CN120813553A

CN120813553A - Laminated glass and glass plate

Info

Publication number: CN120813553A
Application number: CN202480015758.4A
Authority: CN
Inventors: 池上彩夏; 青木时彦
Original assignee: Asahi Glass Co Ltd
Current assignee: AGC Inc
Priority date: 2023-05-10
Filing date: 2024-04-24
Publication date: 2025-10-17
Also published as: WO2024232279A1

Abstract

The present invention relates to a laminated glass comprising a first glass plate, a second glass plate opposed to the first glass plate, and an interlayer interposed between the first glass plate and the second glass plate, wherein the first glass plate and the second glass plate each have a pair of opposed main surfaces, the second glass plate has a display portion on the main surface located on the opposite side from the interlayer, the display portion has a reflectance of 30% or more over the entire wavelength range of 420 to 700nm, and the difference between the maximum value and the minimum value of the reflectance is 20% or less.

Description

Laminated glass and glass plate

Technical Field

The present invention relates to laminated glass and glass sheets.

Background

There is proposed an image display transparent member, i.e., a transparent screen, which can see a scene on the other side of the transparent member when seen from the observer side, and also can display a projected image from a projection device in a visible manner. The transparent member can be used for, for example, a showcase, a window of a building, a vehicle, a glass door, a transparent partition in a room, and the like.

Patent document 1 discloses an image display transparent member in which an image display portion having a first transparent film, a first transparent layer, a reflective film, a second transparent layer, and a second transparent film is bonded to a transparent substrate.

Prior art literature

Patent literature

Patent document 1 Japanese patent No. 6508205

Disclosure of Invention

Technical problem to be solved by the invention

In window glass for vehicles, particularly in front window glass, there is a demand for visible light transmittance that satisfies legal requirements. Therefore, when the laminated glass having the image display unit as described above is applied to a front glass, the front glass needs to have a visible light transmittance that satisfies legal requirements and also needs to have an image display unit with good image visibility, or needs to be provided at a specific position other than the object of legal requirements.

However, when a transparent film having high visible light transmittance as disclosed in patent document 1 is sealed in a laminated glass, external light such as sunlight is scattered while passing through the film, and thus the contrast between the projected image and the external light becomes small. As a result, the visibility of the projection image irradiated from the projection device is reduced.

In addition, after the laminated glass is obtained, the film is sealed and integrated with the laminated glass, so that it is difficult to change the optical characteristics such as the position and reflectance of the image display portion.

Accordingly, an object of the present invention is to provide a laminated glass having excellent visibility of a projected image irradiated from a projector to a display unit and a high degree of freedom in forming the display unit.

In addition, the image display transparent member does not need to be made into laminated glass according to the installation place. Accordingly, another object of the present invention is to provide a glass plate having excellent visibility of a projected image irradiated from a projection device to a display unit and a high degree of freedom in forming the display unit.

Technical proposal adopted for solving the technical problems

The present inventors have conducted intensive studies and as a result, have found that the above-described problems can be solved by providing a display portion having specific optical characteristics on a main surface of one glass plate or on a main surface of a glass plate constituting a laminated glass.

Namely, the main content of the present invention is as follows.

[1] A laminated glass having a first glass plate, a second glass plate opposed to the first glass plate, and an interlayer sandwiched between the first glass plate and the second glass plate,

The first and second glass sheets each have a pair of opposed major faces,

The second glass plate has a display portion on a main surface located on the opposite side to the intermediate film side,

The display unit has a reflectance of 30% or more over the entire wavelength range of 420-700 nm, and a difference between a maximum value and a minimum value of the reflectance of 20% or less.

[2] The laminated glass according to the above [1], wherein the display portion is a portion constituted by an ink layer, a ceramic color layer or a metal layer containing Ag.

[3] The laminated glass according to the above [2], wherein the brightness L ^* of the display portion is 50 or more.

[4] The laminated glass according to any one of [1] to [3], wherein the second glass plate has a plurality of the display portions, and the plurality of display portions form a display area constituted by dot patterns.

[5] The laminated glass according to the above [4], wherein the display portion occupies 13 to 50% of the area of the display region in a plan view.

[6] The laminated glass according to any one of [1] to [5], wherein the reflectance curve of the display portion in a wavelength range of 420 to 700nm shows monotonic decrease in the entire wavelength range.

[7] The laminated glass according to any one of [1] to [5], wherein the reflectance curve of the display portion in a wavelength range of 420 to 700nm shows monotonically increasing over the entire wavelength range.

[8] The laminated glass according to any one of [1] to [7], wherein the surface roughness Ra of the display portion is 1.0 μm or less.

[9] The laminated glass according to any one of [1] to [8], wherein the laminated glass has a light shielding portion at a position overlapping the display portion in a plan view, the light shielding portion being located closer to the first glass plate than the display portion, and a reflectance in an entire wavelength range of 420 to 700nm is 10% or less.

[10] The laminated glass according to the above [9], wherein the light shielding portion has a luminance L ^* of 35 or less.

[11] The laminated glass according to any one of [1] to [10], wherein the display portion displays information by reflecting a projected image from a side opposite to the first glass plate side at the display portion.

[12] The laminated glass according to any one of the above [1] to [11], wherein the laminated glass is used for a vehicle and is provided such that the first glass plate is an outside of the vehicle.

[13] The laminated glass as described in [12], wherein the laminated glass is used for a front glass.

[14] A glass sheet having a pair of opposed major faces, wherein,

A display portion is provided on one main surface,

[15] The glass sheet according to item [14], wherein the display portion is a portion composed of an ink layer, a ceramic color layer or a metal layer containing Ag.

[16] The glass sheet according to item [15], wherein the brightness L ^* of the display portion has a value of 50 or more.

Effects of the invention

The laminated glass of the present invention has excellent visibility of a projected image irradiated from a projector to a display unit, and has a high degree of freedom in forming the display unit.

The glass plate of the present invention has excellent visibility of a projected image irradiated from a projection device to a display portion and has high degree of freedom in forming the display portion, like the laminated glass.

Drawings

Fig. 1 is a schematic plan view showing one embodiment of a laminated glass according to the present embodiment.

Fig. 2 is a cross-sectional view taken along line A-A of fig. 1.

Fig. 3 is a schematic plan view showing another embodiment of the laminated glass according to the present embodiment.

Fig. 4 is a sectional view taken along line a '-a' of fig. 3.

Fig. 5 is a partially schematic cross-sectional view showing another embodiment of the laminated glass of the present embodiment.

Fig. 6 is a partially schematic cross-sectional view showing another embodiment of the laminated glass of the present embodiment.

Detailed Description

The present invention will be described in detail below, but the present invention is not limited to the following embodiments, and may be implemented by any modification within the scope of the present invention. The term "displaying the numerical value range" is used in a sense including the numerical values described before and after the term "displaying the numerical value range" as a lower limit value and an upper limit value.

In the description of the present embodiment, with reference to the drawings, the same or corresponding structures in the drawings are denoted by the same reference numerals, and description thereof may be omitted. Furthermore, the embodiments depicted in the drawings are illustrative for clarity of description of the invention and are not necessarily intended to represent exact dimensions or scale of the actual article.

Laminated glass

Fig. 1 is a schematic plan view of a laminated glass 10 according to one embodiment of the present embodiment, when used as a front window glass for a vehicle. Fig. 2 is a cross-sectional view taken along line A-A of fig. 1. As shown in fig. 2, for example, the laminated glass 10 of the present embodiment includes a first glass plate 1, a second glass plate 2 opposed to the first glass plate 1, and an interlayer 3 interposed between the first glass plate 1 and the second glass plate 2.

The first glass plate 1 and the second glass plate 2 each have a pair of opposed main faces. The second glass plate 2 has a display portion 4 on a main surface 2b located on the opposite side to the interlayer film 3 side.

The laminated glass 10 of the present embodiment is mounted such that the first glass plate 1 is disposed on the vehicle exterior side and the second glass plate 2 is disposed on the vehicle interior side when used in a vehicle. That is, the display unit 4 is provided on the vehicle interior side.

< Display portion >

The reflectance of the display section 4 in this embodiment is 30% or more over the entire wavelength range of 420 to 700 nm.

The wavelength of 420-700 nm represents the visible light range. By setting the reflectance to 30% or more, the visibility of the projected image becomes good. Therefore, the visibility of the projected image is excellent even in the presence of external light.

In the present specification, the reflectance in the entire wavelength range of 420 to 700nm is measured at 10nm intervals in a wavelength region of 420 to 700nm using a 45 DEG/0 DEG spectrophotometer in which the incident light is 2 DEG and annular illumination is used in the one-way illumination system. In the present specification, the presence of external light means that the illuminance of light on the side of the laminated glass from the outside, that is, the first glass plate 1 side is 3000 lux or more.

