Glass article and method for manufacturing same

Abstract

Provided are: a glass article which has excellent appearance and in which the occurrence of whitening after thermoforming can be suppressed; and a method for producing the glass article. The glass article is provided with a functional layer (3) and a silicon oxide-containing layer (4) in this order on a glass substrate (1), and the amount of removed Ar of the silicon oxide-containing layer (4) at a temperature higher than 550 DEG C is 1.86 nm at% or less. The glass article may have a dielectric layer (2) between the glass substrate (1) and the functional layer (3), or may have a shielding layer (5) on the silicon oxide-containing layer (4). This glass article can be used as a window glass for an automobile. In addition, this method for producing a glass article forms the functional layer (3) and the silicon oxide-containing layer (4) by dry coating in this order on the glass substrate (1), and the amount of removed Ar of the silicon oxide-containing layer (4) at a temperature higher than 550 DEG C is 1.86 nm at% or less.

Description

Technical Field

[0001] The present invention relates to a glass article and a method for manufacturing the same. Background Art

[0002] Glass articles typified by window glass for vehicles or buildings are given desired properties by coating the surface of a glass substrate with various materials according to their uses.

[0003] Patent Document 1 discloses a glass plate having a heat radiation reflective coating on a substrate, the heat radiation reflective coating including a functional layer containing a transparent conductive oxide (TCO) and a SiO2 layer. Further, Patent Document 1 discloses that the glass plate having a SiO2 layer as the outermost layer has adaptability to an opaque shielding print formed of a black enamel layer provided in a peripheral region, and a good appearance can be obtained. In addition, it is known that a peripheral portion of a glass article for vehicles (for example, window glass for automobiles) is provided with a shielding layer to which a black pigment, glass frit, or the like is applied for the purpose of preventing deterioration of an adhesive caused by sunlight and improving appearance. Prior Art Documents Patent Documents

[0004] Patent Document 1: International Publication No. 2016 / 184732 Summary of the Invention Technical Problem to be Solved by the Invention

[0005] In the glass plate having the structure described in Patent Document 1, depending on the type of the shielding print, that is, the shielding layer, bubbles may be generated during the heat forming process and voids may be formed in the shielding layer portion. As a result, there is a case where the surface of the glass article looks white (whitening) and the appearance is impaired.

[0006] The present disclosure has been made in view of the above problems, and an object thereof is to provide a glass article having excellent appearance in which whitening after heat forming can be suppressed and a method for manufacturing the same. Means for Solving the Technical Problem

[0007] The glass article of the present disclosure sequentially includes a functional layer and a silicon oxide-containing layer on a glass substrate, and the silicon oxide-containing layer has an Ar desorption amount at a temperature higher than 550 °C of 1.86 nm·atomic% or less. In the above glass article, the Ar desorption amount of the silicon oxide-containing layer at a temperature higher than 550 °C may be 0.92 nm·atomic% or less. In any of the above glass articles, the ratio of the Ar desorption amount of the silicon oxide-containing layer at a temperature of 550 °C or lower to the total Ar desorption amount may be 95.0% or more. In the glass article of any one of the above, a shielding layer may be provided on the above silicon oxide-containing layer, and the Bi / Si ratio in the shielding layer may be 3.8 or less. In the glass article of any one of the above, the SiO2 content in the shielding layer may be 15% by mass or more. In the glass article of any one of the above, the silicon oxide-containing layer may contain an element selected from Al and Zr. In the glass article of any one of the above, a dielectric layer may be provided between the glass substrate and the functional layer, and the dielectric layer may contain an element selected from Si, C, Ti, Zr, Nb, Zn, Sn, and Al, or an oxide, nitride, or oxynitride of these elements. In the glass article of any one of the above, the functional layer may contain an element selected from In, Sn, Al, Ni, Cr, Zr, Ti, Nb, W, Fe, and F, or an oxide, nitride, or oxynitride of these elements. The glass article of any one of the above can be used as an automotive window glass. The method for manufacturing the glass article of the present invention is to sequentially form a functional layer and a silicon oxide-containing layer on a glass substrate by dry coating, and the Ar desorption amount of the silicon oxide-containing layer at a temperature higher than 550 °C is 1.86 nm·atomic% or less. In the method for manufacturing the above glass article, the power density during sputtering of the silicon oxide-containing layer may be 9.8 W / cm 2 or less. In the method for manufacturing the glass article of any one of the above, the process gas pressure during sputtering of the silicon oxide-containing layer may be 2.0 mTorr or more. In the method for manufacturing the glass article of any one of the above, the average O2 mixing ratio in the process gas during sputtering of the silicon oxide-containing layer may be 80 vol% or less. Advantages of the Invention

[0008] According to the present invention, there is provided a glass article with excellent appearance capable of suppressing whitening after thermoforming and a method for manufacturing the same. Description of the Drawings

[0009] Figure 1A is a schematic cross-sectional view of an embodiment of the glass article of the present disclosure. Figure 1B is a schematic cross-sectional view of an embodiment of the glass article of the present disclosure. Figure 1C is a schematic plan view of an embodiment of the glass article of the present disclosure. Figure 2It is a graph showing an example of a curve of each atomic concentration measured by a Rutherford backscattering spectrometry apparatus in the depth direction. Detailed Description of the Invention

[0010] In this specification, "~" indicating a numerical range means that the numerical values described before and after it are included as the lower limit value and the upper limit value. In the numerical ranges described hierarchically in this specification, the upper limit value or the lower limit value described in one numerical range can also be replaced with the upper limit value or the lower limit value of other hierarchically described numerical ranges. In addition, in the numerical ranges described in this specification, the upper limit value or the lower limit value of this numerical range can also be replaced with the value shown in the examples.

[0011] As described above, when various shielding layers are applied to the glass plate having the structure described in Patent Document 1, depending on the type of the shielding layer, whitening may occur on the surface of the obtained glass plate due to voids generated during the thermoforming process.

[0012] The present inventors speculate that the occurrence of whitening due to the thermoforming (and subsequent cooling as needed) operation is due to the following reasons. That is, during the formation of the coating film (for example, a dry coating film), the gas contained in the coating film (for example, process gas in the dry coating: inert gas such as Ar) is degassed when heated. Subsequently, due to thermoforming, the material for forming the shielding layer melts, and the gas stays near the interface between the coating film and the shielding layer or in the shielding layer, and finally voids (pores) of various shapes are formed in this part. Then, it is speculated that light is scattered due to the generated voids, and when observing the glass article from the side where the shielding layer is not provided, a whitish appearance (whitening) occurs.

[0013] As a result of intensive studies by the present inventors, it has been found that by making the Ar desorption amount at a specific temperature in the silica-containing layer provided in the glass article within a specific range, whitening can be suppressed regardless of the type of the shielding layer.

[0014] Hereinafter, embodiments of the glass article (hereinafter also referred to as "this glass article") of the present disclosure will be described in detail with reference to the drawings, but the present disclosure is not limited to this embodiment. In addition, within the scope not departing from the gist of the present disclosure, modifications can be arbitrarily made.

[0015] <Glass Article> This glass article can be suitably used as vehicle glass for vehicles such as automobiles, particularly automotive window glass, and can also be used at any position on the front, rear, side, and top of the vehicle body. In addition, this glass article can be used without limitation for applications other than vehicles, such as buildings. Further, this glass article only needs to have the structure shown below at least in a part thereof. For example, it can be used as a single-piece glass including one glass substrate, or can be used as laminated glass including multiple glass substrates. The manufacturing method of this glass article is not particularly limited, but it can be manufactured using the conventionally well-known float method described later.

[0016] As shown in this glass article Figure 1A , a functional layer 3 and a silicon oxide-containing layer 4 are sequentially provided on a glass substrate 1. In addition, this glass article can also have a dielectric layer 2 between the glass substrate 1 and the functional layer 3 as shown in Figure 1B . It can also have a shielding layer 5 on at least a part of the silicon oxide-containing layer 4 as shown in Figure 1C . In this glass article, these layers only need to be sequentially laminated on at least a part of one surface of the glass substrate. These layers can be laminated on the entire glass substrate constituting the glass article, or can not be laminated. In addition, the dielectric layer 2 can be in contact with the glass substrate 1, or other layers can be disposed between the glass substrate 1 and the dielectric layer 2 so that the glass substrate 1 and the dielectric layer 2 are not directly in contact. Other layers can also be disposed between the dielectric layer 2 and the functional layer 3, or between the functional layer 3 and the silicon oxide-containing layer 4 so that these layers are not directly in contact. For example, coating films such as a dielectric layer 2, a functional layer 3, and a silicon oxide-containing layer 4 can be disposed on the entire glass substrate, and a frame-shaped shielding layer 5 can be disposed at a position on the coating film that becomes the peripheral portion of the glass substrate as shown in Figure 1C .

