can be formed, for example, in the peripheral area of any surface of laminated glass and tempered glass.

(coating film)
Coating film 20 can include one or more functional materials. Functional materials include ultraviolet shielding agents, infrared shielding agents, antibacterial agents, antireflection agents, water repellent agents, oil repellent agents, and the like.

A known ultraviolet shielding agent can be used, and it may be of an ultraviolet absorption type or an ultraviolet reflection type, and an ultraviolet absorber is preferable.
UV absorbers include benzotriazoles such as 2-(2'-hydroxy-5'-methylphenyl)benzotriazole and 2-(2'-hydroxy-3',5'-di-t-butylphenyl)benzotriazole Compounds; 2,2′,4,4′-tetrahydroxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 5,5′-methylenebis ( benzophenone compounds such as 2-hydroxy-4-methoxybenzophenone); 2-(2-hydroxy-4-octoxyphenyl)-4,6-bis(2,4-di-t-butylphenyl)-s-triazine, 2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-s-triazine and 2-(2-hydroxy-4-propoxy-5-methylphenyl)-4,6-bis(2,4 hydroxyphenyltriazine compounds such as -di-t-butylphenyl)-s-triazine; ethyl-α-cyano-β,β-diphenylacrylate and methyl-2-cyano-3-methyl-3-(p-methoxyphenyl) cyanoacrylate compounds such as acrylates; organic dyes such as polymethine compounds, imidazoline compounds, coumarin compounds, naphthalimide compounds, perylene compounds, azo compounds, isoindolinone compounds, quinophthalone compounds and quinoline compounds;
The concentration of the UV absorber in the coating film 20 can be designed according to the type and thickness of the UV absorber, preferably 3 to 40% by mass, more preferably 6 to 30% by mass, and particularly preferably 8 to 18% by mass. %.

<Infrared shielding agent>
As the infrared shielding agent, a known one can be used, and an infrared absorbing type or an infrared reflecting type may be used, and an infrared absorbing agent is preferable.
Examples of infrared absorbers include polymethine compounds, cyanine compounds, phthalocyanine compounds, naphthalocyanine compounds, naphthoquinone compounds, anthraquinone compounds, dithiol compounds, immonium compounds, diimonium compounds, aminium compounds, pyrylium compounds, cerium compounds, squarylium compounds, and benzene. Organic infrared absorbers such as counterion conjugates of dithiol metal complex anions and cyanine dye cations; tungsten oxide, tin oxide, indium oxide, magnesium oxide, titanium oxide, chromium oxide, zirconium oxide, nickel oxide, aluminum oxide, oxide inorganic infrared absorbers such as zinc, iron oxide, ammonium oxide, lead oxide, bismuth oxide, lanthanum oxide, tungsten oxide, indium tin oxide (ITO), and antimony tin oxide;
As the infrared absorbing agent, an inorganic infrared absorbing agent is preferable, and its form is preferably fine particles.
The concentration of the infrared absorbing agent in the coating film 20 can be designed according to the type and thickness of the infrared absorbing agent, preferably 5 to 30% by mass, more preferably 7 to 20% by mass, and particularly preferably 10 to 18% by mass. %.

The coating film 20 may further contain one or more metal oxides including silica in order to ensure the strength of the coating film 20, especially its abrasion resistance.
As a metal oxide material, one or more kinds of metal oxide fine particles and/or one or more kinds of hydrolyzable metal compounds can be used.
The coating film 20 can further contain one or more optional ingredients as needed.
The coating film 20 can be formed by a coating method including a step of applying a liquid composition for coating film formation (coating film composition).
The method of forming the coating film 20 includes one or more functional materials such as an ultraviolet shielding agent and an infrared shielding agent and a solvent, and more preferably a liquid coating film composition containing a metal oxide or its material. It can include a step of preparing, a step of applying this coating film composition onto the engraved glass plate 10 (coating step), and a step of drying the coating film (drying step).
Examples of metal oxides or their materials, examples of optional components, and film formation methods can be applied to the description of the antifogging film described later.

Coating film 20 may contain one or more known resins instead of or in combination with metal oxides. Examples of resins include epoxy-based resins, acrylic-based resins, and silicone-based resins.