The reflectance is not less than 30%, but is preferably 30 to 100%, more preferably 40 to 95%, further preferably 45 to 90%, particularly preferably 50 to 90%. Here, from the viewpoint of achieving better visibility, the reflectance is preferably 40% or more, more preferably 45% or more, and still more preferably 50% or more. The upper limit of the reflectance is not particularly limited and may be 100%, but from the viewpoint of the material composition, it is preferably 95% or less, more preferably 90% or less.

In the display unit 4 of the present embodiment, the difference between the maximum value and the minimum value of the reflectance is 20% or less. Thereby, the color of the display portion becomes weak. Therefore, in addition to good visibility of the projected image, the image projected onto the display section 4 can be seen in a form close to the original color.

The difference in reflectance is 20% or less, preferably 18% or less, more preferably 15% or less, and still more preferably 10% or less. The lower limit of the difference in reflectance is not particularly limited, and may be 0% or 1% or more.

The above-mentioned reflectance or difference in reflectance can be adjusted by changing the kind or content of pigment contained in the layer constituting the display section 4. In the case where the layer constituting the display portion 4 contains a metal, the metal can be adjusted by changing the type, content, or the like of the metal.

The display portion 4 in the present embodiment is not particularly limited as long as the above optical characteristics are satisfied, but is preferably a portion composed of, for example, an ink layer, a ceramic color layer, or a metal layer containing Ag.

The value of the luminance L ^* of the display portion 4 is preferably 50 or more, more preferably 60 or more, still more preferably 70 or more, and the upper limit is not particularly limited and may be 100, from the viewpoint of improving the visibility of the image projected onto the display portion 4.

In addition, the luminance L ^* in the present specification means a value of a luminance index L ^* in the CIE 1976 (L ^*a^*b^*) color space (CIELAB) defined in the international commission on illumination (CIE). The closer the luminance L ^* is to 0, the darker, the closer to 100, the whiter.

The display unit 4 in the present embodiment is provided in a region of the laminated glass 10 in the present embodiment where an image is to be projected and displayed.

As shown in fig. 1 and 2, the display portion 4 may be 100% dots, that is, full-spread. The full-face application means a state in which the second glass plate 2 is applied without any gap so as not to be seen. In this case, the display section 4 is identical to the display area 6.

In the case where the display portion 4 is provided at 100% dots, the display portion 4 is provided in a partial region on the main surface 2b of the second glass plate 2 so that the outside is visible in a region other than the region where the display portion 4 is not provided.

Fig. 3 is a schematic plan view of a laminated glass 20 used as a front window glass for a vehicle, as another embodiment of the laminated glass of the present embodiment. Fig. 4 is a sectional view taken along line a '-a' of fig. 3. Instead of the entire painting, a plurality of display portions 4 may be provided as shown in fig. 3 and 4 to form a display area 6 constituted by a dot pattern. In this case, each dot becomes the display portion 4, and a region where the display portion 4 is not formed is defined between dots. The aggregate of the area between the dots where the display section 4 is not formed and the display section 4 constituting each dot is the display area 6.

When a plurality of display units 4 are provided to form a display area 6 composed of a dot pattern, the area ratio of the dots in the display area, that is, the ratio of the area occupied by the display units in the display area 6 is not particularly limited. The area ratio of the halftone dots is set to an appropriate value from various viewpoints such as external visibility, visibility of a projected image, and designability.

Furthermore, the area ratio of the dots may not be constant. For example, in the case where the display region 6 is formed at the peripheral edge portion of the front glass, the area ratio of the dots may be increased as the dot is closer to the outer peripheral edge.

For example, in the case where the display area 6 is formed at the peripheral edge portion of the front glass, the area ratio of the halftone dots in the display area 6 may be, for example, 100%.

When it is desired to display a projected image on the entire surface of the front window glass or in a region where the outside is visible, the area ratio of the screen dots in the display region 6, that is, the total ratio of the areas occupied by the plurality of display units 4 in the display region 6 in a plan view is preferably 13 to 50%, for example, and more preferably 18 to 30%. Here, the above area ratio is preferably 13% or more, more preferably 18% or more, from the viewpoint of good visibility of the projected image. In addition, the above area ratio is preferably 50% or less, more preferably 30% or less, from the viewpoint of good visibility from the outside.

As an index of the external visibility, the area ratio of the halftone dots is preferably set so that the transmittance of the region excluding the peripheral edge portion of the laminated glass 20 is 70% or more over the entire wavelength range of 420 to 700 nm.

When each point is circular, its diameter is, for example, 100 to 1000 μm. The area of each dot in plan view is preferably 0.007 to 0.8mm ², although it varies depending on the area ratio of the dot. Here, the area is preferably 0.007m ² or more from the viewpoint of sufficiently reflecting the light irradiated from the projection device to the display region 6. In addition, from the viewpoint of preventing a decrease in visibility due to various points when viewing the outside, the area is preferably 0.8mm ² or less.

The shape of each point is not limited to a circle, and any shape such as an ellipse, a square, a polygon, a diamond, a needle pad, a hexagon, or a T-shape may be used.

In addition, 2 or more kinds of dots having different sizes and shapes may be mixed in the display area 6.

The display portion 4 or the display region 6 in the present embodiment may be provided in a desired region on the main surface 2b of the second glass plate 2. For example, the display portion 4 or the display area 6 may be provided at a peripheral edge portion of the front window glass. The display unit 4 or the display area 6 may display various pieces of information such as the vehicle speed, the number of revolutions, and the like, and the speed limit.

In the case where a plurality of display portions 4 are provided to form a display region 6 formed of a dot pattern, the display region 6 may be provided on the entire surface of the main surface 2b of the second glass plate 2. In such a display area 6, various information such as navigation information may be displayed in addition to meter information.

As described above, in the case of projecting an image to the display area 6, by adjusting the area ratio of the halftone dots or the like, good visibility of the outside from the inside of the vehicle can also be ensured.

The thickness of the display portion 4 in the present embodiment is not particularly limited, but is preferably, for example, 1 to 50 μm, more preferably 1 to 40 μm. Here, the thickness of the display portion 4 is preferably 50 μm or less, more preferably 40 μm or less, from the viewpoint of adjusting the reflectance. In addition, from the viewpoint of preventing defects such as voids, the thickness of the display portion 4 is preferably 1 μm or more.

The thickness of the display portion 4 was measured by a stylus using a surface roughness measuring instrument according to JIS B0601:1994.

The surface roughness Ra of the display portion 4 in this embodiment is preferably 1.0 μm or less, more preferably 0.01 to 1.0 μm, further preferably 0.03 to 0.8 μm, and still further preferably 0.05 to 0.8 μm. Here, from the viewpoint of adhesion of the display portion 4 to the main surface 2b of the second glass plate 2, the surface roughness Ra is preferably 0.01 μm or more, more preferably 0.03 μm or more, and still more preferably 0.05 μm or more. On the other hand, from the viewpoint of obtaining better visibility and shape clarity of the projected image, the surface roughness Ra is preferably 1.0 μm or less, more preferably 0.8 μm or less.

In addition, the surface roughness Ra in the present specification means a value of an arithmetic average roughness Ra measured by a stylus type using a surface roughness measuring instrument according to JIS B0601:1994.

When the display portion 4 is a portion constituted by an ink layer, the surface roughness Ra can be adjusted by the particle diameter of the ink composition.

In the case where the display portion 4 is a portion formed of a ceramic color layer, the surface roughness Ra can be adjusted by the crystallinity or the particle diameter of the ceramic coloring composition.

When the display portion 4 is a portion formed of a metal layer containing Ag, the surface roughness Ra can be adjusted by the particle size of the composition.

The reflectance curve of the display unit 4 in the present embodiment preferably shows monotonic decrease over the entire wavelength range in the wavelength range of 420 to 700 nm. The monotonically decreasing is that the reflectance decreases as the wavelength becomes longer, and there is no peak at a specific wavelength in the above wavelength region.

When the display portion 4 is a portion constituted by an ink layer or a ceramic color layer, the monotonic decrease is easily observed.

On the other hand, the reflectance curve of the display unit 4 in the present embodiment preferably increases monotonically over the entire wavelength range even in the wavelength range of 420 to 700 nm. The monotonically increasing appearance means that the reflectance increases as the wavelength becomes longer, and that there is no peak at a specific wavelength in the above wavelength region.

When the display portion 4 is a portion formed of a metal layer containing Ag, the monotonic increase is easily observed.

The display portion 4 in the present embodiment is formed by applying an ink composition, which is an ink precursor, to the main surface 2b of the second glass plate 2 by printing or the like, and curing the ink composition.

The ink layer is easily formed on the main surface 2b of the second glass plate 2, and is preferable from the viewpoints of productivity of the display portion 4 and high degree of freedom in the position where the display portion 4 is formed.