[0017] In addition, within the range where the effects of the present disclosure can be obtained, other layers can be provided between or on each layer, such as a tone adjustment layer for adjusting the tone, a heat insulating film layer, a UV cut-off film layer, etc. From the viewpoint of improving the whitening resistance, this glass article preferably forms a silicon oxide-containing layer 4 as the outermost layer of the coating film, and a shielding layer is disposed on the silicon oxide-containing layer 4. A sealing layer (not shown) such as a sealing lip or an adhesive layer (not shown) for fixing other components can also be provided on the silicon oxide-containing layer 4 (for example, on the shielding layer 5 in the case of having a shielding layer 5) with a primer layer interposed therebetween. The primer layer, the sealing layer, and the adhesive layer can appropriately use conventionally well-known materials. In addition, an abrasion resistance layer can also be disposed on the silicon oxide-containing layer. The abrasion resistance layer can be constituted by, for example, at least one selected from ZrBO, ZrO2, Ta2O5, Al2O3, TiO2, Nb2O5, SiN, and BN. In addition,Figure 1A and Figure 1B respectively show schematic cross-sectional views of two embodiments of the present glass article, Figure 1C and show schematic plan views thereof when viewed from the side of the shielding layer 5.

[0018] [Silicon Oxide-Containing Layer] In the present glass article, the amount of Ar desorbed from the silicon oxide-containing layer at a temperature higher than 550 °C is 1.86 nm·atomic% or less. When the amount of Ar desorbed is 1.86 nm·atomic% or less, the film density of the silicon oxide-containing layer is within an appropriate range, and before reaching the temperature at which the glass frit contained in the shielding layer starts to melt (for example, 550 to 600 °C), the Ar in the coating film is almost completely removed. Therefore, generation of voids caused by the Ar can be suppressed, and as a result, whitening of the glass article can be suppressed, and an excellent appearance can be obtained. For example, even if the total amount of Ar desorbed from the silicon oxide-containing layer is large, as long as the coating film satisfies the above conditions, most of the Ar amount is degassed at a temperature of 550 °C or lower, and whitening caused by voids can be suppressed, and a glass article having an excellent appearance can be provided. From the same viewpoint, the amount of Ar desorbed from the silicon oxide-containing layer at a temperature higher than 550 °C is preferably 0.92 nm·atomic% or less, more preferably 0.14 nm·atomic% or less. In addition, when the present glass article includes multiple layers (for example, two layers) of the above-described silicon oxide-containing layers, the total amount of Ar desorbed from these multiple layers of silicon oxide-containing layers at a temperature higher than 550 °C satisfies the above range.

[0019] In addition, from the viewpoint of preventing a decrease in heat resistance, the amount of Ar desorbed from the silicon oxide-containing layer at a temperature higher than 550 °C is preferably 0.03 nm·atomic% or more, more preferably 0.05 nm·atomic% or more, and further preferably 0.07 nm·atomic% or more.

[0020] Here, the amount of Ar desorbed from the silicon oxide-containing layer of the present glass article at a temperature higher than 550 °C can be determined by measuring the amount of Ar desorbed from the silicon oxide-containing layer from a temperature higher than 550 °C to, for example, the upper limit temperature (for example, 750 °C) that will be reached during actual manufacture of the glass article. However, generally, the amount of Ar desorbed from the silicon oxide-containing layer at a temperature higher than 650 °C is almost zero. Therefore, the amount of Ar desorbed from the silicon oxide-containing layer at a temperature higher than 550 °C can also be determined by measuring the amount of Ar desorbed from the silicon oxide-containing layer at a temperature from higher than 550 °C to 650 °C or lower. The specific measurement method for the amount of Ar desorbed from the silicon oxide-containing layer at a temperature higher than 550 °C will be described later.

[0021] Such a glass article having a silica-containing layer with a specific Ar removal amount has excellent anti-whitening properties, can suppress the occurrence of whitening caused by voids, and can have an excellent appearance. Therefore, even when the glass article is formed into a curved shape for vehicles at a high temperature (e.g., 600 to 750 °C), the occurrence of whitening can be easily avoided.

[0022] In addition, in this glass article, it is preferable that the ratio of the Ar removal amount at a temperature of 550 °C or lower to the total Ar removal amount of the silica-containing layer is 95.0% or more. When this ratio is 95.0% or more, almost no Ar remains in the coating film during the formation process of the shielding layer, void generation can be easily suppressed, and regardless of the type of the shielding layer, whitening of the glass article can be easily suppressed. From the same viewpoint, this ratio is more preferably 96.0% or more, and further preferably 97.0% or more.

[0023] Here, the total Ar removal amount of the silica-containing layer of this glass article can be determined, for example, by measuring the total Ar removal amount from room temperature (e.g., 25 °C) to the upper limit temperature (e.g., 750 °C) that the glass article will reach during actual manufacturing. However, as described above, generally, the Ar removal amount at a temperature of 650 °C or higher of the silica-containing layer is almost zero. Therefore, the total Ar removal amount of the above silica-containing layer can also be determined by measuring the Ar removal amount of the silica-containing layer at a temperature of 650 °C or lower. Therefore, the ratio of the Ar removal amount at a temperature of 550 °C or lower to the total Ar removal amount of the silica-containing layer can be replaced by measuring the ratio of the Ar removal amount at a temperature of 550 °C or lower to the Ar removal amount at a temperature of 650 °C or lower of the silica-containing layer.

[0024] In this glass article, the silica-containing layer may be a layer containing silica (SiO x : for example, x = 1, 2). Therefore, the silica-containing layer may be a layer composed of pure silica (SiO2), or may contain one or more other elements selected as dopants from aluminum (Al), boron (B), tin (Sn), titanium (Ti), zirconium (Zr), hafnium (Hf), and nitrogen (N), etc. That is, the silica-containing layer can be composed of, for example, one layer or two or more layers selected from SiO2, SiO2:Al, SiO2:B, SiO2:Sn, SiO2:Ti, SiO2:Zr, SiO2:Hf, and SiO2:N, or a silica-containing layer containing two or more of the above dopants. More specifically, for example, the silica-containing layer may have only one SiO x layer on the glass substrate, or may sequentially have a SiO x layer and a SiO x layer doped with other elements. In the silicon oxide-containing layer, from the viewpoint of improving the whitening resistance, it is preferable to contain an element selected from Al and Zr. In addition, the dopant is not limited to the above substances, and conventionally known substances may be appropriately contained.

[0025] The content of silicon oxide (SiO x ) in the silicon oxide-containing layer is not particularly limited, but from the viewpoints of suppressing void formation and improving whitening resistance, it is preferably 85% by mass or more, more preferably 90% by mass or more, and further preferably 92% by mass or more.

[0026] The thickness of the silicon oxide-containing layer is not particularly limited, but from the viewpoints of antireflectivity and adhesion, it is preferably 20 nm or more, more preferably 40 nm or more, and further preferably 80 nm or more. In addition, from the viewpoint of whitening resistance, the thickness of the silicon oxide-containing layer is preferably 150 nm or less, more preferably 130 nm or less, and further preferably 110 nm or less. In addition, in the case of forming a multilayer silicon oxide-containing layer, it is preferable that the total thickness of the entire silicon oxide-containing layer is within the above range. For example, in the case where the silicon oxide-containing layer includes a SiO x layer and a SiO x layer doped with other elements, from the viewpoint of improving whitening resistance, the thickness ratio of the two (thickness of the SiO x layer: thickness of the doped SiO x layer) is preferably 2:1 to 5:1, and more preferably 3:1 to 4:1.

[0027] The silicon oxide-containing layer is provided on the outer surface side of the functional layer on the glass substrate as described above. The method of laminating a coating film including a dielectric layer as needed and including a functional layer and a silicon oxide-containing layer on the glass substrate is not particularly limited. However, from the viewpoint of more effectively exerting the excellent effects of the present disclosure, it is preferable to form a dry coating film by dry coating using a vapor deposition method to form a thin film in a vacuum. Examples of the dry coating film include a hot wire reflection coating film, a low-emissivity coating film (Low-E film), a low-reflection coating film, a p-polarized light reflection coating film, etc. Among them, from the viewpoint of more effectively exerting the excellent effects of the present disclosure, the coating film is more preferably a low-emissivity coating film and a p-polarized light reflection coating film having two or more layers or three or more layers with the silicon oxide-containing layer as the uppermost layer, and further preferably a low-emissivity coating film. As a method for forming each film, conventionally known methods can be appropriately used.

[0028] In addition, the composition of the coating film can be determined by energy dispersive X-ray spectroscopy (SEM-EDX). The acceleration voltage at this time can be appropriately set, but from the viewpoint of performing more accurate measurement, it is preferably 5 to 25 keV, and more preferably 15 to 20 keV.