(Anti-fogging film)
As the functional film 50 that can be included in the member 3 with an adhesive layer, an anti-fogging film can be mentioned.
The anti-fogging film can contain one or more water absorbing resins or hydrophilic resins.
The anti-fogging coating preferably further contains one or more metal oxides including silica in order to ensure the strength of the anti-fogging coating, particularly its abrasion resistance.
The content of the water absorbing resin and/or hydrophilic resin in the antifogging film is not particularly limited, and is preferably 50% by mass or more, more preferably 60% by mass, from the viewpoint of film hardness, water absorption, and antifogging properties. As described above, the content is particularly preferably 65% by mass or more, preferably 95% by mass or less, more preferably 90% by mass or less, and particularly preferably 85% by mass or less.
In this specification, unless otherwise specified, the "content of water-absorbing resin and/or hydrophilic resin" means the total content when the anti-fogging film contains multiple types of water-absorbing or hydrophilic resins. .

<Water Absorbent Resin or Hydrophilic Resin>
The water absorbent resin or hydrophilic resin is not particularly limited, and may be polyethylene glycol, polyether resin, polyurethane resin, starch resin, cellulose resin, acrylic resin, epoxy resin, polyester polyol, hydroxyalkyl cellulose, polyvinyl. alcohol, polyvinylpyrrolidone, polyvinyl acetal resin, polyvinyl acetate, and the like.
Among them, hydroxyalkyl cellulose, polyvinyl alcohol, polyvinylpyrrolidone, polyvinyl acetal resin, polyvinyl acetate, epoxy resin and polyurethane resin are preferable, polyvinyl acetal resin, epoxy resin and polyurethane resin are more preferable, and polyvinyl acetal resin and Epoxy resins and the like are particularly preferred.

Polyvinyl acetal resin can be synthesized by condensing polyvinyl alcohol with aldehyde to acetalize it. Methods for acetalizing polyvinyl alcohol include a precipitation method using an aqueous medium in the presence of an acid catalyst, and a dissolution method using a solvent such as alcohol. Acetalization may be carried out in parallel with the saponification of the polyvinyl acetate.

Aliphatic aldehydes and aromatic aldehydes can be mentioned as aldehydes to be condensed with polyvinyl alcohol. Aliphatic aldehydes include formaldehyde, acetaldehyde, butyraldehyde, hexylcarbaldehyde, octylcarbaldehyde, decylcarbaldehyde, and the like. Aromatic aldehydes include benzaldehyde; alkyl group-substituted benzaldehydes such as 2-methylbenzaldehyde, 3-methylbenzaldehyde, and 4-methylbenzaldehyde; halogen atom-substituted benzaldehydes such as chlorobenzaldehyde; Substituted benzaldehyde in which a hydrogen atom is substituted with a functional group other than an alkyl group such as group; condensed aromatic ring aldehydes such as naphthaldehyde and anthraldehyde;

The degree of acetalization of the polyvinyl acetal resin is not particularly limited, and is advantageous for forming an anti-fogging film having good water absorption and water resistance. Especially preferably 5 to 20 mol %, most preferably 5 to 15 mol %. The degree of acetalization can be measured, for example, by ¹³ C nuclear magnetic resonance spectroscopy.
The average polymerization degree of polyvinyl alcohol is not particularly limited, and is preferably 200 to 4500, more preferably 500 to 4500, because it is advantageous for forming an antifogging film having good water absorption and water resistance. The saponification degree of polyvinyl alcohol is preferably 75 to 99.8 mol %.

Examples of epoxy-based resins include glycidyl ether-based epoxy resins, glycidyl ester-based epoxy resins, glycidylamine-based epoxy resins, and cycloaliphatic epoxy resins. Among them, cycloaliphatic epoxy resins and the like are preferable.

The polyurethane-based resin is a polyurethane obtained by copolymerizing one or more polyisocyanates having two or more isocyanate groups in one molecule and one or more polyols having two or more hydroxyl groups in one molecule. system resin and the like. Preferred polyols include acrylic polyols and polyoxyalkylene polyols.