The ink layer may be formed using a polymer resin composition containing a pigment as a colorant. The polymer resin composition contains a resin, a dispersant, a solvent, and the like as required in addition to the pigment. In this specification, the polymer resin composition is referred to as an "ink composition". The pigment may be any one of coloring materials such as an organic pigment, an organic dye, and an inorganic pigment, and may be used alone or in combination of 2 or more. The coloring material may be appropriately selected according to the desired color.

Specifically, the coloring material may be, for example, a white pigment.

Examples of the white pigment include titanium oxide and zinc oxide.

The resin in the polymer resin composition may be a resin having any of properties such as a thermoplastic resin, a photocurable resin, and a thermosetting resin, and preferably a photocurable resin and a thermosetting resin.

Specifically, known resins such as polyurethane-based resins, phenol-based resins, epoxy-based resins, urea melamine-based resins, silicone-based resins, phenoxy resins, methacrylic resins, acrylic resins, polyarylate resins, polyester-based resins, polyolefin-based resins, polystyrene-based resins, polyvinyl chloride, vinyl chloride-vinyl acetate copolymers, polyvinyl acetate, polyvinylidene chloride, polycarbonates, polyethylene terephthalate, polyethersulfone, acrylonitrile-butadiene-styrene (ABS) resins, transparent ABS resins, celluloses, polyacetal and the like can be exemplified.

The resin may be a resin composed of a homopolymer or a copolymer of a monomer of the resin and a monomer copolymerizable therewith. The binder may be used alone or in combination of 2 or more.

The photocurable resin is preferably cured by irradiation with UV light from the viewpoint of simplifying the resin curing process and eliminating the need for a firing furnace. The resin shown above may be prepared by adding a photopolymerization initiator to an acrylic resin or the like, for example, to prepare a photocurable resin, and irradiating the resin with light to obtain a photocurable film.

As the thermosetting resin, curing at a temperature lower than the annealing point of the glass sheet is preferable from the viewpoint of maintaining the shape of the glass sheet. Specifically, the thermosetting temperature of the resin is preferably 500 ℃ or less, more preferably 400 ℃ or less, and further preferably 300 ℃ or less. In addition, from the viewpoint of curing stability of the resin and adhesion to the glass plate, the heat curing temperature of the resin is preferably 100 ℃ or higher, more preferably 150 ℃ or higher, and still more preferably 200 ℃ or higher.

Examples of such a thermosetting resin include an acrylic resin and a silicone resin among the resins shown above.

The dispersant is not particularly limited, and examples thereof include cellulose derivatives, organic acids, terpene compounds, and the like. The organic acid may be, for example, an unsaturated carboxylic acid polymer, but may be other organic acids. The dispersant may be used alone or in combination of at least 2.

The solvent is not particularly limited, and examples thereof include known solvents such as water, alcohols, esters, ketones, aromatic hydrocarbon solvents, and aliphatic hydrocarbon solvents.

Examples of alcohols that can be used include isopropanol, methanol, and ethanol. As the esters, for example, ethyl acetate and the like can be used. Examples of the ketones include methyl ethyl ketone. As the aromatic hydrocarbon solvent, toluene, xylene, solvesso (registered trademark) 100,150, and the like can be used, for example. As the aliphatic hydrocarbon solvent, hexane or the like can be used, for example.

The solvent may be used alone or in combination of at least 2 kinds.

The ink composition preferably contains, for example, 0.1 to 10 mass% of a coloring material, 1 to 50 mass% of a resin, and 20 to 80 mass% of a solvent.

The display portion 4 in the present embodiment is a ceramic color layer when the display portion is a portion constituted by a ceramic color layer, and is a firing layer formed by applying a paste or liquid ceramic coloring composition as a precursor to the main surface 2b of the second glass plate 2 and firing the composition by heat treatment.

The ceramic color layer is preferably bonded to the main surface 2b of the second glass plate 2 to prevent peeling from the second glass plate 2.

The ceramic coloring composition is a paste or liquid composition obtained by mixing an inorganic component including a glass frit and a pigment with an organic component.

In order to obtain various characteristics, 1 kind of glass frit may be used alone, or 2 or more kinds may be mixed and used. In addition, 2 or more kinds of glass frits having the same composition but different particle diameters may be appropriately mixed and used.

The softening point Ts of the frit is preferably 500 to 580 ℃, more preferably 520 to 540 ℃. That is, the softening point Ts is preferably 500 ℃ or higher, more preferably 520 ℃ or higher, and preferably 580 ℃ or lower, more preferably 540 ℃ or lower. When 2 or more kinds of glass frits are mixed and used, it is more preferable that the softening point of 1 or more kinds of glass frits is within the above range, and it is still more preferable that the softening points of all glass frits are within the above range.

The particle diameter D ₅₀ of the glass frit is preferably 0.1 μm to 3.0 μm, more preferably 0.3 μm to 2.5 μm, still more preferably 0.5 μm to 2.0 μm. Here, from the viewpoint of preventing the specific surface area from increasing due to excessive atomization, adsorbing moisture and carbon dioxide gas in the atmosphere, foaming at the time of forming the ceramic color layer, and causing a decrease in transmittance, strength, and the like, the particle diameter D ₅₀ of the frit is preferably 0.1 μm or more, more preferably 0.3 μm or more, and still more preferably 0.5 μm or more. The particle diameter D ₅₀ is preferably 3.0 μm or less, more preferably 2.5 μm or less, and even more preferably 2.0 μm or less.

The particle diameter D ₅₀ of the frit is the cumulative median particle diameter D ₅₀ of the volume-based particle size distribution, which is determined by laser diffraction scattering.

In the case of screen-printing a ceramic color layer on the surface of a glass plate, the maximum particle diameter D _max of the frit is preferably 30 μm or less, more preferably 20 μm or less, and still more preferably 15 μm or less from the viewpoint of preventing clogging. Further, from the viewpoint of preventing deterioration of sinterability and strength of the ceramic color layer due to undissolved coarse particles, the maximum particle diameter D _max of the frit is more preferably 10 μm or less.

The pigment in the ceramic color layer is not particularly limited as long as the reflectance of the obtained display portion 4 satisfies the above optical characteristics, and conventionally known inorganic pigments can be used. Among them, the ceramic color layer is preferably made into a white ceramic layer using a white pigment.

Examples of the white pigment include titanium oxide and zinc oxide.

The ceramic coloring composition as a precursor of the ceramic color layer preferably contains a filler in addition to the glass frit and the pigment.

Examples of the "filler" may include a crystallization accelerator and a so-called low-expansion filler.

The crystallization accelerator is preferably added when it is desired to enlarge the crystallization area of the ceramic color layer. In firing the ceramic color layer composition, the crystallized regions are formed by heat treatment at a temperature higher than the crystallization temperature of the frit. If the ceramic color layer composition contains a crystallization accelerator, the crystallization accelerator becomes a crystal nucleus, so that crystallization starts at a temperature lower than the above-mentioned crystallization temperature to increase the crystallization area.

The kind of crystallization promoter varies depending on the composition of the frit. For example, when the glass frit contains Bi, a bismuth silicate-based crystallization accelerator is preferable. In addition, in the case where the crystal phases have similar patterns, crystallization may sometimes be promoted even if the compositions of the frits are different.

From the viewpoint of improving the strength of the laminated glass, it is preferable to add a low-expansion filler.

As the low expansion filler, conventionally known low expansion fillers can be used, and examples thereof include cordierite, zircon, alumina, titania, zirconium phosphate, silica, and forsterite. 1 kind of them may be used alone, or 2 or more kinds may be used in combination.

Among them, at least one selected from cordierite, zircon and silica is more preferably contained.

The ceramic color layer may further contain an oxidizing agent within a range that does not impair the effects of the present invention. As the oxidizing agent, conventionally known oxidizing agents such as CeO ₂、MnO₂ can be used.

When the display portion 4 in the present embodiment is a portion formed of an Ag-containing metal layer, the Ag-containing metal layer is a layer formed of an Ag-containing metal, and is formed on the main surface 2b of the second glass plate 2 by firing or the like of an Ag-containing metal paste.

The Ag-containing metal layer may contain other components than Ag, such as a metal, as long as the metal layer satisfies the optical characteristics required for the display portion 4.

Examples of the metals other than Ag include Al, cr, mo, in, ni, ta, ti, cu, W, sn, co.

The Ag-containing metal layer may be a layer of an alloy of Ag and a metal other than Ag, or may be a layer of a metal oxide or a layer of a metal nitride. The content of Ag in the metal layer is preferably 60 mass% or more, or may be 100 mass%, that is, a metal layer composed of Ag alone.

In the case of forming the display region 6 formed of dot patterns by providing a plurality of display portions 4, it is also preferable to form the Ag-containing metal layer by coating a metal paste containing Ag or the like using a masking tape.

Further, after forming the Ag-containing metal layer, patterning may be performed by photolithography, etching, or the like.

