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 total amount of Ar in the silicon oxide-containing layer (4) is 52.0 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 is characterized in that the functional layer (3) and the silicon oxide-containing layer (4) are sequentially formed on the glass substrate (1) by dry coating, and the total amount of Ar in the silicon oxide-containing layer (4) is set to 52.0 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 reflecting coating on a substrate, the heat radiation reflecting 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 on the outermost layer has adaptability to an opaque shielding print formed of a black glaze layer provided in a peripheral region and can provide a good appearance. In addition, it is known that a shielding layer applied with a black pigment, glass frit, or the like, like the above-described shielding print, is provided at the peripheral portion of a glass article for vehicles (for example, automotive window glass) 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, i.e., 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 are cases 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 total Ar amount in the silicon oxide-containing layer is 52.0 nm·atomic% or less. In the above glass article, the total Ar amount in the silicon oxide-containing layer may be 19.0 nm·atomic% or less. In the glass article according to any one of the above, the total H amount in the silicon oxide-containing layer may be 5.7×10 23 nm / cm 3 or less. In the glass article according to any one of the above, the total H amount in the silicon oxide-containing layer may be 2.9×1023 nm / cm 3 as follows. 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. In the method for manufacturing the glass article of the present disclosure, a functional layer and a silicon oxide-containing layer are sequentially formed on a glass substrate by dry coating, and the total Ar amount in the silicon oxide-containing layer is 52.0 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 8.7 W / cm 2 or more. 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 3.0 mTorr or less. 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% by volume 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 90% by volume or more. Advantageous Effects of the Invention

[0008] According to the present invention, there is provided a glass article having excellent appearance in which whitening after heat forming can be suppressed and a method for manufacturing the same. BRIEF 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 2 is a graph showing curves of the atomic concentrations measured by a Rutherford backscattering spectrometry apparatus in Example 1 in the depth direction. Figure 3 is a graph showing the relationship between the secondary ion intensity of the sample constituent elements measured by a secondary ion mass spectrometry apparatus in Example 1 and the sputtering time. Figure 4 is a graph showing the relationship between the secondary ion intensity of the sample constituent elements measured by a secondary ion mass spectrometry apparatus in Example 7 and the sputtering time. Figure 5 is a graph showing the relationship between the secondary ion intensity of the sample constituent elements measured by a secondary ion mass spectrometry apparatus in Example 6 and the sputtering time. 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. Additionally, 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 presume that the whitening occurs due to the following reasons during the thermoforming (and subsequent cooling as needed) operation. 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) degasses upon heating. Subsequently, since the material for forming the shielding layer melts due to thermoforming, the gas is trapped 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 presumed that light is scattered due to the generated voids, and when observing the glass article from the side where the shielding layer is not disposed, a whitish appearance (whitening) occurs.

[0013] As a result of intensive studies by the present inventors, it has been found that by making the total amount of Ar in the silica-containing layer included 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 accompanying drawings. However, 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 in the front, rear, side, and top of the vehicle body. In addition, this glass article can be used without limitation for uses other than vehicles, such as buildings, etc. In addition, this glass article only needs to have the structure shown below in at least 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] This glass article, as Figure 1A shown, sequentially includes a functional layer 3 and a silicon oxide-containing layer 4 on the 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 Figure 1B shown. It can also have a shielding layer 5 on at least a part of the silicon oxide-containing layer 4 as Figure 1C shown. In this glass article, these layers only need to be sequentially laminated on at least a part of one surface of the glass substrate. They can be laminated on the entire glass substrate constituting the glass article, or may 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 the position of the peripheral portion of the glass substrate on this coating film as Figure 1C shown.

[0017] In addition, within the range where the effects of the present disclosure can be obtained, other layers may 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 may also be provided on the silicon oxide-containing layer 4 (for example, on the shielding layer 5 when the shielding layer 5 is present) with a primer layer interposed therebetween. The primer layer, the sealing layer, and the adhesive layer may appropriately use conventionally known materials. In addition, a scratch-resistant layer may be disposed on the silicon oxide-containing layer. The scratch-resistant layer may be composed of, for example, at least one selected from ZrBO, ZrO2, Ta2O5, Al2O3, TiO2, Nb2O5, SiN, and BN. In addition, Figure 1A and Figure 1B Schematic cross-sectional views showing two embodiments of this glass article are respectively shown, Figure 1C and schematic plan views thereof when viewed from the shielding layer 5 side are shown.