<Metal oxide>
Metal oxides include oxides of at least one metal element selected from Si, Ti, Zr, Ta, Nb, Nd, La, Ce, and Sn. In order to ensure the strength of the anti-fog coating, especially its abrasion resistance, the anti-fog coating can contain one or more metal oxides, including silica.
The content of the metal oxide in the antifogging film (the total content when the antifogging film contains multiple kinds of metal oxides) is not particularly limited. As the content of the metal oxide increases, the strength of the anti-fogging film, particularly the abrasion resistance, increases. From the viewpoint of the balance between the strength and antifogging properties of the antifogging film, the preferred content of the metal oxide is as follows.
The content of the metal oxide is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, still more preferably 0.1 part by mass or more, with respect to 100 parts by mass of the content of the water absorbent resin and/or the hydrophilic resin. It is 2 parts by mass or more, more preferably 1 part by mass or more, most preferably 5 parts by mass or more, and may be 10 parts by mass or more or 20 parts by mass or more. The content of the metal oxide is preferably 50 parts by mass or less, more preferably 45 parts by mass or less, still more preferably 40 parts by mass or less, particularly preferably 35 parts by mass or less, and most preferably 33 parts by mass or less. It may be less than or equal to parts by mass.

The form of the metal oxide contained in the antifogging film is not particularly limited. At least some of the metal oxides can be particulate. The metal oxide fine particles have an excellent effect of transmitting the stress applied to the antifogging film to the glass plate supporting the antifogging film, and have high hardness. Therefore, the addition of metal oxide fine particles is advantageous from the viewpoint of improving the wear resistance of the antifogging film. In addition, when metal oxide fine particles are added to the antifogging film, minute voids are formed at the sites where the fine particles are in contact or close to each other, and water vapor is easily taken into the film through these voids. Therefore, the addition of metal oxide fine particles may act advantageously for improving the anti-fogging property.
Metal oxide fine particles can be added to an antifogging film by adding metal oxide fine particles or a dispersion containing the same to a liquid composition for forming an antifogging film (also referred to as an antifogging film composition). . Colloidal silica etc. are mentioned as a dispersion liquid containing metal oxide microparticles|fine-particles.

The average particle diameter of the metal oxide fine particles is not particularly limited, and is preferably 1 to 20 nm, more preferably 5 to 20 nm, from the viewpoints of suppression of white turbidity of the antifogging film and uniform dispersion of the fine particles.
The "average particle size" referred to here is the average particle size of primary particles, and is the average value of the particle sizes of 50 arbitrarily selected fine particles measured by scanning electron microscope (SEM) observation.
The content of the metal oxide fine particles is not particularly limited, and from the viewpoint of suppressing clouding of the anti-fogging film and ensuring anti-fogging properties, it is preferably 0 per 100 parts by mass of the content of the water-absorbing resin and/or hydrophilic resin. to 50 parts by weight, more preferably 2 to 30 parts by weight, particularly preferably 5 to 25 parts by weight, and most preferably 10 to 20 parts by weight.

<Hydrolyzable metal compound>
A metal compound having a hydrolyzable group (also referred to as a hydrolyzable metal compound) and/or a hydrolyzate thereof can be used as a material for the metal oxide. Hydrolyzable metal compounds include silicon compounds having a hydrolyzable group represented by the following formula (I) (also referred to as silicon compounds (I)).
The antifogging film can contain silica derived from the silicon compound (I) and/or its hydrolyzate. In this specification, silica includes a silicon compound containing a siloxane bond in which an organic metal is directly bonded to a part of silicon.

R _m SiX _4-m (I)
In the above formula (I), R is a hydrocarbon group having 1 to 3 carbon atoms in which a hydrogen atom may be substituted with a reactive functional group. Examples of hydrocarbon groups having 1 to 3 carbon atoms include alkyl groups having 1 to 3 carbon atoms (specifically, methyl group, ethyl group, n-propyl group, and isopropyl group) and alkenyl groups having 2 to 3 carbon atoms. (specifically, a vinyl group, an allyl group, and a propenyl group) and the like.

The reactive functional group is preferably at least one selected from oxyglycidyl groups and amino groups. The hydrolyzable metal compound having a reactive functional group firmly bonds the water-absorbing resin and/or hydrophilic resin, which are organic substances, and the silica, which is a metal oxide, to improve the wear resistance and hardness of the anti-fogging film. can contribute to improvement.

In formula (I) above, X is a hydrolyzable group or a halogen atom. Examples of hydrolyzable groups include at least one selected from alkoxyl groups, acetoxy groups, alkenyloxy groups, and amino groups. Alkoxyl groups include alkoxyl groups having 1 to 4 carbon atoms (specifically, methoxy, ethoxy, propoxy, and butoxy groups) and the like. The hydrolyzable group is preferably an alkoxyl group, more preferably an alkoxyl group having 1 to 4 carbon atoms. Chlorine etc. are mentioned as a halogen atom.