< Light shielding portion >

As shown in fig. 5 and 6, the laminated glasses 30 and 40 of the present embodiment may have a light shielding portion 5 at a position overlapping the display portion 4 in a plan view. The light shielding portion 5 is located closer to the first glass plate 1 than the display portion 4.

The reflectance of the light shielding portion 5 is preferably 10% or less over the entire wavelength range of 420nm to 700 nm.

Due to the presence of the light shielding portion 5, when an image is projected onto the display portion 4, the contrast between the projected image and external light becomes large, and therefore, the reduction in the visibility of the projected image can be suppressed. Further, when the laminated glasses 30, 40 are viewed from the vehicle outside, the display portion 4 becomes invisible and the appearance becomes good, so that the light shielding portion 5 is also preferable from the viewpoint of aesthetic properties. In addition, when the laminated glass 30, 40 of the present embodiment is used for a front window glass of a vehicle, the display unit 4 can be prevented from reflecting outside light to the outside of the vehicle, and thus, the driver of the oncoming vehicle can be prevented from being impaired.

The light shielding portion 5 in this embodiment preferably has a reflectance of 8% or less or may have a reflectance of 0% or less over the entire wavelength range of 420nm to 700 nm.

In order to further obtain the above-described effect of the light shielding portion 5, the value of the luminance L ^* of the light shielding portion 5 in the present embodiment is preferably 35 or less, more preferably 30 or less, and may be 0.

The light shielding portion 5 may be located closer to the first glass plate 1 than the display portion 4, and may be located between the second glass plate 2 and the display portion 4 and provided on the main surface 2b of the second glass plate 2, as shown in fig. 5, for example. As shown in fig. 6, the first glass plate 1 may be provided on the main surface 1b on the interlayer film 3 side. The light shielding portion 5 is not limited to the configuration shown in fig. 5 and 6, and may be provided on the main surface 1a of the first glass plate 1 on the opposite side of the interlayer 3, or may be provided on the main surface 2a of the second glass plate 2 on the side of the interlayer 3, for example.

The light shielding portion 5 does not have to have the same size as the display portion 4 in plan view, and may be larger than the display portion 4 or smaller than the display portion 4.

The light shielding portion 5 is not particularly limited as long as the reflectance is 10% or less, and for example, the light shielding portion 5 is preferably a portion that shields light by an opaque ceramic color layer.

In the case where the light shielding portion 5 is an opaque ceramic color layer, the color is arbitrary, but it is preferably a dark color such as black, brown, gray, or dark navy, and more preferably black.

The ceramic color layer to be the light shielding portion 5 preferably contains at least one pigment or dye selected from carbon black, graphite, and metal oxides.

Examples of the metal oxide-containing pigment include cuo—cr ₂O₃ (black), coo—cr ₂O₃ (black), fe ₂O₃ (brown), coo—al ₂O₃ (blue), nio—cr ₂O₃ (green), and the like, and they may be used in combination. In the case of using these pigments, desired color, gloss, and opacity, i.e., transmittance characteristics, can be imparted.

In the case of making black using a metal oxide, at least one oxide pigment selected from Cu, fe, co, ni, cr, si, mn, al and Zn is preferable, a composite oxide pigment containing 2 or more of these is more preferable, and a composite oxide pigment selected from Cu(Cr,Mn)₂O₄、CuCrO₄、Cr₂O₃:Fe₂O₃、Cr₂O₃:Fe₂O₃:CoO、(Fe,Mn)(Mn,Fe)₂O₄、(Co,Fe)(Fe,Cr)₂O₄、(Co,Fe,Mn)(Fe,Cr,Mn)₂O₄、(Co,Fe)(Ni,Cr)₂O₄ and at least one of (Cu, fe, mn) (Fe, mn, al) ₂O₄ is further preferable.

The light shielding portion 5 may be a colored intermediate film or a colored film having light shielding properties, a combination of a colored intermediate film and a ceramic color layer, or a layer having a light adjusting function. The colored film may be integrated with an infrared ray reflection film or the like.

The light shielding portion 5 may be a portion shielded from light by the ink layer. The coloring material contained in the ink layer may be an organic pigment, an organic dye, an inorganic pigment, or the like, and is preferably a dark color such as black, brown, gray, or dark navy, and more preferably black.

The ink layer constituting the light shielding portion 5 may contain a resin, a dispersant, a solvent, or the like as necessary, in addition to the coloring material, as in the ink layer constituting the display portion 4.

< Intermediate film >

As shown in fig. 2, the intermediate film 3 in the present embodiment is a film that bonds the first glass plate 1 and the second glass plate 2. That is, the interlayer 3 is sandwiched between the main surface 1b of the first glass plate 1 and the main surface 2a of the second glass plate 2.

The end face of the intermediate film 3, which becomes the outer periphery, is preferably subjected to edge treatment. Specifically, it is preferable that the end face of the intermediate film 3 is subjected to edge treatment so as not to protrude significantly from the end faces of the first glass plate 1 and the second glass plate 2, which are outer peripheries.

The amount of protrusion of the interlayer film 3 from the end surfaces of the first glass plate 1 and the second glass plate 2, which are the outer circumferences, is preferably 150 μm or less.

The intermediate film 3 may be made of a conventionally known material, for example, a thermoplastic resin. However, the thermoplastic resin is not limited thereto.

Examples of the thermoplastic resin include thermoplastic polyvinyl acetal resins, plasticized polyvinyl chloride resins, saturated polyester resins, plasticized saturated polyester resins, polyurethane resins, plasticized polyurethane resins, ethylene-vinyl acetate copolymer resins, ethylene-ethyl acrylate copolymer resins, cycloolefin polymer resins, and ionomer resins. Further, a resin composition containing a modified block copolymer hydride described in Japanese patent publication No. 6065221 may be suitably used.

These thermoplastic resins may be used alone or in combination of 2 or more. In the above examples, "plasticizing" means plasticizing by adding a plasticizer.

Among them, the thermoplastic polyvinyl acetal resin is more preferable from the viewpoint of excellent balance of various properties such as transparency, weather resistance, strength, adhesive force, penetration resistance, impact energy absorption, moisture resistance, heat insulation and sound insulation.

When a substance having a specific function is enclosed in the interlayer film 3, the substance may be degraded by a specific plasticizer depending on the kind of the enclosed substance. In this case, a resin substantially free of the plasticizer is more preferable.

Examples of the plasticizer-free resin include ethylene-vinyl acetate copolymer (EVA) resins.

Examples of the polyvinyl acetal resin include a polyvinyl formal resin obtained by reacting polyvinyl alcohol (PVA) with formaldehyde, a polyvinyl acetal resin in a narrow sense obtained by reacting PVA with acetaldehyde, and a polyvinyl butyral (PVB) resin obtained by reacting PVA with n-butyraldehyde. Among them, PVB resins are preferred from the viewpoint of excellent balance of properties such as transparency, weather resistance, strength, adhesion, penetration resistance, impact energy absorption, moisture resistance, heat insulation, and sound insulation.

The polyvinyl acetal resin may be used alone or in combination of 2 or more kinds.

The intermediate film 3 may further contain a plasticizer such as triethylene glycol di-2-ethylhexanoate, tetraethylene glycol di-N-heptanoate, and the like.

The intermediate film 3 may further contain functional particles such as an infrared absorber, an ultraviolet absorber, and a luminescent agent.

The intermediate film 3 may have a colored portion called a shading band.

In the case where the intermediate film 3 has a colored portion, a conventionally known colored pigment can be used as a colored pigment for forming the colored portion. For example, a coloring pigment which can be used for plastics can be exemplified. The amount of the coloring pigment to be added may be adjusted so that the visible light transmittance of the colored portion is 40% or less.

Examples of the coloring pigment include organic coloring pigments such as azo pigments, phthalocyanine pigments, quinacridone pigments, perylene pigments, pyrenone pigments, dioxazine pigments, anthraquinone pigments, and isoindolinone pigments, and inorganic coloring pigments such as oxides, hydroxides, sulfides, chromic acid, sulfates, carbonates, silicates, phosphates, arsenate, ferrocyanide pigments, carbon pigments, and metal powders.

These coloring pigments may be used alone or in combination of 2 or more.

The intermediate film 3 may be formed of only one layer or may be formed of a plurality of layers.

In the case where the intermediate film 3 is formed of a plurality of layers, the layers included in the intermediate film 3 may be formed of the same material or may be formed of different materials, but are preferably formed of the same material.

Even when the interlayer 3 is formed of different materials, it is preferable that 50% or more of the thickness of the interlayer 3 is a thermoplastic resin from the viewpoints of adhesion to the first glass plate 1 and the second glass plate 2, protection of the functional material enclosed in the laminated glass 10, and the like.

In the case where the interlayer 3 is formed of three or more layers, from the viewpoint of improving the sound insulation of the laminated glass 10, it is preferable that the shear elastic modulus of any layer other than the pair of outermost layers closest to the first glass plate 1 and the second glass plate 2 is smaller than the shear elastic modulus of the pair of outermost layers. In this case, the shear elastic moduli of the pair of outermost layers may be the same or different.