[0018] [Silicon oxide-containing layer] In this glass article, the total Ar amount in the silicon oxide-containing layer is 52.0 nm·atomic% or less (52.0 nm or less). When the total Ar amount is 52.0 nm·atomic% or less, the Ar amount in the silicon oxide-containing layer can be suppressed to a low level, so that the generation of voids and the whitening of the glass article caused by this Ar can be suppressed, and a glass article having excellent appearance regardless of the type of the shielding layer can be provided. From the same viewpoint, the total Ar amount in the silicon oxide-containing layer is more preferably 38.0 nm·atomic% or less (0.38 nm or less), and still more preferably 19.0 nm·atomic% or less (19.0 nm or less). In addition, when this glass article includes multiple layers (for example, two layers) of the above-mentioned silicon oxide-containing layer, the total Ar amount of the total of these multiple layers of silicon oxide-containing layer satisfies the above range. Among them, the specific measurement method for the total Ar amount in the silicon oxide-containing layer will be described later.

[0019] In addition, the total Ar amount in the silicon oxide-containing layer is preferably 5.0 nm·atomic% or more (0.05 nm or more). When the total Ar amount in the silicon oxide-containing layer is 5.0 nm·atomic% or more, it is easy to prevent the heat resistance of this glass article from decreasing, and it is easy to adjust the film formation rate during the formation of the coating film to an appropriate range. From the same viewpoint, the total Ar amount in the silicon oxide-containing layer is more preferably 7.0 nm·atomic% or more (0.07 nm or more).

[0020] This glass article having a silica-containing layer with a specific total Ar amount has excellent anti-whitening properties, can suppress the occurrence of whitening caused by voids, and can have excellent appearance. Therefore, even when this glass article is formed into a curved shape for vehicles at a high temperature (for example, 600 to 750 °C), the occurrence of whitening can be easily avoided.

[0021] In addition, in this glass article, the total H amount in the silica-containing layer is preferably 5.7×10 23 nm / cm 3 (nm·atom / cm 3 ) or less. When the total H amount is 5.7×10 23 nm / cm 3 or less, the amount of moisture (H amount) in the silica-containing layer can be easily suppressed to a low level. In conjunction with this, the amount of Ar in the SiO x structure trapped in the silica-containing layer can also be easily suppressed to a low level. As a result, the generation of voids and the whitening of the glass article caused by this Ar can be suppressed, and a glass article having excellent appearance regardless of the type of the shielding layer can be provided. Furthermore, from the same viewpoint, the total H amount in the silica-containing layer is more preferably 4.0×10 23 nm / cm 3 or less, and even more preferably 2.9×10 23 nm / cm 3 or less.

[0022] Furthermore, the total H amount in the silica-containing layer is preferably 1.0×10 23 nm / cm 3 or more. When the total H amount in the silica-containing layer is 1.0×10 23 nm / cm 3 or more, it is possible to easily prevent an increase in the restrictions on manufacturing conditions and also to easily prevent an increase in the standby time during film formation. Furthermore, from the same viewpoint, the total H amount in the silica-containing layer is more preferably 1.2×10 23 nm / cm 3 or more.

[0023] In this glass article, as long as the silica-containing layer contains silica (SiO x: For example, a layer with x = 1, 2) is sufficient. Therefore, the silicon oxide-containing layer can be a layer composed of pure silicon oxide (SiO2), or can contain one or more other elements selected from aluminum (Al), boron (B), tin (Sn), titanium (Ti), zirconium (Zr), hafnium (Hf), and nitrogen (N), etc. as dopants. That is, the silicon oxide-containing layer can be composed of 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, for example. More specifically, for example, the silicon oxide-containing layer can have only one SiO x layer on the glass substrate, or can have SiO x layer and a SiO x layer doped with other elements in sequence. In the silicon oxide-containing layer, from the viewpoint of improving the anti-whitening property, it is preferably to contain elements selected from Al and Zr. In addition, the dopant is not limited to the above substances, and conventionally known substances can also be appropriately contained.

[0024] 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 the anti-whitening property, the silicon oxide content is preferably 85% by mass or more, more preferably 90% by mass or more, and further preferably 92% by mass or more.

[0025] The thickness of the silicon oxide-containing layer is not particularly limited, but from the viewpoints of antireflection property 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 the anti-whitening property, 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, when forming a multi-layer silicon oxide-containing layer, it is preferable that the total thickness of the overall silicon oxide-containing layer is within the above range. For example, when the silicon oxide-containing layer includes a SiO x layer and a SiO x layer doped with other elements, from the viewpoint of improving the anti-whitening property, 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.