In the above formula (I), m is an integer of 0-2, preferably an integer of 0-1.

Preferred specific examples of the silicon compound (I) include silicon alkoxides in which X is an alkoxyl group. The silicon alkoxide preferably contains a compound with m=0 (SiX ₄ , tetrafunctional silicon alkoxide). Specific examples of tetrafunctional silicon alkoxides include tetramethoxysilane and tetraethoxysilane.

The silicon alkoxide more preferably contains the above tetrafunctional silicon alkoxide and a compound with m=1 (RSiX ₃ , trifunctional silicon alkoxide).
Specific examples of trifunctional silicon alkoxides having no reactive functional groups include methyltriethoxysilane, ethyltriethoxysilane, n-propyltriethoxysilane, and the like. Specific examples of trifunctional silicon alkoxides having a reactive functional group include glycidoxyalkyltrialkoxysilanes (eg, 3-glycidoxypropyltrimethoxysilane), aminoalkyltrialkoxysilanes (eg, 3-aminopropyl triethoxysilane, etc.).

A silicon alkoxide having a reactive functional group is also called a silane coupling agent. Compounds in which m=2 (R ₂ SiX ₂ , bifunctional silicon alkoxide), in which at least one R is a reactive functional group, are silane coupling agents. Specific examples of bifunctional silicon alkoxides in which at least one R has a reactive functional group include glycidoxyalkylalkyldialkoxysilanes (eg, 3-glycidoxypropylmethyldimethoxysilane) and aminoalkylalkyldialkoxysilanes. and alkoxysilanes (eg, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, etc.).

When the hydrolysis and polycondensation of silicon compound (I) proceed to completion, a compound represented by the following formula (II) (also referred to as silicon compound (II)) is produced. R and m in formula (II) are as described above.
_RmSiO ( _4-m)/2 (II)
The silicon compound (II) can form a three-dimensional network structure of siloxane bonds (Si--O--Si) in the antifogging film.

Antifogging films must be flexible enough to swell or shrink as they absorb or release moisture. From the viewpoint of the flexibility of the antifogging film, the content of silica derived from tetrafunctional silicon alkoxide in the antifogging film is preferably 0 to 0 with respect to 100 parts by mass of the content of the water-absorbing resin and/or hydrophilic resin. 30 parts by mass, more preferably 1 to 20 parts by mass, and particularly preferably 3 to 10 parts by mass. The content of silica derived from trifunctional silicon alkoxide is preferably 0 to 30 parts by mass, more preferably 0.05 to 15 parts by mass, with respect to 100 parts by mass of the content of the water-absorbent resin and/or hydrophilic resin. Especially preferably, it is in the range of 0.1 to 10 parts by mass.

<Crosslinked structure>
The antifogging film may contain a crosslinked structure derived from a crosslinker comprising an organometallic compound such as an organoaluminum compound, an organoboron compound, an organotitanium compound, and an organozirconium compound. Introduction of a crosslinked structure can improve the abrasion resistance and water resistance of the antifogging film. The introduction of the crosslinked structure facilitates improving the durability of the antifogging film without degrading its antifogging performance.
The cross-linking agent composed of an organometallic compound is not particularly limited as long as it can cross-link the water absorbent resin and/or hydrophilic resin used, and examples thereof include metal alkoxides, metal chelate compounds, and metal acylates.
Here, a specific example of the cross-linking agent will be given by taking as an example the case where the metal contained in the organometallic compound is titanium. Titanium alkoxides include titanium tetraisopropoxide, titanium tetra-n-butoxide, titanium tetraoctoxide, and the like. Titanium chelate compounds include titanium acetylacetonate, titanium acetoethyl acetate, titanium octylene glycol, titanium triethanolamine, and titanium lactate. The titanium lactate may be an ammonium salt (ie titanium lactate ammonium). Examples of titanium acylate include titanium stearate.

<Optional component>
The antifogging film can contain one or more optional components other than the above, if necessary. Optional ingredients include glycols such as glycerin and ethylene glycol that function to improve antifogging properties; surfactants, surface modifiers, slipping agents, leveling agents, antifoaming agents, preservatives; .

<Film thickness>
The thickness of the antifogging film can be designed according to the required antifogging performance and the like, and is preferably 1 to 20 μm, more preferably 2 to 15 μm, particularly preferably 3 to 10 μm.