In addition, the shear modulus of elasticity of each layer can be adjusted by adjusting a plasticizer or the like.

The thickness of the intermediate film 3 is preferably 0.5mm or more at the thinnest part, and the maximum value of the thickness is preferably 3mm or less. When the interlayer 3 is formed of a plurality of layers, the thickness of the interlayer 3 is the total thickness of the respective layers.

From the viewpoint of impact resistance of the laminated glass, the thickness of the thinnest part of the interlayer film 3 is preferably 0.5mm or more. In addition, from the viewpoint of weight reduction of the laminated glass, the maximum value of the film thickness of the interlayer 3 is preferably 3mm or less, more preferably 2.8mm or less, and still more preferably 2.6mm or less.

In the case of mounting the laminated glass 10 on a vehicle, the film thickness of the upper side and the lower side of the intermediate film 3 may be different. For example, the intermediate film 3 may have a wedge shape, and the film thickness thereof gradually increases from the lower side to the upper side. In the case of mounting a head-Up Display (HUD) on a vehicle, the wedge shape is one form suitable for displaying an image from a projector.

The intermediate film 3 is formed by appropriately selecting a resin material, extruding the resin material in a heated and melted state using, for example, an extruder, and stretching the obtained resin film as necessary so as to have curvatures at the upper and lower sides in accordance with the design of the laminated glass. The extruder is preferably set to have uniform extrusion conditions such as extrusion speed.

< First glass plate, second glass plate >

The first glass plate 1 and the second glass plate 2 in the present embodiment may be inorganic glass or organic glass, respectively. The first glass plate 1 and the second glass plate 2 may be the same glass plate, or may be different glass plates, and may have the same or different dimensions and thicknesses.

Examples of the inorganic glass include soda lime glass, aluminosilicate glass, borosilicate glass, alkali-free glass, and quartz glass.

Among them, when the laminated glass 10 of the present embodiment is used in a vehicle, the first glass plate 1 positioned on the vehicle outer side is preferably an inorganic glass from the viewpoint of scratch resistance, and soda lime glass from the viewpoint of formability.

When the first glass plate 1 and the second glass plate 2 are soda lime glass, it is more preferable to use transparent glass, green glass containing a predetermined amount or more of iron component, or dark green glass.

The inorganic glass may be any of unreinforced glass and tempered glass.

The unreinforced glass is a glass obtained by forming molten glass into a flat plate shape and annealing the glass.

The tempered glass is a glass in which a compressive stress layer is formed on the surface of unreinforced glass. In addition, in the case of the tempered glass, the residual stress can be reduced by isotropically distributing the stress.

The tempered glass may be physically tempered glass such as air-cooled tempered glass, or may be chemically tempered glass.

The physical strengthening treatment is a method of strengthening the surface of a glass sheet by generating a compressive stress layer on the surface of the glass sheet by using a temperature difference between the surface and the inside of the glass sheet. Specifically, by an operation other than annealing, for example, a cooling medium is sprayed onto a glass sheet heated to a temperature equal to or higher than the annealing point of the glass sheet (for example, 500 to 600 ℃ or higher), the surface of the glass sheet is rapidly cooled, and a compressive stress layer is generated on the surface of the glass sheet.

The chemical strengthening treatment is a method of strengthening the surface of a glass plate by generating a compressive stress layer on the surface of the glass plate by an ion exchange method or the like. Specifically, the chemical strengthening treatment is a treatment in which a glass plate is brought into contact with a metal salt by immersing the glass plate in a metal salt solution containing metal ions having a large ionic radius, and the metal ions having a small ionic radius in the glass are replaced with metal ions having a large ionic radius. Typically, lithium ions are replaced with sodium or potassium ions, and sodium ions are replaced with potassium ions.

In the case of performing the chemical strengthening treatment, a molten metal salt, that is, a molten salt, may be used as the molten metal salt. The conditions of the chemical strengthening treatment may be appropriately selected in consideration of the glass composition, the type of molten salt, and the like. The chemical strengthening treatment may be performed in a plurality of stages, or may be performed by cleaning with an alkaline solution, cleaning with plasma irradiation, or the like.

In the case where the laminated glass 10 of the present embodiment is used for a front window glass of a vehicle, it is preferable that the first glass plate 1 located on the vehicle outer side and the second glass plate 2 located on the vehicle inner side are unreinforced glass which has not been subjected to tempering treatment, from the viewpoint of preventing crack propagation to the entire surface of the glass plates at the time of breakage.

The first glass plate 1 and the second glass plate 2 may be glass plates that absorb ultraviolet rays or infrared rays, with or without strengthening treatment. The first glass plate 1 and the second glass plate 2 may be colored glass plates within a range that does not impair the desired transmittance.

On the other hand, examples of the material of the organic glass include polycarbonate, an acrylic resin such as polymethyl methacrylate, and a transparent resin such as polyvinyl chloride and polystyrene.

In the present embodiment, at least one of the first glass plate 1 and the second glass plate 2 has a transmittance of 70% or more, more preferably 80% or more, still more preferably 90% or more, in the entire wavelength range of 420nm to 700nm, from the viewpoint of visibility of the outside when a laminated glass is produced, and the upper limit is not particularly limited, but is usually less than 100%.

As the glass plate having the above transmittance, the first glass plate 1 and the second glass plate 2 in the present embodiment are preferably green glass or transparent glass, and more preferably transparent glass.

The green glass is glass with high transparency. The transmittance of green glass in the entire wavelength range of 420 to 700nm is, for example, about 83 to 88% when the thickness is 1.6 to 2.0 mm.

Transparent glass is glass having higher transparency than green glass. The transmittance of the transparent glass in the entire wavelength range of 420 to 700nm is, for example, about 88 to 92% when the plate thickness is 1.8 to 2.0 mm.

The thickness of the first glass plate 1 in this embodiment is not particularly limited, and is preferably 1.1 to 3mm, more preferably 1.8 to 2.8mm, further preferably 1.8 to 2.6mm, further preferably 1.8 to 2.2mm, and particularly preferably 1.8 to 2.1mm, for example.

Here, in the case where the obtained laminated glass 10 is used in a vehicle, the above-mentioned plate thickness is preferably 1.1mm or more, more preferably 1.8mm or more, from the viewpoint of obtaining sufficient strength such as flyrock resistance. The thickness of the sheet is preferably 3mm or less, more preferably 2.8mm or less, even more preferably 2.6mm or less, even more preferably 2.2mm or less, and particularly preferably 2.1mm or less, from the viewpoint of the total weight of the laminated glass 10 obtained, particularly from the viewpoint of improving fuel efficiency when used in a vehicle.

The thickness of the second glass plate 2 in this embodiment is not particularly limited, but is preferably 0.3 to 2.3mm, more preferably 0.5 to 2.2mm, and even more preferably 0.7 to 2.1mm, for example.

Here, from the viewpoint of workability and glass quality such as residual stress after press-contact with the first glass plate 1 when producing a glass having a large bend, the plate thickness is preferably 0.3mm or more, more preferably 0.5mm or more, and still more preferably 0.7mm or more. From the viewpoint of the total weight of the laminated glass 10 and the glass quality, the thickness of the sheet is preferably 2.3mm or less, more preferably 2.2mm or less, and even more preferably 2.1mm or less.

In addition, from the viewpoint of improving the light transmittance in the visible light range and making the secondary image inconspicuous, the plate thickness is preferably 2.0mm or less, more preferably 1.8mm or less. The secondary image is a ghost image generated by the light reflected by the main surface 2a of the second glass plate 2 on the intermediate film 3 side and the light reflected and scattered by the display portion 4.

The thicknesses of the first glass plate 1 and the second glass plate 2 in the present embodiment may be different at the upper side and the lower side of the glass plates. For example, the plate thickness of the first glass plate 1 and/or the second glass plate 2 may have a wedge shape, which becomes gradually thicker from the lower side toward the upper side. In the case of mounting a head-up display (HUD) on a vehicle, the wedge-shaped form may be formed into a laminated glass suitable for displaying an image from a projection device.

In general, in a vehicle equipped with a head-up display, a concave lens is added to widen an image or a space is provided to ensure a focal length between a light source and the concave lens in order to display a virtual image, and therefore, the capacity of a projection apparatus increases.

In contrast, in the laminated glasses 10 and 20 of the present embodiment, when an image is projected onto the display portion 4 or the display region 6, light can be scattered in the display portion 4 or the display region 6, and therefore, a large capacity is not required for the projection device. Therefore, by sorting the display contents between the head-up display portion and the display section 4 or the display area 6, the capacity of the entire projection apparatus can be reduced.

The first glass plate 1 and the second glass plate 2 in the present embodiment may be provided with a film, a device, or the like having a specific function on one of the main surfaces.