[0029] In addition, the film thickness of each layer of the coating film can be measured using a stylus profilometer after forming a single film by film formation, or can be determined by optical simulation based on spectroscopic measurement or observation using a transmission electron microscope (TEM) in the laminate. The acceleration voltage in TEM observation can be set appropriately, but from the viewpoint of performing more accurate measurement, it is preferably 40 to 1000 kV, more preferably 60 to 300 kV. For magnification calibration, for example, a standard sample GaAs / AlAs superlattice certified reference material (NIMC CRM5201-a (trade name)) produced by the National Institute of Advanced Industrial Science and Technology can be used.

[0030] In this glass article, other layers can be formed on the silicon oxide-containing layer, but from the viewpoint of suppressing the whitening of the glass article, when a shielding layer is provided, it is preferably formed on the silicon oxide-containing layer, more specifically, on the surface of the silicon oxide-containing layer.

[0031] [Dielectric layer] The dielectric layer can be disposed on the glass substrate, specifically, between the glass substrate and the functional layer. In addition, the dielectric layer can be formed by the above dry coating method, and preferably contains elements selected from Si, C, Ti, Zr, Nb, Zn, Sn, and Al, or contains oxides, nitrides, or oxynitrides of these elements. In addition, a combination of two or more of these components can also be contained. For example, the dielectric layer can use Si(Al)N, SiO2, TiO2, ZnO, or a layer containing a dopant (e.g., Zr) in these layers. In addition, the dielectric layer can be composed of one layer or two or more layers. The thickness of the dielectric layer is not particularly limited, but from the viewpoint of imparting excellent various properties, the total thickness is preferably 20 to 100 nm, more preferably 30 to 90 nm, and further preferably 40 to 80 nm.

[0032] [Functional layer] The functional layer can be formed by the above dry coating method, and preferably contains, for example, elements selected from In, Sn, Al, Ni, Cr, Zr, Ti, Nb, W, Fe, and F, or contains oxides, nitrides, or oxynitrides of these elements. In addition, a combination of two or more of these components can also be contained. For example, the functional layer can use SnO2, In2O3 (ITO), ZrN, TiN, CrN, or a layer containing a dopant in these layers. In addition, the functional layer can be composed of one layer or two or more layers. The thickness of the functional layer is not particularly limited, but from the viewpoint of imparting excellent various properties, the total thickness is preferably 40 to 200 nm, more preferably 50 to 180 nm, and further preferably 60 to 160 nm.

[0033] The total thickness of the coating film including the above functional layer and the silicon oxide-containing layer (and also including a dielectric layer as required) is not particularly limited. However, from the viewpoint of imparting excellent various properties, the total thickness of the coating film is preferably 25 to 500 nm, more preferably 50 to 450 nm, and still more preferably 100 to 400 nm.

[0034] As described above, various dry coating films having a silicon oxide-containing layer formed on the surface can be applied to the present glass article. Hereinafter, each dry coating film will be briefly described mainly focusing on the portion other than the silicon oxide-containing layer formed on the surface.

[0035] For example, the hot-line reflection coating film can be composed of one or more layers, and can be composed of multiple layers (such as 10 to 18 layers). Specifically, in addition to the above dielectric layer and functional layer, the hot-line reflection coating film can further include a barrier layer. For example, the hot-line reflection coating film can be composed of a first dielectric layer, a functional layer, a barrier layer, and a second dielectric layer (such as a silicon oxide-containing layer) in this order from the glass substrate side. In addition, the above functional layer can be composed of any one of Ag, Au, Cu, Al, Nb, W, Fe, and Pt or a combination thereof. Among them, as the above functional layer, it is preferably composed of any one of Au, Cu, Al, and Pt or a combination thereof. In addition, the above dielectric layer and the above barrier layer can be composed of any one of Ti, Zn, Sn, Si, Al, and Ni or a combination thereof. Further, the dielectric layer and the barrier layer can also be composed of oxides, nitrides, or oxynitrides of these elements.

[0036] The low-emissivity coating film can be composed of one or more layers, and can be composed of multiple layers (such as 2 to 6 layers) for example. For example, the low-emissivity coating film can be composed of a first dielectric layer, a functional layer, and a second dielectric layer (such as a silicon oxide-containing layer) in this order from the glass substrate side. In addition, the above functional layer can be composed of any one of In, Sn, Al, Ni, Cr, Zr, Ti, and F or a combination thereof. Further, the functional layer can also be composed of oxides, nitrides, or oxynitrides of these elements. The above dielectric layer can be composed of any one of Si, C, Ti, Zr, Nb, Zn, Sn, and Al or a combination thereof. Further, the dielectric layer can also be composed of oxides, nitrides, or oxynitrides of these elements.

[0037] In addition, when forming a low-emissivity coating film on a transparent glass substrate, in the case where the above functional layer contains a transparent conductive oxide (TCO), desired characteristics can be obtained by adjusting its degree of oxidation. Further, the degree of oxidation can be appropriately adjusted by adjusting the oxygen addition amount of the film-forming gas when forming the functional layer, and the degree of oxidation can be appropriately set according to the desired characteristics. However, particularly in the case of forming an ITO (indium tin oxide) layer as the functional layer using an indium tin oxide target, it is preferable to add 0.1 to 3.0 vol% of oxygen to Ar which is the main film-forming gas. For example, by forming a low-emissivity coating film on a 1 to 3 mm transparent glass substrate by this method and heating it in the range of 500 to 700 °C for 2 to 10 minutes, a glass substrate with a low-emissivity coating film having a visible light transmittance of 85% or more and a resistance value of 25 Ω / sq or less can be obtained. At this time, the dielectric layer can be, for example, an oxynitride. Thus, by adding a small amount of oxygen to the film-forming gas to adjust the degree of oxidation of the transparent conductive oxide film, various characteristics such as the resistance and visible light transmittance of the glass article with a low-emissivity coating film can be easily adjusted to an appropriate range.

[0038] In addition, when forming a low-emissivity coating film on a transparent glass substrate, in the case where the functional layer contains a transparent conductive oxide (TCO), by containing moisture in the film-forming gas, excessive crystallization during heating can be easily suppressed, and crack generation can be easily suppressed. Further, the amount of moisture contained in the film-forming gas can be appropriately adjusted, but particularly in the case of forming an ITO (indium tin oxide) layer as the functional layer using an indium tin oxide target, the following method is preferable. That is, it is preferable that moisture is present in the film-forming gas in the range where the H2O / Ar partial pressure ratio in the film-forming gas measured using a quadrupole mass spectrometer is 2.0% or less. For example, by forming a low-emissivity coating film on a 1 to 3 mm transparent glass substrate by this method and heating it in the range of 500 to 700 °C for 2 to 10 minutes, a glass substrate with a low-emissivity coating film without cracks can be obtained. At this time, the dielectric layer can be, for example, an oxynitride. Thus, by containing a specified amount of moisture and other components in the film-forming gas, crack generation can be easily suppressed.

[0039] The low-reflection coating film may be composed of more than one layer, for example, it may be composed of multiple layers (such as three layers). For example, in terms of refractive index, the low-reflection coating film may be composed of a low-refractive-index layer, a high-refractive-index layer, and a silicon oxide-containing layer in sequence from the glass substrate side, or may be composed of a high-refractive-index layer, a low-refractive-index layer, a high-refractive-index layer, and a silicon oxide-containing layer in sequence, or may be composed of a low-refractive-index layer, a high-refractive-index layer, a low-refractive-index layer, a high-refractive-index layer, and a silicon oxide-containing layer in sequence, or may be composed of a high-refractive-index layer, a low-refractive-index layer, a high-refractive-index layer, a low-refractive-index layer, a high-refractive-index layer, and a silicon oxide-containing layer in sequence. In this case, these low-refractive-index layers and high-refractive-index layers become functional layers. That is, the low-reflection coating film may have multiple functional layers. In addition, the functional layer closest to the glass substrate side (for example, the layer directly above the glass substrate) may be a low-refractive-index layer or a high-refractive-index layer, but the functional layer closest to the silicon oxide-containing layer side (for example, the layer directly below the silicon oxide-containing layer) is preferably a high-refractive-index layer. More specifically, for example, the above-mentioned low-refractive-index layer may be composed of Si, and the above-mentioned high-refractive-index layer may be composed of any one of Ti, Nb, Ta, and Sn or a combination thereof. In addition, any one of these refractive index layers may also be composed of oxides, nitrides, or oxynitrides of these elements.

[0040] The p-polarized light reflection coating film may be composed of more than one layer, for example, it may be composed of multiple layers (such as two layers). For example, in terms of refractive index, the p-polarized light reflection coating film may be composed of a high-refractive-index layer and a low-refractive-index layer in sequence from the glass substrate side, or may be composed of a high-refractive-index layer, a low-refractive-index layer, a high-refractive-index layer, and a low-refractive-index layer in sequence. In this case, the low-refractive-index layer on the outermost surface side becomes a silicon oxide-containing layer, and the other layers become functional layers. That is, in the p-polarized light reflection coating film, the functional layer may be one layer or multiple layers of two or more layers. The high-refractive-index layer may be composed of any one of Au, Ag, Cu, Al, Zn, Zr, Sn, Nb, Ni, In, Ce, W, Mo, Sb, Cr, B, Y, La, Ta, Bi, and Ti or a combination thereof, or may be composed of oxides, nitrides, or oxynitrides of these elements. For example, the high-refractive-index layer may be Zr:TiO2 containing TiO2 and other elements as dopants. The low-refractive-index layer may be composed of oxides, nitrides, or oxynitrides of Si, and may also contain Al or Zr, but at least the low-refractive-index layer on the outermost surface side is the above-mentioned silicon oxide-containing layer.