<Method of forming anti-fogging film>
As a method of providing the functional film 50 on the glass plate 10 with a stamp, a method 1 of sticking a film with an adhesive layer having a laminated structure of functional film/base film/adhesive layer on the surface of the glass plate, and a glass plate. Method 2, in which a release film having a laminate structure of release film/functional film/adhesive layer and a functional film with an adhesive layer are attached to the surface of the adhesive layer, and then the release film is peeled off.

The anti-fogging film can be formed on the surface of the substrate film or release film by a known method.
A method for forming an anti-fogging film includes the step of preparing a liquid anti-fogging film composition containing a water-absorbing resin and/or a hydrophilic resin and a solvent, more preferably a metal oxide or a material thereof; A step of applying the composition for an antifogging film onto a substrate film or a release film (coating step) and a step of drying the coating film (drying step) can be included.

The coating method is not particularly limited, and includes die coating, spin coating, flow coating, roll coating, and the like.
The coating process is preferably carried out in an atmosphere of low relative humidity (RH) in order to prevent the coating film from excessively absorbing moisture from the atmosphere and residual moisture from reducing the strength of the antifogging film. The relative humidity (RH) is preferably 40% or less, more preferably 30% or less.

The drying method is not particularly limited, and includes air drying, drying under reduced pressure, drying by heating, drying by heating under reduced pressure, and combinations thereof.
The air-drying process is preferably performed in an atmosphere with a low relative humidity (RH), like the coating process.
The drying step preferably includes a heat drying step.
When the anti-fog film composition contains a hydrolyzable metal compound such as a hydrolyzable silicon compound, the drying step includes a heat drying step. Heating causes hydrolysis and polycondensation of the hydrolyzable metal compounds to produce metal oxides.
The heating temperature is a temperature at which hydrolysis and polycondensation of the hydrolyzable metal compound proceed and the water-absorbent resin and/or hydrophilic resin are not decomposed, preferably 80 to 300°C, more preferably 100 to 200°C. .

As a method for producing the anti-fogging film with an adhesive layer used in Method 1, there are a step of forming an anti-fogging film on one surface of the base film and a step of forming an adhesive layer on the other surface of the base film. a step of preparing an adhesive film having a base film and an adhesive layer formed on one surface thereof; and forming an anti-fogging film on the other surface of the base film of the adhesive film. and a method having a step of performing.
Materials for the base film are not particularly limited, and include polyethylene terephthalate (PET), polycarbonate (PC), cycloolefin polymer (COP), and combinations thereof. The base film may have a single layer structure or a laminated structure.

The method for producing the anti-fogging film with a release film and an adhesive layer used in method 2 includes a step of forming an anti-fogging film on the surface of the release film and a step of forming an adhesive layer on the anti-fogging film. A method including and the like.
The release film is not particularly limited, and includes a film obtained by subjecting the surface of a resin film such as a polyethylene terephthalate (PET) film to a release treatment such as silicone coating.

Since the method for forming the anti-fogging film has been described above, it will be omitted here.
The adhesive layer can be formed by applying a known adhesive by a known method. Examples of adhesives include acrylic adhesives, urethane adhesives, silicone adhesives, and the like.

As described above, according to the present embodiment, a glass laminate having a stamped coating glass plate 2 and an adhesive layer-attached member 3 and having good visibility of the stamp 10L and good adhesion of the adhesive layer-attached member 3 (Vehicle side glass) 1 can be provided.

EXAMPLES The present invention will be described below based on Examples, but the present invention is not limited to these. Examples 1 to 5 are examples, and Examples 11 to 13 are comparative examples.

[Evaluation items and evaluation methods]
Evaluation items and evaluation methods are as follows.
(Average haze value of engraving formation area)
The engraving formation region of the obtained glass laminate (vehicle side glass) was divided into 1 cm squares, and the haze value was measured for each divided region to obtain an average value.
The haze value was measured using a haze meter "HZ-V3" manufactured by Suga Test Instruments Co., Ltd. A light source was used as the light source, and the vehicle interior surface of the glass laminate (vehicle side glass) was used as the incident surface of the measurement light.

(Visibility of engraving)
The visibility of the engraving on the obtained glass laminate (vehicle side glass) was visually evaluated according to the following criteria.
5 (excellent): The engraving can be seen very well.
4 (Good): Engraving can be seen well,
3 (Possible): The engraving can be seen without problems.
2 (slightly poor): Engraving is hard to see,
1 (defective): Engraving cannot be seen at all.