Examples of the functions of the film and the device include water repellency, antifogging, heat insulation, low reflection, reflection of infrared rays, cut-off of infrared rays, light emission, power generation, light adjustment, touch panels, reflection of visible light, reduction of visible light, scattering, decoration, and absorption. The film and the device may be conventionally known films and devices.

For example, by providing a film having an infrared cut-off function, heat insulation can be ensured while maintaining high visible light transmittance.

Further, by providing a film having low reflection characteristics, the visible light transmittance can be improved, and at the same time, external scenery and the like can be easily seen through the display region 6.

Further, a coating for improving the visible light reflectance may be applied on all or part of the main surface 2b of the second glass plate 2 on the opposite side from the intermediate film 3. As a result, the reflectance of the display unit 4 is also improved, and therefore, the visibility of the projected image is improved even when the illuminance of the external light is high. Therefore, the ratio of the area occupied by the display section 4 in the display area 6 constituted by the plurality of display sections 4 can also be reduced, thereby improving the external visibility.

Examples of such a coating layer include an optical interference film in which high refractive index layers and low refractive index layers are alternately laminated.

As the high refractive index layer, zn, sn, ti, nb, zr, ni, in, al, ce, W, mo, sb or oxide or mixed oxide of Bi, or Si, al, zr, B, Y, ce or nitride or oxynitride of La, etc. can be exemplified. The refractive index of the high refractive index layer at a wavelength of 550nm is preferably 1.8 or more, more preferably 2.0 or more.

Examples of the low refractive index layer include silicon oxide, silicon oxycarbide, aluminum oxide, mixed silicon zirconium oxide, aluminum-doped zinc oxide, magnesium fluoride, and a mixture thereof. The refractive index of the low refractive index layer at a wavelength of 550nm is preferably 1.7 or less, more preferably 1.6 or less.

In addition to the above, as a coating layer capable of improving the visible light reflectance, a coating layer in which a layer made of Ag or an Ag compound which is a conductive material and a layer made of a metal oxide or a metal nitride are alternately laminated, and the like can be exemplified.

< Laminated glass >

The laminated glass 10 of the present embodiment may be a laminated glass formed of three or more constituent glass plates, but from the viewpoint of weight reduction, two sheets are preferable.

When the number of glass sheets constituting the laminated glass 10 is three or more, the glass sheet closest to the vehicle interior side is preferably the second glass sheet 2.

In the present embodiment, the materials of the first glass plate 1 and the second glass plate 2 may be the same or different. The first glass plate 1 and the second glass plate 2 may be the same or different in size and shape, but from the standpoint of no need for shape processing when the laminated glass 10 is mounted on a vehicle, it is preferable that the first glass plate 1 and the second glass plate 2 are identical or substantially identical in size and shape, that is, their planar shapes are identical or substantially identical.

In the present embodiment, the end face of at least one of the first glass plate 1 and the second glass plate 2 may have a chamfer. The chamfering may be performed by a conventionally known method. For example, chamfering may be performed using a diamond grinding wheel, a rotating grinding wheel, a laser, or the like.

The laminated glasses 10 and 20 of the present embodiment are preferably used as an image display transparent member having the display section 4 or the display region 6. In this case, the display unit 4 or the display area 6 reflects the projection image from the display unit 4 side, that is, the side opposite to the first glass plate 1 side, at the display unit 4 or the display area 6, and displays information.

Here, in the image display transparent member disclosed in patent document 1, when a transparent film having high visible light transmittance is sealed in a laminated glass, wrinkles may occur in the transparent film. If wrinkles are generated, the external scene and the projected image may appear distorted, and thus visibility may be degraded.

In contrast, the laminated glasses 10 and 20 of the present embodiment do not need to originally have a transparent film enclosed in the laminated glass, and thus the visibility of the external scene and the projected image is good.

The laminated glass 10 of the present embodiment is preferably used for a vehicle, and more preferably used for a front window glass. In this case, the first glass plate 1 is disposed so as to be the vehicle outside.

The laminated glass 10 of the present embodiment is preferably a multi-curved shape that curves in both the vertical direction and the horizontal direction when mounted on a vehicle. However, the present invention is not limited to a multi-curved shape that curves in the vertical direction and the horizontal direction when mounted on a vehicle, nor does it exclude a multi-curved shape that curves in any of the different two directions.

The laminated glass 10 of the present embodiment may be a single curved shape that is curved only in a single direction, i.e., in the vertical direction or the horizontal direction, when mounted on a vehicle. But is not limited to a single Qu Xingzhuang that is bent only in a single direction, either the vertical direction or the horizontal direction, when mounted on a vehicle, nor does it exclude a single curved shape that is bent only in any single direction.

The laminated glass 10 of the present embodiment is preferably curved so as to protrude toward the vehicle outside. That is, the first glass plate 1 is preferably bent to protrude toward the opposite side of the intermediate film 3, and the second glass plate 2 is preferably bent to protrude toward the intermediate film 3.

In the laminated glass 10 of the present embodiment, the minimum value of the radius of curvature is preferably 500 to 100000mm. Here, the radii of curvature of the first glass plate 1 and the second glass plate 2 may be the same or different. In the case where the radii of curvature of the first glass plate 1 and the second glass plate 2 are different, it is preferable that the radius of curvature of the second glass plate 2 is smaller than the radius of curvature of the first glass plate 1.

In the laminated glass 10 of the present embodiment, the method of bending the first glass plate 1 and the second glass plate 2 is not particularly limited. Examples of the method include gravity molding, press molding, and roll molding.

In the case where the first glass plate 1 and the second glass plate 2 are inorganic glass having a curved shape, the first glass plate 1 and the second glass plate 2 may be curved and formed after being formed by a float method or the like and before being bonded by the interlayer film 3. The bending is performed by softening the glass sheet by heating. The heating temperature of the glass sheet during bending is, for example, 550 to 700 ℃.

The method for forming the first glass plate 1 and the second glass plate 2 is not particularly limited. For example, in the case of inorganic glass, a glass plate formed by float method or the like is preferable.

In the case of a glass sheet formed by the float process, the tin concentration in one major surface of the glass sheet may be high due to the manufacturing method thereof. In this case, for example, the main surface 1a of the first glass plate 1 and the main surface 2a of the second glass plate 2 may be the side having a high tin concentration, or the main surface 1b of the first glass plate and the main surface 2b of the second glass plate 2 may be the side having a high tin concentration.

In the case where the display portion 4 is made of a metal layer containing Ag, the main surface 2b of the second glass plate 2 is preferably made to be the side having a higher tin concentration, and more preferably the main surface 1b of the first glass plate and the main surface 2b of the second glass plate 2 are made to be the side having a higher tin concentration, from the viewpoint of easy fixation of Ag.

The total thickness of the laminated glass 10 of the present embodiment is preferably 2.8 to 10mm. Here, the total thickness is preferably 2.8mm or more from the viewpoint of securing sufficient rigidity. Further, the total thickness is preferably 10mm or less from the viewpoint of obtaining a sufficient transmittance and reducing haze.

From the viewpoint of obtaining a good appearance, the plate deviation of the first glass plate 1 from the second glass plate 2 is preferably 1.5mm or less, more preferably 1mm or less, at least one side of the laminated glass 10 of the present embodiment. Here, the plate deviation refers to the amount of deviation between the outer peripheral side surface of the first glass plate 1 and the outer peripheral side surface of the second glass plate 2 in plan view.

< Manufacturing method >

The method for producing the laminated glass 10 of the present embodiment is not particularly limited.

For example, the display portion 4, and optionally the light shielding portion 5, etc., may be provided on the main surface 2b of the second glass plate 2 on the opposite side from the intermediate film 3 side, and then joined together with the first glass plate 1 and the intermediate film 3 to obtain the laminated glass 10.

After the laminated glass is obtained by the conventionally known method, the display portion 4, the optional light shielding portion 5, and the like may be provided on the main surface 2b of the second glass plate 2, as necessary, to obtain the laminated glass 10.

In the following, a method for manufacturing the laminated glass 10 according to the present embodiment is shown as one mode of a method for providing the display portion 4 on the main surface 2b of the second glass plate 2.

In the case where the display portion 4 is a portion constituted by an ink layer, for example, the ink composition is applied to the main surface 2b of the second glass plate 2 by printing or the like, and then dried, thereby forming the display portion 4.

Examples of the printing method include, but are not limited to, gravure printing, flexography, offset printing, relief printing, screen printing, pad printing, spray printing, inkjet printing, brush coating, and spin coating.

If the thermosetting resin is contained in the ink composition, curing thereof can be promoted by heating after the ink composition is coated on the main surface 2b of the second glass plate 2. Further, if the ink composition contains a photocurable resin, the curing of the ink composition can be accelerated by irradiation of light such as ultraviolet rays after the ink composition is applied to the main surface 2b of the second glass plate 2.