[0026] 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 required, 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, a dry coating film formed by dry coating using a vapor growth method to form a thin film in a vacuum is preferably used. 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, and the like. 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 a silicon oxide-containing layer as the uppermost layer, and a low emissivity coating film is further preferred. As a method for forming each film, a conventionally known method can be appropriately used.

[0027] 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 a more accurate measurement, it is preferably 5 to 25 keV, and more preferably 15 to 20 keV.

[0028] In addition, the film thickness of each layer of the coating film can be measured using a stylus profilometer after separately forming a single film, or can be determined by optical simulation based on spectroscopic measurement or transmission electron microscope (TEM) observation in a laminate. The acceleration voltage in TEM observation can be appropriately set, but from the viewpoint of performing a more accurate measurement, it is preferably 40 to 1000 kV, and more preferably 60 to 300 kV. For example, magnification calibration can use 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.

[0029] 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.

[0030] [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 oxides, nitrides, or oxynitrides of these elements. In addition, a combination of two or more of these components can also be contained. The dielectric layer can be, for example, Si(Al)N, SiO2, TiO2, ZnO, or a layer containing a dopant (such as 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 various excellent properties, the total thickness is preferably 20 to 100 nm, more preferably 30 to 90 nm, and further preferably 40 to 80 nm.

[0031] [Functional layer] The functional layer can be formed by the above dry coating method, and preferably contains elements selected from, for example, In, Sn, Al, Ni, Cr, Zr, Ti, Nb, W, Fe, and F, or oxides, nitrides, or oxynitrides of these elements. In addition, a combination of two or more of these components can also be contained. For example, SnO2, In2O3 (ITO), ZrN, TiN, CrN, or a layer containing a dopant in these layers can be used for the functional layer. 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.

[0032] 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 needed) is not particularly limited. However, from the viewpoint of imparting excellent various properties, the total thickness of this coating film is preferably 25 to 500 nm, more preferably 50 to 450 nm, and further preferably 100 to 400 nm.

[0033] As described above, various dry coating films having a silicon oxide-containing layer formed on the surface can be applied to the surface of this glass article. Hereinafter, regarding each dry coating film, a simple description will be given mainly focusing on the portion other than the silicon oxide-containing layer formed on the surface.

[0034] 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 also 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 or a combination of Ag, Au, Cu, Al, Nb, W, Fe, and Pt. Among them, as the above functional layer, it is preferably composed of any one of or a combination of Au, Cu, Al, and Pt. In addition, the above dielectric layer and the above barrier layer can each be composed of any one of or a combination of Ti, Zn, Sn, Si, Al, and Ni. In addition, the dielectric layer and the barrier layer can also be composed of oxides, nitrides, or oxynitrides of these elements.

[0035] The low-emissivity coating film can be composed of more than 1 layer, for example, it can be composed of multiple layers (such as 2 to 6 layers). 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 sequence from the glass substrate side. Additionally, the above functional layer can be composed of any one of In, Sn, Al, Ni, Cr, Zr, Ti, and F or a combination thereof. Furthermore, 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. Additionally, the dielectric layer can also be composed of oxides, nitrides, or oxynitrides of these elements.

[0036] 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 adjusting its oxidation degree, the desired characteristics can be obtained. Furthermore, the above oxidation degree can be appropriately adjusted by adjusting the oxygen addition amount of the film-forming gas when forming the functional layer, and this oxidation degree can be appropriately set according to the desired characteristics. However, especially in the case of using an indium tin oxide target to form an ITO (indium tin oxide) layer as the functional layer, it is preferable to add 0.1 to 3.0 vol% of oxygen to Ar as 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 / □ or less can be obtained. At this time, the dielectric layer can be an oxynitride, for example. In this way, by adding a small amount of oxygen to the film-forming gas to adjust the oxidation degree 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.

[0037] 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 including moisture in the film-forming gas, excessive crystallization during heating can be easily suppressed, and crack generation can be easily inhibited. Further, the amount of moisture contained in the film-forming gas can be appropriately adjusted. In particular, 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 preferred. That is, it is preferred that moisture is present in the film-forming gas in a 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 - 3 mm transparent glass substrate using this method and heating it in the range of 500 - 700°C for 2 - 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 including a specified amount of moisture and other components in the film-forming gas, crack generation can be easily inhibited.