(Adhesion of film with adhesive layer)
The obtained glass laminate (vehicle side glass) was left in an environment of 50° C. and 95% relative humidity (RH). The time required for at least part of the adhesive layer-attached film to peel off from the glass plate was visually determined, and the adhesiveness of the adhesive layer-attached film was evaluated according to the following criteria.
Excellent (⊚): No peeling was observed even after 2000 hours.
Good (◯): Peeling was observed after more than 1500 hours and 2000 hours or less.
Acceptable (Δ): Peeling was observed after more than 1000 hours and 1500 hours or less.
Poor (x): Peeling was observed after 1000 hours or less.

[Example 1]
(Production of film with adhesive layer)
<Preparation of chelate compound solution>
3.0 g of aluminum trisacetylacetonate (manufactured by Sigma-Aldrich) and 97.0 g of methanol (manufactured by Junsei Chemical Co., Ltd., special grade) are mixed and stirred at 25° C. for 10 minutes to give a clean A compound solution (CL1) was obtained.

<Preparation of composition for antifogging film>
In a glass container, 31.4 g of water-soluble epoxy resin (manufactured by Nagase ChemteX Corporation, Denacol EX1610), 33.4 g of chelate compound solution (CL1), 18.4 g of alcohol mixed solvent (Daishin Chemical Co., Ltd., Neo Alcohol IPM, a mixed solvent of ethanol, methanol and isopropyl alcohol), 8.5 g of ion-exchanged water, 0.09 g of 60% by mass nitric acid (manufactured by Junsei Chemical Co., Ltd.), and 8.1 g of epoxy A silane compound (KBM-403, 3-glycidoxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) was charged and stirred at room temperature (20 to 25° C.) for 60 minutes to obtain an antifog film composition.

<Deposition of anti-fogging film>
A polyethylene terephthalate (PET) film (manufactured by Toyobo Co., Ltd., A4300) with a thickness of 100 μm was prepared as a base film. On one surface of this base film, the antifogging film composition was applied by a spin coating method and held at 100° C. for 30 minutes to form an antifogging film containing a water-soluble epoxy resin and silica. formed.
Next, an adhesive (CS9861UAS manufactured by Nitto Denko Corporation) was applied to the other surface of the base film to form an adhesive layer having a thickness of 25 μm.
As described above, a film with an adhesive layer (anti-fog film with an adhesive layer) was obtained.

(Preparation of coating film composition)
In a round-bottomed flask, 2.09 g of benzophenone-based ultraviolet absorber (Uvinu13050, manufactured by BASF), 5.24 g of epoxysilane compound (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd., 3-glycidoxypropyltrimethoxysilane), 4.25 g of butyl acetate and 0.03 g of benzyltriethylammonium chloride were charged, heated to 105° C., and stirred for 4 hours.
To the resulting solution, 39.44 g of methyl ethyl ketone, 8.87 g of methanol, 13.80 g of pure water, a methoxy-type alkylsilane compound (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-3066, 1,6-bis(trimethoxy silyl) hexane) 0.86 g, 90 mass% acetic acid aqueous solution 9.52 g, epoxy resin (manufactured by Sakamoto Yakuhin Kogyo Co., Ltd., SR-SEP) 0.95 g, polymaleic acid aqueous solution (manufactured by NOF Corporation, non-pol 0.17 g of PMA-50W), 0.01 g of maleic acid and 0.06 g of a surface conditioner (BYK377 manufactured by BYK-Chemie) were added and stirred at 50° C. for 2 hours.
Finally, 3.87 g of a 30% by mass indium tin oxide fine particle dispersion (manufactured by Mitsubishi Materials Corporation, ITO dispersion) was added as an infrared shielding agent.
As described above, a liquid coating film composition containing an ultraviolet shielding agent and an infrared shielding agent and having a solid concentration of 12.5% was obtained.

(Manufacturing of engraved glass plate)
As a glass plate for evaluation, a side glass (5.0 mm thick tempered glass) on the driver's side of a commercial automobile having a planar shape as shown in FIG. 1 was prepared.
The glass plate for evaluation has a front side (length: about 500 mm), a rear side (length: about 800 mm), an upper side (length: about 1000 mm), and a lower side in plan view. and the total area was about 300000 mm ² .
A stencil cut out from a 50 mm square, 0.3 mm thick square brass plate with car manufacturer name, glass manufacturer name, product number, and engraving (character line width: 0.5 to 1.0 mm) including the JIS mark. prepared the plate.