[0041] [Glass substrate] The glass substrate (glass plate) of the present glass article may appropriately use a conventionally well-known glass substrate. For example, a heat ray absorbing glass, a transparent glass, a soda-lime glass, a quartz glass, a borosilicate glass, an alkali-free glass, a green glass, a UV green glass, etc. may be used as the glass substrate. However, when the present glass article is used as a vehicle glass, it is required that the glass substrate has a visible light transmittance that conforms to the safety standards of the country where the vehicle is used. In the case of being used for other purposes, it is required to have the characteristics necessary for that purpose. Therefore, it is preferable to appropriately adjust the composition of the glass substrate to achieve the required characteristics. As the composition of the glass substrate, expressed in mass% based on oxides, for example, the following compositions can be cited. In addition, the composition of the glass substrate can be determined by fluorescent X-ray analysis. Silicon dioxide (SiO2): 70 to 73 mass% Aluminum oxide (Al2O3): 0.6 to 2.4 mass% Lime (CaO): 7 to 12 mass%, Magnesium oxide (MgO): 1.0 to 4.5 mass% R2O: 13 to 15 mass% (R is an alkali metal, such as Na or K) Total iron oxide (T-Fe2O3) converted to Fe2O3: 0 to 1.5 mass%.

[0042] In addition, the glass substrate may be substantially transparent or may be given a hue, that is, colored. In addition, a glass substrate that has been strengthened as needed may also be used as the glass substrate. As the strengthening treatment, it may be a chemical strengthening treatment or a physical strengthening treatment (air-cooled strengthening treatment).

[0043] In addition, the shape of the glass substrate only needs to be able to be formed into a shape corresponding to the desired use and is not particularly limited. For example, it may be rectangular. As the formed shape of the present glass article, a curved shape can be cited. The form of the curve is not particularly limited. For example, it can be formed into a shape that is curved in the vertical direction of the paper surface shown in Figure 1A In addition, the present glass article includes a glass article before forming the glass substrate provided with a coating film (and a shielding layer) and a glass article after forming the glass substrate into a desired shape. Therefore, the glass substrate of the present glass article may be a rectangular glass substrate before forming, or a curved glass substrate after forming. In addition, the forming of the present glass article can be carried out, for example, by performing heat bending processing called firing bending when firing a shielding layer provided as needed to form a curved surface on the glass substrate. In addition, the forming of the present glass article can be carried out by performing firing bending separately after forming a shielding layer or the like on the glass substrate, or can be carried out by performing firing bending after pre-firing once after forming a shielding layer or the like. In this way, the forming period of the present glass article can be appropriately selected.

[0044] The thickness of the glass substrate can be set according to the purpose and is not particularly limited. For example, in the case of an automobile used in a vehicle, the thickness of the glass substrate is, for example, 0.2 to 5.0 mm, preferably 0.3 to 3.0 mm. In the case of being used for an automobile, especially for a windshield or a sunroof, considering the strength such as the anti-flyrock performance, the thickness of the glass substrate on the outer side of the vehicle when the laminated glass is installed on the automobile is preferably 1.1 mm or more, more preferably 1.8 mm or more. In addition, considering the weight reduction of the laminated glass, the thickness of the glass substrate is preferably 3.0 mm or less, more preferably 2.8 mm or less. In this laminated glass, considering the operability, the thickness of the glass substrate on the inner side of the vehicle when installed on the automobile is preferably 0.3 mm or more, and considering the weight reduction of the laminated glass, it is preferably 2.3 mm or less. In addition, this glass article can be used not only as a single piece of glass but also as a laminated glass and can be used for various purposes. In addition, the thicknesses of the two glass substrates used in the laminated glass can be the same or different.

[0045] The glass substrate can be appropriately manufactured by a conventionally known method (such as the float method, the fusion method, and the roll pressing method), and its manufacturing method is not particularly limited. In addition, as the glass substrate, commercially available products can also be used.

[0046] [Masking layer] This glass article can have a masking layer on the silicon oxide-containing layer. The masking layer is disposed on at least a part of one surface of the glass substrate, specifically, on at least a part of the coating film. However, when this glass article is used as a vehicle glass article, it is preferably provided to cover the peripheral portion of the glass substrate. By means of this masking layer, the mounting components or the terminals of electrical components mounted on the vehicle body cannot be seen from the outside of the vehicle. Therefore, this masking layer can be an opaque masking layer. In addition, the shape of the masking layer can be various shapes such as a frame edge shape, a strip shape, and a dot shape. Figure 1C In the figure, a frame edge-shaped masking layer 5 is provided on the peripheral portion of the glass substrate, more specifically, on the peripheral portion of the silicon oxide-containing layer 4. The masking layer 5 can be provided, for example, to cover a specific area from the edge of the glass substrate 1. More specifically, the masking layer 5 can cover at least a part within 30 mm (for example, within 50 mm from the edge) from the edge of the glass substrate 1.

[0047] The shielding layer may contain a crystalline component, a pigment, and additives (such as a resin), etc. The components (elements) constituting the shielding layer are not particularly limited. For example, the following elements may be contained: Si, Bi, O, Fe, Ni, C, B, Al, Li, Na, K, Mg, Ca, Ba, Sr, Zn, Ti, Ce, Zr, Cu, Cr, Mn, Co.

[0048] From the viewpoint of preventing the formation of the above-mentioned voids and the occurrence of whitening, it is preferable to adjust the composition in the shielding layer. Specifically, it is preferable that the composition ratio of Si (silicon), which has the effect of raising the melting start temperature during heat forming, and Bi (bismuth), which has the effect of lowering the above-mentioned melting start temperature, that is, the Bi / Si ratio (mass% ratio) in the above-mentioned shielding layer is 3.8 or less. When the Bi / Si ratio is 3.8 or less, the sintering temperature of the components in the shielding layer can be made higher, and before the shielding layer is sintered, more gas (Ar) can be degassed from the silicon oxide-containing layer. As a result, the amount of Ar degassing in the silicon oxide-containing layer at a temperature higher than 550 °C can be suppressed, the formation of voids can be suppressed, and a glass article with excellent appearance can be easily obtained. Furthermore, from the same viewpoint, the Bi / Si ratio is more preferably 3.7 or less, further preferably 3.5 or less, and particularly preferably 3.3 or less.

[0049] In addition, the composition of the shielding layer can be determined by energy dispersive X-ray spectroscopy (SEM-EDX). The acceleration voltage at this time can be set appropriately, but from the viewpoint of performing a more accurate measurement, it is preferably 5 to 25 keV, and more preferably 15 to 20 keV.

[0050] The said shielding layer (for example, a black ceramic layer) can be formed by coating a material for forming a shielding layer (ceramic paste) on a glass substrate, more specifically, on a desired position (for example, on the peripheral part) of a coating film and heating and sintering at a high temperature. The firing temperature can be set appropriately. For example, it can be set to 500 to 700 °C (for example, 600 °C or higher). The material for forming the shielding layer before firing may include a glass frit (equivalent to the crystalline component when forming the shielding layer), a pigment (such as a heat-resistant black pigment), an (organic) carrier for dispersing the pigment as needed, a conductive metal, a reducing agent, a dispersant surfactant, a fluidity modifier, a fluidity aid, a bonding promoter, a stabilizer, a colorant, and other additives. In addition, as the material for forming the shielding layer, a commercially available product can also be used. By forming the shielding layer into a fired layer, the shielding layer is joined to the glass substrate.

[0051] The above-mentioned frit can contain, for example, one or more components such as SiO2, Bi2O3, Cr2O3, Cs2O, Na2O, B2O3, ZnO, TiO2, La2O3, Nb2O5, MnO2, CeO2, MoO3, WO3, F, Al2O3, BaO, MgO, CaO, K2O, etc. In addition, it is known that a frit having a high melting point range has excellent chemical resistance and a low coefficient of thermal expansion. SiO2 in the frit forms a glass network and is also a crystallization component. Moreover, it also controls chemical, thermal, and mechanical properties and has the property of increasing the melting point of the frit. SiO2 may not simply contain SiO2, but may also contain, for example, Bi4Si3O 12 such a composite. From the viewpoint of improving the whitening resistance, the content of SiO2 in the shielding layer is preferably 15% by mass or more, more preferably 18% by mass or more, and further preferably 20% by mass or more. In addition, from the viewpoint of maintaining the sinterability, the content of SiO2 in the shielding layer is preferably 30% by mass or less, more preferably 28% by mass or less. On the other hand, Bi2O3 in the frit is a component that forms a glass network and has the property of lowering the melting point. From the viewpoint of improving the whitening resistance, the content of Bi2O3 in the shielding layer is preferably 60% by mass or less, more preferably 55% by mass or less. In addition, from the viewpoint of fluidity, the content of Bi2O3 in the shielding layer is preferably 30% by mass or more, more preferably 35% by mass or more.