In the above case, the display portion 4 is preferably formed after the second glass plate 2 is bent and formed. Compared with a method in which the second glass plate 2 is bent after the display portion 4, which is a portion made of an ink layer, is formed, deformation due to residual stress can be reduced.

When the display portion 4 is a portion constituted by a ceramic color layer, the display portion 4 is formed using a ceramic coloring composition in a paste or liquid state as a ceramic color layer precursor.

Specifically, the ceramic coloring composition is applied to the main surface 2b of the second glass plate 2 by printing or the like, and fired. The firing is performed, for example, in a range of 600 to 800 ℃.

In the above case, the display portion 4 is preferably formed after the second glass plate 2 is bent and formed.

If the second glass plate 2 is subjected to bending processing after the display portion 4, which is a portion made of a ceramic color layer, the portion where the display portion 4 is provided may be difficult to cool during slow cooling, and the portion where the display portion 4 is not provided may be easy to cool. As a result, residual stress may be high in the region of the second glass plate 2 after bending and forming, which is close to the display portion 4. However, this does not exclude a method of bending the second glass plate 2 after forming the display portion 4, which is a portion formed of the ceramic color layer.

Further, the heat treatment at the time of forming the ceramic color layer may be set to be equal to or higher than the firing temperature of the annealing point of the glass plate, and the second glass plate 2 may be subjected to bending forming while the ceramic color layer is formed.

In the case where the display portion 4 is a portion formed of an Ag-containing metal layer, for example, the Ag-containing metal paste may be applied to the main surface 2b of the second glass plate 2 by printing or the like, and then fired.

In the above case, from the viewpoint of reducing deformation due to residual stress, it is preferable to form the display portion 4 before bending the second glass sheet 2.

In the case where the display area 6 formed of the dot pattern is formed by providing the plurality of display portions 4, the ink composition, the ceramic coloring composition, or the Ag-containing metal paste is applied in the dot pattern on the main surface 2b of the second glass plate 2 by printing or the like, and dried or fired.

When the light shielding portion 5 is provided at a position overlapping the display portion 4 in a plan view, the light shielding portion 5 is located closer to the first glass plate 1 than the display portion 4.

The light shielding portion 5 may be provided on any one of the main surfaces 1a, 1b of the first glass plate 1 and the main surfaces 2a, 2b of the second glass plate 2. In the case where the light shielding portion 5 is provided on the main surface 2b of the second glass plate 2, the light shielding portion 5 is located between the second glass plate 2 and the display portion 4.

The light shielding portion 5 is formed of an ink layer or a ceramic color layer, but the value of reflectance, brightness L ^*, and the like is different from the display portion 4 due to the difference in pigment and the like contained therein. The light shielding portion 5 may be formed by the same method as the method for forming the display portion 4.

The types of layers forming the display portion 4 and the light shielding portion 5 may be the same or different. For example, the display portion 4 and the light shielding portion 5 may be portions that are shielded from light by the ink layer or portions that are shielded from light by the ceramic color layer. The display portion 4 may be a portion blocked by the ink layer, and the light shielding portion 5 may be a portion blocked by the ceramic color layer. The display portion 4 may be a portion shielded from light by a metal layer containing Ag, and the light shielding portion 5 may be a portion shielded from light by a ceramic color layer. Other combinations are also possible.

When the display portion 4 and the light shielding portion 5 are present and the plurality of display portions 4 form the display area 6 formed of the dot pattern, the plurality of light shielding portions 5 may form a light shielding area formed of the dot pattern corresponding to the display portion 4.

In this case, the area of each point of the light shielding portion 5 constituting the light shielding region is preferably 0.8 to 1.2 times the area of each point of the display portion 4 overlapped in a plan view. The above area ratio is preferably 0.8 times or more from the viewpoint of visibility of an image when the image is projected onto the display portion 4 of the laminated glass 10. In addition, from the viewpoint of aesthetic properties from the outside of the vehicle when the laminated glass 10 of the present embodiment is used in the vehicle, the above-mentioned area ratio is preferably 1.2 times or less.

Next, one mode of bending the first glass plate 1 and the second glass plate 2 will be described.

The first glass plate 1 and the second glass plate 2 are bent to form a desired shape predetermined by a design drawing or CAD data or the like.

The bending of the first glass sheet 1 and the second glass sheet 2 may be performed by a conventionally known method, such as a gravity molding method. Gravity forming is a method in which a glass sheet is placed on an annular mold, passed through a heating furnace, softened by heating, and bent by gravity to a desired shape. In addition to the gravity molding method, a press molding method in which a glass plate is sandwiched between a male mold and a female mold and press molded may be used.

The interlayer 3 may be sandwiched between the first glass plate 1 and the second glass plate 2 by a conventionally known method. For example, the first glass plate 1, the interlayer film 3, and the second glass plate 2 are laminated and bonded in this order.

Specifically, the laminate is placed in a rubber bag, a rubber chamber, a resin bag, or the like, and then heated to bond the laminate.

The lamination method and heating conditions and temperature conditions at the time of bonding can be appropriately selected. For example, the bonding may be performed in a vacuum at a gauge pressure of-100 to-65 kPa at a temperature range of 70 to 110 ℃.

In addition to the above bonding, for example, by performing a pressure-bonding treatment under heating and pressure under conditions of a temperature controlled in the range of 100 ℃ to 150 ℃ and an absolute pressure controlled in the range of 0.6mpa to 1.5mpa, a laminated glass 10 having more excellent durability can be obtained. However, in consideration of simplification of the process and the characteristics of the material enclosed in the laminated glass 10, the heating and pressurizing process may be omitted.

Further, a method called "cold bending" may be employed in which at least one of the first glass plate 1 and the second glass plate 2 is joined in a state of elastic deformation. The cold bending can be achieved by using a laminate composed of the first glass plate 1, the interlayer film 3, and the second glass plate 2 fixed by temporary fixing means such as an adhesive tape, a pre-press device such as a conventionally known pinch roll, a rubber bag, or a rubber chamber, and an autoclave.

Glass plate

The present invention also relates to a glass plate having a pair of opposed main surfaces, and a display portion provided on one of the main surfaces.

The display portion in the glass plate of the present embodiment has a reflectance of 30% or more over the entire wavelength range of 420 to 700nm, and a difference between the maximum value and the minimum value of the reflectance is 20% or less.

That is, the display portion in the glass plate of the present embodiment is the same as the display portion 4 in the above-described laminated glass, and the preferred form and manufacturing method are also the same. In other words, the glass plate of the present embodiment is a single plate corresponding to the second glass plate 2 in the above-described laminated glass.

The display portion in this embodiment is preferably a portion formed of, for example, an ink layer, a ceramic color layer, or a metal layer containing Ag.

Further, the luminance L ^* of the display portion is more preferably 50 or more.

The glass sheet of the present embodiment is suitable for use as, for example, a side window glass or a rear window glass of a vehicle.

Examples

The present invention will be specifically described with reference to the following examples, but the present invention is not limited to these examples. Examples 1 to 5 are examples, and example 6 is a comparative example. The glass sheets of these test examples were single sheets of flat glass having a thickness of 100mm×100mm×2.0mm, and a display portion was formed thereon, not laminated glass. However, in order to verify the effect of the present invention, it is considered that the same results as those of examples and comparative examples are obtained in the case of laminated glass, and thus they can also be considered as examples and comparative examples for laminated glass.

Test examples

< Example 1>

The ceramic coloring composition containing the white pigment was applied on the bottom surface of a flat glass plate having a thickness of 100mm×100mm×2.0mm (surface in contact with the molten metal in the float bath) by screen printing, dried at 120 ℃ for 15 minutes, and then fired at 640 ℃ for 240 seconds, thereby obtaining a glass plate having a display portion.

As the flat glass, green glass which is soda lime glass obtained by float method is used.

As the ceramic colorant composition containing a white pigment, a paste composition formed by mixing an inorganic component containing titanium oxide and glass frit as white pigments with an organic component is used. After firing, a display portion having a size of 90mm×90mm and a dot area ratio of 100% was formed, and the thickness thereof was 13.9 μm.

< Example 2>

The ceramic coloring composition containing the black pigment was coated on the bottom surface of a plate-like glass of 100mm×100mm×2.0mm in plate thickness by screen printing, and dried at 120 ℃ for 15 minutes. Next, a ceramic coloring composition containing a white pigment was coated thereon by screen printing, dried at 120 ℃ for 15 minutes, and then fired at 640 ℃ for 240 seconds, thereby obtaining a glass plate having a light shielding portion and a display portion.

The same glass as in example 1 was used as the flat glass.

As the ceramic colorant composition containing a black pigment, a paste composition formed by mixing an inorganic component containing a copper-chromium oxide and glass frit as black pigments with an organic component is used. After firing, a light shielding portion and a display portion having a size of 30mm×30mm and a dot area ratio of 100% were formed, and the total thickness thereof was 28.1 μm.