[0038] The low-reflection coating film can be composed of one or more layers. For example, it can be composed of multiple layers (such as three layers). For example, focusing on the refractive index, the low-reflection coating film can be composed, from the glass substrate side, of a low-refractive-index layer, a high-refractive-index layer, and a silicon oxide-containing layer in sequence, 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, 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 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 can have multiple functional layers. In addition, the functional layer closest to the glass substrate side (for example, the layer directly above the glass substrate) can 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 can be composed of Si, and the above-mentioned high-refractive-index layer can be composed of any one of Ti, Nb, Ta, and Sn or a combination thereof. In addition, any of these refractive index layers can also be composed of oxides, nitrides, or oxynitrides of these elements.

[0039] The p-polarized light reflecting coating film can be composed of more than 1 layer, for example, it can be composed of multiple layers (such as 2 layers). For example, focusing on the refractive index, the p-polarized light reflecting coating film can be composed of a high refractive index layer and a low refractive index layer in sequence from the glass substrate side, or 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 silica-containing layer, and the other layers become functional layers. That is, in the p-polarized light reflecting coating film, the functional layer can be 1 layer or a multi-layer of 2 layers or more. The high refractive index layer can 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 composed of oxides, nitrides, or oxynitrides of these elements. For example, the high refractive index layer can be Zr:TiO2 containing TiO2 and other elements as dopants. The low refractive index layer can be composed of oxides, nitrides, or oxynitrides of Si, and can also contain Al or Zr, but at least the low refractive index layer on the outermost surface side is the above-mentioned silica-containing layer.

[0040] [Glass substrate] The glass substrate (glass plate) of this glass article can be appropriately used with conventionally well-known glass substrates. For example, hot wire absorbing glass, transparent glass, soda-lime (soda-lime) glass, quartz glass, borosilicate glass, non-alkali glass, green glass, UV green glass, etc. can be used as the glass substrate. However, when this glass article is used as automotive glass, it is required that the glass substrate has a visible light transmittance that meets the safety standards of the country where the vehicle is used. In the case of other uses, it is required to have the characteristics necessary for that use. 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 oxide (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%.

[0041] In addition, the glass substrate may be substantially transparent or may be tinted, i.e., colored. Further, the glass substrate may also be a glass substrate that has been strengthened as needed. As the strengthening treatment, it may be a chemical strengthening treatment or a physical strengthening treatment (air-cooled strengthening treatment).

[0042] In addition, the shape of the glass substrate is not particularly limited as long as it can be formed into a shape corresponding to the desired use. For example, it may be rectangular. As the formed shape of the present glass article, a bent shape can be cited, and the form of the bend is not particularly limited. For example, it can be formed into a shape bent in the vertical direction of the paper surface shown Figure 1A in the drawing. Further, 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 included in the present glass article may be a rectangular glass substrate before forming, for example, or a bent-shaped glass substrate after forming, for example. In addition, the forming of the present glass article can be performed, 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. Further, the forming of the present glass article can be performed by performing firing bending separately after forming a shielding layer or the like on the glass substrate, or can be performed by performing firing bending after performing pre-firing once after forming a shielding layer or the like. In this way, the forming time of the present glass article can be appropriately selected.

[0043] 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 a windshield or a sunroof glass, from the viewpoint of strength such as anti-chip performance, the thickness of the glass substrate on the outside 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. Further, from the viewpoint of lightening the weight 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, from the viewpoint of workability, the thickness of the glass substrate on the inside of the vehicle when installed on the automobile is preferably 0.3 mm or more, and from the viewpoint of lightening the weight of the laminated glass, it is preferably 2.3 mm or less. In addition, the present 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 may be the same or different.

[0044] The glass substrate can be appropriately manufactured by a conventionally known method (for example, the float method, the melting 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.

[0045] [Masking layer] This glass article may have a masking layer on the silicon oxide-containing layer. The masking layer may be 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 so as to cover the peripheral portion of the glass substrate. By means of this masking layer, terminals of mounting components or electrical components mounted on the vehicle body cannot be seen from the outside of the vehicle. Therefore, this masking layer may be an opaque masking layer. In addition, the shape of the masking layer may be various shapes such as a frame-like shape, a band-like shape, a dot-like shape, etc. Figure 1C In [the figure], a frame-like 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 may be provided, for example, so as to cover a specific area from the edge of the glass substrate 1. More specifically, the masking layer 5 may cover at least a part within 30 mm (for example, within 50 mm from the edge) from the edge of the glass substrate 1.