[0052] When forming the shielding layer, the frit may have a crystal form different from that in the raw material stage (material for forming the shielding layer) before firing, or may not have it. In addition, the crystalline component in the shielding layer may be composed of one type of frit, or may be composed by fusing multiple frits by firing, for example.

[0053] In addition, the frit can be manufactured by a conventionally well-known method. For example, by mixing starting materials corresponding to the desired composition and then melting them at the desired temperature and time, and cooling them with water as needed, a frit having the desired composition can be manufactured. The frit can be pulverized into the desired particle size (for example, 1 to 8 μm) using a well-known pulverization technique as needed. In addition, commercially available products can also be used as the frit.

[0054] The content of the frit in the material for forming the shielding layer can be appropriately set, but from the viewpoint of obtaining good sinterability, it is preferably 60% by mass or more, more preferably 65% by mass or more, and further preferably 70% by mass or more. On the other hand, from the viewpoint of maintaining the glass strength, the content of the frit in the material for forming the shielding layer is preferably 99% by mass or less, more preferably 98% by mass or less, and further preferably 96% by mass or less. In addition, the content in the material for forming the shielding layer in this specification refers to the content in the total inorganic components of the components constituting the material for forming the shielding layer, and does not include the content of organic components. Therefore, the frit content in the material for forming the shielding layer is the amount after removing the content of fillers and the like contained in the material for forming the shielding layer.

[0055] As the above pigments, pigments conventionally known in the past can be appropriately used. For example, one or more pigments derived from composite inorganic pigments such as corundum - hematite, olivine, johannsenite, pyrochlore, rutile, and spinel can be used. As pigments, for example, metal oxide pigments (spinel pigments) containing copper (Cu), chromium (Cr), iron (Fe), cobalt (Co), nickel (Ni), manganese (Mn), aluminum (Al), magnesium (Mg), zinc (Zn), zirconium (Zr), niobium (Nb), yttrium (Y), tungsten (W), antimony (Sb), and calcium (Ca) can be used. These black spinel pigments can be suitably used in the automotive industry, and in other industries such as construction, household appliances, and the beverage industry, other metal oxide pigments that produce other colors can be appropriately used as pigments.

[0056] In addition, the spinel structure is a conventional pigment structure having the general formula AB2X4, where X is usually O 2- or F - . Here, A and B represent the tetrahedral and octahedral lattice points of the standard spinel lattice. The spinel structure can be formed by various different elements including the first row transition elements, thus becoming the structure of various inorganic pigments. Most spinel compounds have a cubic space group, but the distorted spinel structure can take a tetragonal phase and sometimes an orthorhombic phase.

[0057] More specific examples of the metal oxide pigments include CuO·CrO3, CuCr2O4, (Co, Fe)(Fe, Cr)2O4, MnCr2O4, NiMnCrFe, CuCrMnO, and pigments obtained by modifying these pigments with modifiers. Here, the performance of the pigments can be determined by raw materials, synthesis techniques and conditions, and post - firing treatment, etc. The pigments can be synthesized by conventionally known methods, such as the method described in Japanese Patent Application Laid - Open No. 2019 - 509959, or commercially available products can be purchased. The pigments can be formed, for example, by combining or calcining fine metal oxides or salts containing the target metal to form the desired pigments. At this time, the size of the fine metal oxide can be appropriately set, but it is preferably 1 nm to 10 μm, more preferably 10 nm to 1 μm, and further preferably 50 to 500 nm.

[0058] In addition, as pigments, pigments derived from rare - earth manganese oxide pigments can also be used. For example, (Yx (Mn)O y 、(La x (Mn)O y 、(Ce x (Mn)O y 、(Pr x (Mn)O y 、(Nd x (Mn)O y Here, in the above chemical formula, x is preferably from 0.01 to 99, more preferably from 0.08 to 12, and still more preferably from 0.25 to 4. Additionally, in the above chemical formula, y is the number of oxygen atoms required to maintain electrical neutrality, preferably from x + 1 to 2x + 2. As this pigment, specifically, CeMnO3, PrMnO3, NdMnO3, and pigments obtained by modifying these pigments with a modifier can be cited, etc. Additionally, the rare earth manganese oxide pigment preferably has a perovskite crystal structure or an orthorhombic crystal structure. By using the rare earth manganese oxide pigment, a very high infrared reflectance can be obtained, and the heat generation characteristics can be reduced. Moreover, since the pigment does not contain a cobalt material, even in an acidic solution such as acid rain, hexavalent chromium dissolution will not occur.

[0059] The pigment content in the material for forming the shielding layer can be appropriately set. However, from the viewpoint of obtaining the desired hue, it is preferably 0.1% by mass or more, more preferably 1% by mass or more, still more preferably 2% by mass or more, and particularly preferably 5% by mass or more. Additionally, from the viewpoint of maintaining the sinterability of the shielding layer, the pigment content is preferably 50% by mass or less, more preferably 30% by mass or less, still more preferably 25% by mass or less, and particularly preferably 15% by mass or less.

[0060] As the organic carrier for dispersing and suspending the above frit and pigment, vegetable oil, mineral oil, low molecular weight petroleum fractions, tridecanol, synthetic resins, and natural resins can be cited, etc. As the conductive metal, for example, silver (silver particles) can be used. As the reducing agent, for example, silicon metal can be used. The dispersing surfactant plays an auxiliary role in wetting the pigment when using an inert particulate inorganic pigment. The dispersing surfactant usually contains a block copolymer, which has a group having an affinity for the pigment, and also contains a solvent (such as xylene, butyl acetate, methoxypropyl acetate) as required. The dispersing surfactant can be appropriately used with conventionally known surfactants. For example, Disperbyk 162 (trade name, produced by BYK Chemie) can be used. The fluidity modifier is used to adjust the viscosity, and conventionally known fluidity modifiers can be appropriately used. For example, the Viscobyk series (produced by BYK Chemie) can be used. The fluidity aid is an additive used to adjust viscosity and fluidity. Conventionally known fluidity aids can be used. For example, Additol VXW6388 (trade name, manufactured by UCB Surface Speciality) can be used. The adhesion promoter is used to improve the compatibility with the layer (coating film) where the shielding layer is provided, and can be appropriately selected according to the composition of the coating film used. As the stabilizer, for example, a light stabilizer or a UV shielding agent can be used. In addition, the compounding amount of these additives can be appropriately set and is not particularly limited.

[0061] The composition of the shielding layer (the overall shielding layer including glass frit, pigment, additives, etc.) is expressed in mass % based on oxides. For example, it can be the following composition. In addition, the composition of the shielding layer can be regarded as the same as the composition of the material for forming the shielding layer before firing. Bi2O3: 35 - 60 mass % SiO2: 15 - 30 mass % Cr2O3: 5 - 25 mass % CuO: 3 - 9 mass % MnO2: 3 - 6 mass % Al2O3: 0.2 - 4 mass % MgO: 0 - 2 mass % CaO: 0 - 3 mass % BaO: 0 - 8 mass % Na2O: 0 - 5 mass % K2O: 0 - 3 mass % TiO2: 0 - 5 mass % ZnO: 0 - 8 mass %.

[0062] The thickness of the shielding layer affects the UV transmittance, acid resistance, weather resistance, concealment, glass strength, and cost. From the viewpoints of UV transmittance, acid resistance, weather resistance, concealment, etc., the thickness of the shielding layer is preferably 5 μm or more, more preferably 8 μm or more, and further preferably 10 μm or more. In addition, from the viewpoints of glass strength and cost, the thickness of the shielding layer is preferably 30 μm or less, more preferably 20 μm or less. The thickness of the shielding layer can be determined using a scanning electron microscope (SEM).

[0063] The firing conditions of the shielding layer can be appropriately set within the range that can achieve the effects of the present disclosure. For example, the firing speed (conveyor speed) (mm / s) and firing temperature (°C) when transporting the object to be processed (to which the material for forming the shielding layer has been applied) in the automotive glass forming process can be adjusted, and the temperature curve can be adjusted when changing the firing temperature during firing. For example, the firing time can be 3 to 30 minutes (preferably 4 to 20 minutes), and the firing temperature can be 550 to 730 °C (preferably 580 to 710 °C, more preferably 600 to 710 °C).

[0064] <Method for manufacturing a glass article> In the method for manufacturing a glass article of the present disclosure (hereinafter also referred to as "the present manufacturing method"), a functional layer and a silicon oxide-containing layer are sequentially formed by dry coating on a glass substrate. And the amount of Ar desorbed from the silicon oxide-containing layer at a temperature higher than 550 °C is 1.86 nm·atomic% or less. Regarding the amount of Ar desorbed, as described above, the description thereof is omitted.