The stencil plate was placed on the vehicle interior surface of the evaluation glass plate, and abrasive sand with a grain size of #100 was blown from above using a commercially available sandblaster to remove the rear side of the vehicle interior surface of the evaluation glass plate. An imprint was formed at the lower end of the side edge. The imprint forming area had a length of 30 mm, a width of 40 mm, and an area of 1200 mm ² .
Vertical separation distance D1 between the lower edge of the engraving formation area and the lowermost edge of the vehicle side glass = 150 mm, horizontal separation distance D2 between the upper edge of the engraving formation area and the rear side of the vehicle side glass = 40 mm, Engraving The lateral separation distance D3 between the lower side of the formation region and the rear side side of the vehicle side glass was D3=30 mm. See FIG. 1 for D1-D3.
When the arithmetic mean surface roughness (Ra) of the stamp was determined according to JIS B 0601 (2013), it was 2.3 to 2.8 μm.
After forming the imprint, water washing and drying were performed.
A glass plate with a stamp was obtained as described above.

(Formation of coating film)
Next, the above coating film composition is applied to substantially the entire interior surface of the obtained glass plate with the engraving in an environment of room temperature (20 to 25° C.) and relative humidity (RH) of 30% by a flow coating method. was applied. After pre-drying the engraved glass plate at room temperature (20 to 25° C.) for about 5 minutes, it was placed in an oven previously heated to 200° C. and heated for 15 minutes. The engraved glass plate was taken out of the oven and allowed to cool to room temperature (20 to 25° C.) to obtain a coated glass plate having an ultraviolet and infrared ray shielding film as a coating film.

(Attachment of film with adhesive layer)
Next, the film with an adhesive layer (anti-fogging film with an adhesive layer) was attached to the vehicle interior surface of the obtained coated glass plate with a stamp in the following manner.

Pure water was sprayed almost entirely on the car exterior surface of the coated glass plate with the engraving, and the resulting adhesive layer-attached film was placed on this surface so as to follow the car exterior surface. At this time, the adhesive layer-attached film was placed on the vehicle outer surface of the glass plate so that the anti-fogging film was in contact with the glass plate. In this state, the adhesive layer-attached film was cut according to the application area set in Example 1.
The cut film with an adhesive layer was attached to the attachment area set in Example 1 on the car interior surface of the engraved coated glass plate. At this time, the adhesive layer-attached film was attached to the vehicle interior surface of the glass plate so that the adhesive layer was in contact with the glass plate.

As shown in FIG. 1A, the anti-fog film with an adhesive layer has a front side, a rear side, an upper side, and a lower side in plan view, and has a shape with chamfered corners. . The angle θ of the corner portion overlapping with or adjacent to the stamp forming region of the antifogging film with an adhesive layer was set to 120°.
The front side of the glass plate and the front side of the antifogging film are substantially parallel, and the rear side of the glass plate and the rear side of the antifogging film are substantially parallel.

The adhesive layer-attached film was attached to a relatively wide area including the center of the engraved glass plate.
As shown in FIG. 1A, in the engraved glass plate, areas where the adhesive layer-attached film did not exist were provided at the front side edge, the rear side edge, the upper edge, and the lower edge of the glass plate. The front side edge of the adhesive layer-attached film was shifted rearward by about 3 mm from the front side edge of the vehicle side glass. The upper side of the adhesive layer-attached film was shifted downward by about 10 mm from the upper side of the vehicle side glass. The rear side of the adhesive layer-attached film was shifted forward from the rear side of the vehicle side glass by about 15 mm.

The area of the film with adhesive layer was about 2100 cm ² . The ratio of the area of the adhesive layer-attached member to the area of the engraved glass plate was 70%.
The ratio of the overlapping area (Sb) between the stamp forming region and the adhesive layer-attached film to the area (Sa) of the stamp forming region was 0%.
As described above, a glass laminate (vehicle side glass) was obtained.
Tables 1 and 2 show main manufacturing conditions and evaluation results. In the examples shown in Table 1, conditions not listed in the table were common conditions.