< Example 3>

An Ag paste (9903, manufactured by dupont) was applied to the bottom surface of a flat glass plate having a thickness of 2.0mm by screen printing, dried at 120 ℃ for 15 minutes, and then fired at 630 ℃ for 400 seconds, thereby obtaining a glass plate having a display portion.

The same glass as in example 1 was used as the flat glass.

After firing the Ag paste, a display portion having a size of 90 mm. Times.90 mm and a dot area ratio of 100% was formed, and the thickness thereof was 10.7. Mu.m.

< Example 4>

In the same manner as in example 2, a ceramic coloring composition containing a black pigment was applied by screen printing to the bottom surface of a plate-like glass having a thickness of 100mm×100mm×2.0mm, and dried at 120 ℃ for 15 minutes. Next, an Ag paste (manufactured by dupont, 9903) was applied thereon by screen printing, and fired at 630 ℃ for 400 seconds, thereby obtaining a glass plate having a light shielding portion and a display portion.

After firing, the Ag paste forms a light-shielding portion and a display portion having a size of 90mm by 90mm and a dot area ratio of 100%, and the total thickness of these portions is 19.8. Mu.m.

< Example 5>

The ink composition containing the white pigment was applied by spin coating to the bottom surface of a plate-like glass having a thickness of 100mm×100mm×2.0mm, and cured at 100 ℃ for 30 minutes, to obtain a glass plate having a display portion.

The same glass as in example 1 was used as the flat glass.

As the ink composition containing a white pigment, a liquid composition containing titanium oxide as a white pigment and a resin in an organic solvent is used. After firing, a display portion having a size of 90mm×90mm and a dot area ratio of 100% was formed, and the thickness thereof was 37.8 μm.

< Example 6>

The ceramic coloring composition containing the black pigment was applied on the bottom surface of a plate-like glass of 100mm×100mm×plate thickness 2.0mm by screen printing, dried at 120 ℃ for 15 minutes, and then fired at 640 ℃ for 240 seconds, thereby obtaining a glass plate having a display portion.

The same glass as in example 1 was used as the flat glass.

As the ceramic colorant composition containing a black pigment, a paste composition formed by mixing an inorganic component containing a copper-chromium oxide and glass frit as black pigments with an organic component is used. After firing, a display portion having a size of 30mm×30mm and a dot area ratio of 100% was formed, and the thickness thereof was 12.5 μm.

Evaluation (evaluation)

< Reflectance >

A reflectance of each 10nm in a wavelength range of 360 to 740nm was measured from the side where the display portion was formed using a 45℃0℃spectrophotometer (CM-25 cG, manufactured by Konikoku Meida Co.).

Wherein the minimum value of the reflectance and the difference between the maximum value and the minimum value are obtained in the whole wavelength range of 420nm to 700 nm. The results are shown in "minimum reflectance (%)" and "maximum difference in reflectance (%)" in "display portion" of table 1.

The reflectance curves of examples 1 and 2 show monotonic decreases, and the reflectance curves of examples 3 and 4 show monotonic increases.

< Brightness L ^* >

The display portion of the obtained glass plate was measured using a spectrophotometer (CM-25 cG, manufactured by konikama, inc.) from the side on which the display portion was formed in accordance with the regulation of JIS Z8781-4:2013, and the value of luminance L ^* in the measured L ^*a^*b^* color system was obtained. The light source adopts D65. The results are shown as "luminance L ^*" in the "display portion" in table 1.

< Surface roughness Ra >

The display part of the obtained glass plate was measured for an arithmetic average roughness Ra in accordance with JIS B0601:1994 by using a stylus surface roughness measuring instrument (ACCRETECH, SURFCOM NEX 001DX-12, manufactured by Tokyo precision Co., ltd.). The results are shown as "surface roughness Ra (μm)" in the "display portion" of table 1.

< Image visibility and shape clarity >

For the display portion of the obtained glass plate, an image was projected from the side where the display portion was formed using a projector having an illuminance of 1900 lux. The image projected on the display unit was visually observed, and the visibility and shape clarity thereof were evaluated. The results are shown in table 1 as "image visibility (no external light)" and "shape clarity".

In the above evaluation, the evaluation criteria for the image visibility are as follows.

The detail of the projection image can be clearly seen, and the method is very good.

Although it is difficult to see the details of the projected image, the entire image can be seen well.

Delta it is difficult to see the details of the projected image, but the entire image can be seen slightly, and the grid.

And X, the whole projection image is difficult to see, and the method is not good.

In the above evaluation, the evaluation criteria for shape clarity are as follows.

Very good, the outline of the projected image can be clearly seen.

The outline of the projected image was slightly curved, and was good.

The contours of the projected image are mostly curved and gratified.

The contour line of the projected image is often bent sharply, which is undesirable.

For the display portions of the glass plates obtained in examples 1 and 2, an image was projected from the side where the display portion was formed using a projector having an illuminance of 1900 lux. The light with illuminance of 10000 lux was irradiated from the opposite side of the glass plate to the side where the display portion was formed, and the presence of external light was simulated. The image projected on the display unit was visually observed, and the visibility thereof was evaluated. The results are shown in table 1 as "image visibility (with external light)". The evaluation criteria are the same as those of the image visibility in the absence of external light.

In the results of evaluation of image visibility (no external light) and shape clarity, the total score was evaluated when ∈3, ∈2, ∈Δ, and × 0 were used. The results are shown in "comprehensive evaluation" in table 1. The evaluation criteria are as follows.

The total division of the materials is 5 to 6

The total score was 4

The delta is that the total division is 2-3

X the total score is 0 to 1

TABLE 1

From the above results, it was found that the visibility when an image was projected on a display portion was very good by having the display portion with a reflectance of 30% or more and a difference between the maximum value and the minimum value of the reflectance of 20% or less over the entire wavelength range of 420 to 700 nm. In particular, good image visibility can be achieved even in the presence of external light.

It was found that, when the display portion is a portion composed of a ceramic color layer, the visibility in the presence of external light is improved by providing the light shielding portion (examples 1 and 2). It is expected that the same result can be obtained even in the case where the display portion is a portion constituted by an ink layer.

Further, it is found that the shape sharpness of the projected image is also good by setting the surface roughness Ra of the display portion to be within an appropriate range of 1.0 μm or less.

While the application has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof. The present application is based on Japanese patent application (Japanese patent application No. 2023-078088) filed 5/10/2023, the contents of which are incorporated herein by reference.

Symbol description

1 First glass plate

2 Second glass plate

3 Intermediate film

4. Display unit

5. Light shielding part

6. Display area

10. 20, 30, 40 Laminated glass.

Claims

1.A laminated glass having a first glass plate, a second glass plate opposed to the first glass plate, and an interlayer sandwiched between the first glass plate and the second glass plate,

The first and second glass sheets each have a pair of opposed major faces,

2. The laminated glass according to claim 1, wherein the display portion is a portion constituted by an ink layer, a ceramic color layer, or a metal layer containing Ag.

3. The laminated glass according to claim 2, wherein a value of brightness L ^* of the display portion is 50 or more.

4. The laminated glass according to claim 1, wherein,

The second glass plate has a plurality of the display portions,

The plurality of display portions form a display area constituted by a dot pattern.

5. The laminated glass according to claim 4, wherein the display portion occupies 13 to 50% of the display area in a plan view.

6. The laminated glass according to claim 1, wherein the reflectance curve of the display portion in a wavelength range of 420 to 700nm shows monotonic decrease over the entire wavelength range.

7. The laminated glass according to claim 1, wherein the reflectance curve of the display portion in a wavelength range of 420 to 700nm shows monotonically increasing over the entire wavelength range.

8. The laminated glass according to claim 1, wherein the surface roughness Ra of the display portion is 1.0 μm or less.

9. The laminated glass according to claim 1, wherein,

A light shielding part is provided at a position overlapping with the display part in a plan view,

The light shielding portion is located closer to the first glass plate side than the display portion, and has a reflectance of 10% or less over a wavelength range of 420 to 700 nm.

10. The laminated glass according to claim 9, wherein the light shielding portion has a luminance L ^* of 35 or less.

11. The laminated glass according to claim 1, wherein the display portion displays information by reflecting a projected image from a side opposite to the first glass plate side at the display portion.

12. The laminated glass according to any one of claims 1 to 11, wherein the laminated glass is used for a vehicle and is arranged such that the first glass sheet is an outside of the vehicle.

13. A laminated glass as in claim 12 wherein the laminated glass is used for a front glazing.

14. A glass sheet having a pair of opposed major faces, wherein,

A display portion is provided on one main surface,

15. The glass sheet according to claim 14, wherein the display portion is a portion composed of an ink layer, a ceramic color layer, or a Ag-containing metal layer.

16. The glass sheet according to claim 15, wherein the brightness L ^* of the display portion has a value of 50 or more.