[0065] Dry coating includes physical vapor deposition (PVD: Physical Vapor Deposition) and chemical vapor deposition (CVD: Chemical Vapor Deposition). Physical vapor deposition is a physical film-forming method including vacuum evaporation or sputtering, and chemical vapor deposition is a chemical film-forming method.

[0066] The PVD method is mainly a method in which, in a high vacuum (10 -1 ~10 -5 Pa) state, the film-forming material for forming the film is evaporated and scattered into particles (atoms and molecules) by heating, sputtering, ion beam irradiation, laser irradiation, etc., and is attached and deposited on the surface of the substrate. Vacuum evaporation refers to a technique in which a film-forming material such as a metal or a metal oxide is heated in a vacuum to be melted and evaporated or sublimated, and the evaporated or sublimated particles (atoms and molecules) are attached and deposited on the surface of the substrate to form a film. In addition, sputtering refers to a technique in which an inert gas and a reactive gas (mainly Ar, O2, N2) are introduced into a vacuum, a negative voltage is applied to a target (for example, a plate-shaped film-forming material) to generate a glow discharge, the inert gas atoms are ionized, the gas ions collide with the surface of the target at high speed and beat violently, so that the particles (atoms and molecules) of the film-forming material constituting the target are violently ejected and then attached and deposited on the surface of the substrate to form a film. In the sputtering method, even materials that are difficult for the vacuum evaporation method, such as high melting point metals or alloys, can be formed into films, and a wide range of film-forming materials can be handled.

[0067] On the other hand, the CVD method is a method in which, in the atmosphere to medium vacuum (100 to 10 -1A method of feeding a gaseous raw material in the state of (Pa), and applying energy such as heat, plasma, light, etc. to excite and promote a chemical reaction to synthesize a thin film or fine particles, and adsorb and deposit them on the surface of a substrate.

[0068] As the dry coating film, a film selected from a hot-line reflection coating film, a low-emissivity coating film (Low-E film), a low-reflection coating film, and a p-polarized light reflection coating film can be used. Among them, from the viewpoint of more effectively exerting the excellent effects of the present disclosure, it is preferable to use a low-emissivity coating film and a p-polarized light reflection coating film, and it is more preferable to use a low-emissivity coating film. As a method of forming each film, a conventionally well-known method can be appropriately used.

[0069] The present manufacturing method is not particularly limited, and for example, it may include the following steps. · A step of preparing a glass substrate (substrate preparation step). · A step of forming a functional layer on the above glass substrate (functional layer formation step). · A step of forming a silicon oxide-containing layer on the above functional layer (silicon oxide-containing layer formation step).

[0070] In addition, the above substrate preparation step (substrate manufacturing step) may include a step of melting glass raw materials and flowing them into a tin bath (melting step), and a step of slowly cooling the molten glass raw materials (slow cooling step). Further, when there is a dielectric layer between the glass substrate and the functional layer, there may be a step of forming a dielectric layer on the above glass substrate (dielectric layer formation step) between the substrate preparation step and the functional layer formation step. In addition, when the dielectric layer, the functional layer, and the silicon oxide-containing layer are each composed of multiple layers, steps of forming each layer may be provided.

[0071] In addition, in the glass article obtained by the present manufacturing method, a shielding layer (shielding layer formation step) may be formed on the above silicon oxide-containing layer to manufacture a glass article having a shielding layer (manufacturing method of a glass article having a shielding layer).

[0072] The above shielding layer formation step may include, for example, the following steps. · A step of preparing a material for forming a shielding layer (preparation step of a material for forming a shielding layer). · A step of coating the above material for forming a shielding layer on the above silicon oxide-containing layer (coating step). · A step of sintering the above material for forming a shielding layer coated on the above silicon oxide-containing layer (sintering step).

[0073] The present manufacturing method may further include the following steps. ·A step of heating and shaping a glass substrate, which is successively provided with a dielectric layer, a functional layer, a silicon oxide-containing layer, and an optional masking layer as needed, into a desired shape (heating and shaping step). ·A step of cooling the glass substrate after heating and shaping (cooling step). These steps can be carried out successively, or multiple steps (such as the masking layer formation step (specifically, the sintering step) and the heating and shaping step) can be carried out simultaneously. The present manufacturing method will be described in detail below.

[0074] First, prepare a rectangular glass substrate (glass plate) (substrate preparation step). At this time, the glass substrate can be a commercially available product, or can be manufactured by, for example, the following method. That is, heat a glass raw material formulated into a desired glass composition at a specified temperature to obtain molten glass. Then, pour the obtained molten glass into a tin bath filled with molten tin (melting step), form it into a plate-shaped glass ribbon, and carry out slow cooling (slow cooling step) to obtain a glass substrate. At this time, processing treatment (such as SO2 treatment or cleaning treatment) can also be performed on the obtained glass ribbon. In addition, the shaping of the glass substrate can be carried out in any one of the above melting step and slow cooling step. Furthermore, when manufacturing the glass substrate, it can be appropriately cut into a desired size. For example, when manufacturing a vehicle glass into a front windshield for an automobile, prepare a glass substrate of (500~1300mm)×(1200~1700mm)×(1.6~2.5mm). The glass substrate can be one piece, or can be a laminated glass formed by pasting two or more pieces of glass.

[0075] Next, form coating films in the order of a dielectric layer, a functional layer, and a silicon oxide-containing layer on at least a part of one surface of the glass substrate, for example, on the entire surface of the glass substrate. The formation conditions of these coating films can be appropriately selected. For example, when forming a low-emissivity coating film (Low-E film) as the coating film, use Ar gas, O2 gas, N2 gas, or a mixed gas thereof as the process gas and form it by sputtering.

[0076] Here, the formation conditions of the silicon oxide-containing layer are preferably as follows. From the viewpoint of easily suppressing the Ar desorption amount of the silicon oxide-containing layer at a temperature higher than 550°C to 1.86 nm·atomic% or less, the power density when sputtering the silicon oxide-containing layer (doped or undoped SiO x layer) is preferably in the following range. That is, this power density is preferably 9.8 W / cm 2 Hereinafter, more preferably 9.4 W / cm 2 Hereinafter, further preferably 8.9 W / cm 2Hereinafter, from the viewpoint of preventing a decrease in heat resistance, the power density is preferably 7.0 W / cm 2 or more, more preferably 7.5 W / cm 2 or more. In addition, the above power density is obtained by dividing the power by the area in the case of a rectangular target, and by dividing the power by the length × diameter × π / 3 in the case of a cylindrical target. From the viewpoint of easily suppressing the Ar removal amount at a temperature higher than 550°C within the above specific range, the process gas pressure during sputtering of the silicon oxide-containing layer (e.g., SiO x layer) is preferably 2.0 mTorr or more. Here, in the case where the silicon oxide-containing layer is a SiO x layer doped with other elements (e.g., Zr, etc.), from the same viewpoint, the process gas pressure is more preferably 2.5 mTorr or more, and further preferably 3.0 mTorr or more. In addition, from the viewpoint of preventing a decrease in heat resistance, the process gas pressure during sputtering of the silicon oxide-containing layer (doped or undoped SiO x layer) is preferably 4.0 mTorr or less. From the viewpoint of easily suppressing the Ar removal amount at a temperature higher than 550°C within the above specific range, the average O2 composition ratio in the process gas during sputtering of the silicon oxide-containing layer (e.g., SiO x layer) is preferably 80 vol% or less, more preferably 78 vol% or less. In addition, from the viewpoint of preventing a decrease in heat resistance, the average O2 composition ratio is preferably 60 vol% or more, more preferably 65 vol% or more. Here, in the case where the silicon oxide-containing layer is a SiO x layer doped with other elements (e.g., Zr, etc.), from the viewpoint of easily suppressing the Ar removal amount at a temperature higher than 550°C within the above specific range, the average O2 composition ratio in the above process gas is preferably in the following range. That is, the average O2 composition ratio is preferably 70 vol% or less, more preferably 60 vol% or less. In addition, from the viewpoint of preventing a decrease in heat resistance, the average O2 composition ratio is preferably 45 vol% or more, more preferably 50 vol% or more. As described above, a glass article in which a dielectric layer, a functional layer, and a silicon oxide-containing layer are sequentially disposed on a glass substrate can be obtained. In addition, the dielectric layer may or may not be formed.

[0077] In addition, for the obtained glass article, a frame-shaped shielding layer can be formed on at least a part of the uppermost layer of the silicon oxide-containing layer, for example, on the peripheral portion of the silicon oxide-containing layer (shielding layer forming step). Specifically, a material for forming the shielding layer (for example, ceramic paste) is coated on at least a part of the region of the glass substrate on which the dielectric layer, the functional layer, and the silicon oxide-containing layer are sequentially formed (coating step), and dried as needed. The coating method of the material for forming the shielding layer is not particularly limited. For example, screen printing method, inkjet method, electroprinting, etc. can be used. Specifically, it is preferably printed on the glass substrate with a screen of #150 to #250 mesh.