[Examples 2-5, Examples 11-13]
In each of Examples 2 to 5 and Examples 11 to 13, the area (Sa) and/or formation location of the imprint forming region was changed, and the area (Sa) of the imprint forming region and the adhesion layer A glass laminate (vehicle side glass) was obtained in the same manner as in Example 1, except that the ratio of the overlapping area (Sb) with the film was changed.
Tables 1 and 2 show main manufacturing conditions and evaluation results.

[Summary of results]
The glass laminates (vehicle side glasses) of Examples 1 to 5, in which the ratio of the overlapping area (Sb) between the stamp forming region and the adhesive layer-attached film to the area (Sa) of the stamp forming region was 0 to 40%, had the stamp The average haze value of the formation area was high, and the visibility of the engraving and the adhesion of the adhesive layer-attached film were good.
The glass laminates (vehicle side glasses) of Examples 11 to 13, in which the ratio of the overlapping area (Sb) of the stamp-forming region and the adhesive layer-attached film to the area (Sa) of the stamp-forming region was 50% or more, had the stamp-forming region. The average haze value of the region was low, and the visibility of the engraving and the adhesion of the adhesive layer-attached film were poor.

1, 1X, 1Y: Glass laminate (vehicle side glass), 2: Engraved coated glass plate, 3: Member with adhesive layer, 3C: Corner, 3X: Film with adhesive layer, 3Y: Film with adhesive layer, 10 : engraved glass plate, 10L: engraved, 10M: engraved area, 11: front side, 12: rear side, 13: upper side, 14: lower side, 20: coating film, 30: adhesive layer, 31: front side, 32: rear side, 33: upper side, 34: lower side, 40: base film, 50: functional film, 71 to 74: non-existing regions.

Claims (10)

A coating with an imprint, which has a glass plate having an imprint made of a rough surface portion having a larger surface roughness than the other part on one surface, and a coating film formed on the surface of the glass plate so as to cover the imprint. a glass plate and
A glass laminate having a member with an adhesive layer attached to the coating film side surface of the engraved coated glass plate,
When the imprint forming area is defined as the smallest imaginary rectangle that inscribes the imprint in plan view,
A glass laminate, wherein a ratio of an overlapping area of the stamp-forming region and the adhesive layer-attached member to the area of the stamp-forming region in plan view is 0 to 40%. 2. The glass laminate according to claim 1, wherein the ratio of the area of the adhesive layer-attached member to the area of the glass plate is 30 to 90% in plan view. The glass laminate according to claim 1 or 2, wherein the adhesive layer-attached member does not have a corner portion with an angle of less than 90° that overlaps or is close to the imprint forming region. The arithmetic mean surface roughness (Ra) of the stamp is 1.0 to 5.0 μm,
The coating film has a thickness of 2 to 30 μm,
The glass laminate according to any one of claims 1 to 3, wherein the adhesive layer included in the adhesive layer-attached member has a thickness of 10 to 200 µm. The member with an adhesive layer is an anti-fogging film with an adhesive layer comprising an adhesive layer, a base film, and an anti-fogging film containing a water absorbent resin or hydrophilic resin, or an adhesive layer and a water absorbent resin or hydrophilic The glass laminate according to any one of claims 1 to 4, which is an anti-fogging film with an adhesive layer containing an anti-fogging film containing a resin. The glass laminate according to any one of claims 1 to 5, wherein the coating film contains at least one functional material selected from the group consisting of ultraviolet shielding agents and infrared shielding agents. A vehicle side glass comprising the glass laminate according to any one of claims 1 to 6. When the forward direction of the vehicle is defined as the forward direction and the backward direction of the vehicle is defined as the rearward direction, the glass plate has a front side edge and a rear side edge when fitted in the vehicle,
The stamp, the coating film, and the adhesive layer-attached member are formed on the surface of the glass plate on the vehicle interior side,
The engraving is formed on a rear side edge portion including the rear side edge of the glass plate and a portion in the vicinity thereof,
8. The vehicle side glass according to claim 7, wherein the rear side edge portion of the glass plate has an area where the adhesive layer-attached member does not exist. The member with an adhesive layer has sides on the front side and the back side,
the front side of the glass plate and the front side of the adhesive layer-attached member are substantially parallel to each other;
The vehicle side glass according to claim 8, wherein the rear side of the glass plate and the rear side of the adhesive layer-attached member are substantially parallel to each other. The adhesive layer-attached member has sides with different lengths on the front side and the back side,
The vehicle side glass according to claim 8 or 9, wherein the longer side edge of the adhesive layer-attached member overlaps with the engraving in plan view.

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