[0078] In addition, a commercially available product can be used as the material for forming the shielding layer, or it can be prepared separately (material preparation step for forming the shielding layer). The material for forming the shielding layer can be prepared, for example, by dispersing the above-mentioned desired glass frit and pigment in an organic carrier.

[0079] Then, using a firing furnace such as a transportable IR furnace, the obtained glass substrate is heated to a specified temperature to sinter the material for forming the shielding layer on the glass substrate (sintering step). The heating (firing) temperature is not particularly limited. For example, it is 500 to 730 °C (preferably 550 to 700 °C). In addition, the firing speed (transport speed) is not particularly limited, and is preferably 5 to 30 mm / s. In addition, the heating time is, for example, 3 to 30 minutes (preferably 4 to 20 minutes). Through the above steps, a shielding layer is formed on the glass substrate.

[0080] In addition, in order to make the glass frit in the material for forming the shielding layer exhibit various properties, 1 type of glass frit can be used, or 2 or more types of glass frits can be mixed and used. 2 or more types of glass frits having the same composition but different particle sizes can also be mixed and used as appropriate. From the viewpoint of reducing the porosity, the melting point of the glass frit is preferably 600 °C or higher, more preferably 630 °C or higher. In addition, from the viewpoint of the adhesion to the glass, the melting point of the glass frit is preferably 700 °C or lower, more preferably 680 °C or lower. In the case of mixing 2 or more types of glass frits, it is preferable that the softening point of 1 or more types in each glass frit is within the above range, and more preferably the softening points of all the glass frits are within the above range.

[0081] Subsequently, the glass substrate on which the coating film and the shielding layer are sequentially arranged is heated and formed into a desired shape (heating and forming step), and a cooling operation (cooling step) is performed as needed. In addition, it is also possible to perform self-weight bending forming or pressure bending forming to form into a desired shape in a state where the glass substrate is maintained at the heating temperature in the above sintering step. That is, the heating and forming step and the above sintering step can be performed simultaneously. In press-bending forming, for example, according to the shape of the desired automotive window glass, a glass plate is bent using a pressing device (hot pressing device). In self-weight bending forming, the glass substrate is bent using a self-weight bending device. Air-cooling strengthening or the like can also be performed according to the safety standards required for automotive window glass.

[0082] The glass article thus obtained has excellent durability, can suppress the occurrence of whitening, and has excellent appearance. Examples

[0083] The present invention will be described in more detail below with multiple examples, but the present disclosure is not limited to these examples. Among them, Examples 1 to 3 are examples of the present glass article, and Examples 4 to 5 are comparative examples.

[0084] [Example 1] (Preparation of glass substrate and production of coating film) On one surface of the glass substrate, a low-emissivity coating film was formed using a sputtering device. Specifically, first, a glass substrate with a thickness of 2.1 mm (product name: FGY1, manufactured by AGC Inc.) was prepared. Next, by sputtering, a zirconium-containing titanium oxide layer was formed as the first dielectric layer on the surface of the glass substrate. In the film formation, a zirconium-doped titanium dioxide target with 35 mass% zirconium was used, and in the optical simulation based on spectroscopic measurement, the film thickness was 10 nm. Then, by sputtering, a silicon oxide layer was formed as the second dielectric layer. In the optical simulation based on spectroscopic measurement, the film thickness was 35 nm. Subsequently, by sputtering, an ITO (indium tin oxide) layer was formed as the functional layer. In the film formation, an indium oxide target doped with 10 mass% tin oxide was used, and the film was formed using a mixed gas with an average oxygen ratio O2 / (O2+Ar) of 0.2 vol%. In the optical simulation based on spectroscopic measurement, the film thickness was 120 nm. Subsequently, a first silicon oxide-containing layer (SiO x ) was formed. A silicon target was used, and the film was formed using a mixed gas with an average oxygen ratio O2 / (O2+Ar) of 80 vol% at a pressure of 2.0 mTorr with a power of 50.0 kW applied (power density: 9.8 W / cm 2 ). In the optical simulation based on spectroscopic measurement, the film thickness was 80 nm. After that, by sputtering, a zirconium-containing silicon oxide-containing layer (SiO x: Zr) as the second silicon oxide-containing layer. A zirconia-doped silica target containing 10% by mass of zirconia was used during film formation, and a mixed gas with an average oxygen ratio of O2 / (O2+Ar) of 70% by volume was used to apply a power of 38.0 kW at a pressure of 3.0 mTorr (power density: 7.5 W / cm 2 ) for film formation. In the optical simulation based on spectroscopic measurement, the film thickness was 25 nm. Through the above process, a glass substrate with a coated film was obtained. In addition, when forming each layer, Ar or O2 or a mixed gas thereof was used without specific mention. The following physical property values of the obtained glass article were measured, and further evaluation was performed based on the evaluation method described below.

[0085] [Examples 2 to 5] In Examples 2 to 5, the power, power density, process gas pressure, and average oxygen ratio during sputtering of the first and second silicon oxide-containing layers are shown in Table 1. Except for this, a glass article with a coated film was produced in the same manner as in Example 1, the following physical property values were measured, and further evaluation was performed based on the evaluation method described below.

[0086] (Method for Measuring Physical Property Values) The measurement methods for the following physical property values of the obtained glass article are as follows.

[0087] [Amount of Ar Desorbed at Temperatures Higher than 550°C] The amount of Ar desorbed (nm·atomic %) from the total of the first and second silicon oxide-containing layers in the obtained glass article at temperatures higher than 550°C was measured according to the following method. More specifically, since the amount of Ar desorbed at temperatures higher than 650°C is almost zero, the amount of Ar desorbed from the total of the first and second silicon oxide-containing layers at temperatures higher than 550°C and 650°C or lower was measured according to the following method. First, unburned samples (the first and second silicon oxide-containing layers), samples fired at 550°C for 4 minutes, and samples fired at 650°C for 4 minutes were prepared. At this time, each sample placed on a metal tray was put into an electric furnace (manufactured by Tokyo Honsha Shokai Co., Ltd., product name: SS-2030PKP) set at a specified temperature (550°C or 650°C) and fired for 4 minutes. Then, for these samples, a fluorescence X-ray analysis device (manufactured by Rigaku Corporation, ZSX PrimusII (product name)) was used, and by making X-rays with a diameter of 30 mmφ and Rh 50 kV-72 mA incident, the Ar signal intensity of each sample was obtained from the difference in intensity between the peak angle of Ar of 57.3° and the background angle of 55.0°. Next, the difference in the Ar signal intensity between the un-fired sample and the sample fired at 650 °C, and the difference in the Ar signal intensity between the un-fired sample and the sample fired at 550 °C are respectively defined as the Ar release amount (A) at 650 °C and the Ar release amount (B) at 550 °C. The difference between the Ar release amounts (A) and (B) is the "Ar release amount at temperatures above 550 °C (cps: count per second)". In addition, Rutherford backscattering spectrometry (RBS) was used in the conversion of the Ar signal intensity obtained by X-ray fluorescence analysis (XRF) to the Ar release amount. Specifically, the following calculations were performed using the above samples containing a certain amount of Ar and the sample without Ar (comparison sample). I) Using an X-ray fluorescence analyzer (manufactured by Rigaku Corporation, ZSX Primus II (trade name)), by irradiating X-rays with 30 mmφ, Rh 50 kV - 72 mA, the Ar signal intensity with an Ar peak angle of 57.3° and a background angle of 55.0° was obtained, and the difference in the Ar signal intensity between the above samples and the comparison sample was calculated. II) Using a Rutherford backscattering spectrometry apparatus (manufactured by National Electrostatics Corporation, Pelletron 3SDH (trade name)), 2300 keV He ++ ions were incident under two conditions of incident angles of 0° and -35°, and the composition depth curve including the Ar atomic concentration [atomic%] in the silicon oxide-containing film was obtained by analog fitting using the detected values. Here, the first order of the depth curve is in the range of 1 - 3 nm. III) In the depth profile of the Ar atom concentration in the silicon oxide-containing film, the portion where three consecutive measurement points fall within the range of the average value ± 0.05 atomic % is defined as the flat part, and this is the part where the Ar atom concentration is read. When there are multiple consecutive measurement points falling within the range of the average value ± 0.05 atomic %, the average value of all corresponding measurement points is taken as the average Ar atom concentration of this layer. Additionally, when there are multiple discontinuous flat parts in one layer, for each flat part, the value obtained by multiplying the above average Ar atom concentration by the film thickness at the time of calculating the average value is calculated, and the value obtained by dividing the sum of these values by the total sum of the film thicknesses of all flat parts is the average Ar atom concentration of this layer. When the average Ar atom concentration is below the detection limit of 0.1 atomic %, 0.05 atomic % is defined as the average Ar atom concentration of this layer. The boundary of the silicon oxide-containing layer for reading the flat part to calculate the average Ar atom concentration is the part where the atomic concentration of the element closest to the flat part of the silicon oxide-containing film is half the value in the curve of the element with the largest amount among the elements not present in the silicon oxide-containing film in the layer adjacent to the silicon oxide-containing film in the atomic concentration depth profile. When there is no flat part, the position that is half the maximum atomic concentration value of this element is taken as the boundary between the two layers, and the average Ar atom concentration inside the boundary is calculated. Here, Figure 2 An example of the depth profile of the atomic concentration measured using a Rutherford backscattering spectrometry (RBS) apparatus is shown. By using RBS in this way, the composition ratio and average Ar atom concentration in the depth direction of each silicon oxide-containing layer can be obtained. The value obtained by multiplying the resulting Ar atom concentration by the film thickness is the Ar amount [nm·atomic %]. When the silicon oxide-containing layer is a single layer, the value obtained by this calculation is the total Ar amount. When it is a multi-layer, the sum of the Ar amounts of each layer is the total Ar amount, and the difference in the total Ar amounts of the above samples and the comparative sample is calculated. IV) By comparing the differences in I) and III) above, the Ar removal amount (nm·atomic %) in the Rutherford backscattering spectrometry per unit intensity obtained by the fluorescence X-ray analysis method is calculated.

[0088] [Ratio of the Ar removal amount at temperatures below 550 °C to the total Ar removal amount] As described above, the Ar removal amount at temperatures above 650 °C is almost zero. Therefore, the following ratio is obtained here as the ratio of the Ar removal amount at temperatures below 550 °C to the total Ar removal amount. That is, the ratio “Ar removal amount at temperatures below 550 °C / Ar removal amount at temperatures below 650 °C × 100” (%) of the Ar removal amount (B) at 550 °C measured using the fluorescence X-ray analysis apparatus to the Ar removal amount (A) at 650 °C is calculated.

[0089] <Evaluation method> Evaluate the obtained glass articles using the following evaluation methods.

[0090] [Evaluation of resistance to whitening] On the above-mentioned glass substrate, specifically on the peripheral portion of the coating film (the second silicon oxide-containing layer), a masking layer A or B with the elemental composition (mass %) shown in Table 2 is formed. Specifically, the materials for forming the masking layer with this elemental composition are respectively printed on the peripheral portion of the coating film by a screen printing method with #150 - #250 mesh and dried. Then, using a firing furnace (IR furnace), firing is carried out under the following firing conditions to sinter the material for forming the masking layer on this glass substrate, forming a frame-shaped masking layer A or B as shown in Figure 1C . The thickness of the masking layer is 15 μm in both cases. Among them, when sintering the masking layer A or B on the glass substrate, bending forming is carried out simultaneously to make a bent-shaped automotive window glass (glass article). In this way, a glass article in which a coating film and a masking layer A or B are sequentially laminated on a glass substrate is made. ·Firing conditions Firing temperature: 650, 660 °C or 670 °C. Temperature rising conditions: Raise the temperature to the firing temperature (650 - 670 °C) at a rate of 3 °C per second. After reaching the firing temperature, maintain it at the firing temperature, and the total firing (heating) time is 240 seconds. In addition, the specific elemental composition (mass %) of the masking layer A recorded in Table 2 is as follows. In addition, the method for determining the masking layer composition will be described later. Bi: 36.1, Si: 8.2, O: 29.1, Cr: 12.4, Cu: 5.5, Mn: 4.0, Na: 1.2, Al: 0.6, Ti: 0.4, K: 0.2, C: 2.3 (total 100). In addition, the specific elemental composition (mass %) of the masking layer B recorded in Table 2 is as follows. Bi: 29.7, Si: 9.1, O: 33.1, Cr: 12.1, Cu: 6.0, Mn: 3.9, Na: 1.4, Al: 0.6, Ti: 0.9, K: 0.4, C: 2.9 (total 100). Visually confirm the degree of whitening of the obtained glass articles (two types of glass articles to which the masking layer A or B has been applied for each case), and evaluate based on the following evaluation criteria. The evaluation results are shown in Table 1. ·Evaluation criteria AA: The colors of the masking layers formed under all temperature conditions of firing temperature: 650 °C - 670 °C are black, and the desired appearance is obtained. A: The colors of the masking layers are black under the conditions of firing temperature: 650 °C and 660 °C, resulting in the desired appearance, but the color of the masking layer is gray under the condition of firing temperature: 670 °C, and the desired appearance cannot be obtained. B: At a firing temperature of 650 °C, the color of the shielding layer is black, achieving the desired appearance. However, at firing temperatures of 660 °C and 670 °C, the color of the shielding layer is gray, and the desired appearance cannot be obtained. C: At all temperature conditions from 650 °C to 670 °C, the color of the shielding layer is gray, and the desired appearance cannot be obtained.

[0091] [Shielding layer composition] In the above evaluation of resistance to whitening, the elemental compositions of the shielding layers A and B used in the glass article are determined by the following methods, respectively. That is, the surface of the sample (shielding layer) is measured by energy dispersive X-ray spectroscopy (SEM-EDX), and the composition (mass %) of each component (element) is quantified. At this time, a scanning electron microscope (SEM) with the trade name: TM4000Plus manufactured by Hitachi, Ltd. is used, and an EDX with the trade name: AZtecOne of Oxford Instruments is used. The measurement results are shown in Table 2.

[0092] [SiO2 content] In the above evaluation of resistance to whitening, the SiO2 content (mass %) contained in the shielding layers A and B used in the glass article is measured by SEM-EDX. The measurement results are shown in Table 2.

[0093] [Bi / Si ratio] Based on the shielding layer composition determined by the above SEM-EDX, the Bi / Si mass % ratios of the shielding layers A and B are calculated respectively. The calculation results are shown in Table 2.

[0094] Table 1 Table 2

[0095] In summary, this glass article having a silicon oxide-containing layer with a specific Ar removal amount at a temperature higher than 550 °C has excellent resistance to whitening regardless of the type of shielding layer used, can suppress the occurrence of whitening caused by voids, and has an excellent appearance.

[0096] This application claims priority based on Japanese Patent Application No. 2022-195207 filed on December 6, 2022, and Japanese Patent Application No. 2023-20066 filed on February 13, 2023, and the entire disclosures thereof are incorporated herein by reference. Symbol description

[0097] 1 Glass substrate 2 Dielectric layer 3 Functional layer Silicon oxide-containing layer 5 Masking layer.

Claims

1. A glass article, characterized in that, A functional layer and a silicon oxide-containing layer are sequentially provided on a glass substrate, and the amount of Ar desorbed from the silicon oxide-containing layer at a temperature higher than 550 °C is 1.86 nm·atomic% or less.

2. The glass article according to claim 1, wherein, The amount of Ar desorbed from the silicon oxide-containing layer at a temperature higher than 550 °C is 0.92 nm·atomic% or less.

3. The glass article according to claim 1, wherein, The ratio of the amount of Ar desorbed from the silicon oxide-containing layer at a temperature of 550 °C or lower to the total amount of Ar desorbed is 95.0% or more.

4. The glass article according to claim 1, wherein, A shielding layer is provided on the silicon oxide-containing layer, and the Bi / Si ratio in the shielding layer is 3.8 or less.

5. The glass article according to claim 4, wherein, The SiO2 content in the shielding layer is 15 mass% or more.

6. The glass article according to claim 1, wherein, The silicon oxide-containing layer contains an element selected from Al and Zr.

7. The glass article according to claim 1, wherein, A dielectric layer is provided between the glass substrate and the functional layer, and the dielectric layer contains an element selected from Si, C, Ti, Zr, Nb, Zn, Sn, and Al, or an oxide, nitride, or oxynitride of these elements.

8. The glass article according to claim 1, wherein, The functional layer contains an element selected from In, Sn, Al, Ni, Cr, Zr, Ti, Nb, W, Fe, and F, or an oxide, nitride, or oxynitride of these elements.

9. The glass article according to any one of claims 1 to 8, wherein, It is used as an automotive window glass.

10. A method for manufacturing a glass article, characterized in that, A functional layer and a silicon oxide-containing layer are sequentially formed on a glass substrate by dry coating, and the amount of Ar desorbed from the silicon oxide-containing layer at a temperature higher than 550 °C is 1.86 nm·atomic% or less.

11. The manufacturing method of the glass article according to claim 10, wherein, The power density during sputtering of the silicon oxide-containing layer is 9.8 W / cm 2 or less.

12. The manufacturing method of the glass article according to claim 10, wherein, The process gas pressure during sputtering of the silicon oxide-containing layer is 2.0 mTorr or more.

13. The manufacturing method of a glass article according to any one of claims 10 to 12, wherein, The average O2 composition ratio in the process gas during sputtering of the silicon oxide-containing layer is 80 vol% or less.

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