[0046] The masking layer may contain a crystalline component, a pigment, an additive (such as a resin), etc. The components (elements) constituting the masking 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.

[0047] 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 masking layer. Specifically, it is preferable that the composition ratio of Si (silicon) having the effect of increasing the melting start temperature during thermoforming and Bi (bismuth) having the effect of decreasing the above-mentioned melting start temperature, that is, the Bi / Si ratio (mass% ratio) in the above-mentioned masking layer, is 3.8 or less. If the Bi / Si ratio is 3.8 or less, the sintering temperature of the components in the masking layer can be made higher, and more gas (Ar) can be degassed from the silicon oxide-containing layer before the masking layer is sintered. As a result, the amount of Ar degassing from 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 having excellent appearance can be easily obtained. Furthermore, from the same viewpoint, this Bi / Si ratio is more preferably 3.7 or less, further preferably 3.5 or less, and particularly preferably 3.3 or less.

[0048] In addition, the composition of the masking layer 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 a more accurate measurement, it is preferably 5 to 25 keV, and more preferably 15 to 20 keV.

[0049] The shielding layer (such as a black ceramic layer) is a fired layer formed by coating a material for forming the shielding layer (ceramic paste) on a glass substrate, more specifically, on a desired position (such as the peripheral portion) of the coating film and heating and sintering it at a high temperature. The firing temperature can be set appropriately, for example, it can be set to 500 to 700 °C (such as 600 °C or higher). The material for forming the shielding layer before firing can contain frit (corresponding to the crystalline components when forming the shielding layer), pigments (such as heat-resistant black pigments), (organic) carriers for dispersing the pigments as needed, conductive metals, reducing agents, dispersant surfactants, fluidity modifiers, fluidity aids, adhesion promoters, stabilizers, colorants and other additives. In addition, commercially available products can also be used as the material for forming the shielding layer. By forming the shielding layer into a fired layer, the shielding layer is bonded to the glass substrate.

[0050] 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. In addition, it is known that frits with a high melting point range have 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, a complex such as Bi4Si3O 12 From the viewpoint of improving the anti-whitening property, the SiO2 content 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 sinterability, the SiO2 content 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 anti-whitening property, the Bi2O3 content 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 Bi2O3 content in the shielding layer is preferably 30% by mass or more, more preferably 35% by mass or more.

[0051] When forming the shielding layer, the frit may have a different crystal form from the raw material stage (material for forming the shielding layer) before firing, or may not. In addition, the crystalline components in the shielding layer can be composed of one type of frit, or can be composed by fusing multiple frits through firing, for example.

[0052] In addition, the frit can be manufactured by conventionally known methods. For example, by mixing starting materials corresponding to the desired composition and melting them at the desired temperature and time, and cooling with water or the like as needed, a frit having the desired composition can be manufactured. The frit can be pulverized to a desired particle size (e.g., 1 to 8 μm) using known pulverization techniques as needed. Alternatively, commercially available products can also be used as the frit.

[0053] The content of the frit in the material for forming the shielding layer can be appropriately set. However, 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 the organic components. Therefore, the content of the frit 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.

[0054] As the above-mentioned pigments, conventionally known pigments can be appropriately used. For example, one or more pigments selected from composite inorganic pigments such as corundum - hematite, olivine, pillarite, pyrochlore, rutile, and spinel can be used. As the pigment, 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.

[0055] 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 of 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.

[0056] As more specific examples of the metal oxide pigments, CuO·CrO3, CuCr2O4, (Co, Fe)(Fe, Cr)2O4, MnCr2O4, NiMnCrFe, CuCrMnO, and pigments obtained by modifying these pigments with modifiers can be cited. Here, the properties 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, for example, the method described in JP-T-2019-509959, or commercially available products can be purchased. The pigments can be formed by, for example, 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.

[0057] In addition, as the pigments, pigments derived from rare earth manganese oxide pigments can also be used. For example, (Y x Mn)O y , (La x Mn)O y , (Ce x Mn)O y , (Pr x Mn)O y , (Nd x Mn)O y can be used. Here, in the above chemical formula, x is preferably 0.01 to 99, more preferably 0.08 to 12, and further preferably 0.25 to 4. In addition, in the above chemical formula, y is the number of oxygen atoms required to maintain electrical neutrality, and is preferably x + 1 to 2x + 2. As the pigments, CeMnO3, PrMnO3, NdMnO3, and pigments obtained by modifying these pigments with modifiers can be specifically cited. In addition, the rare earth manganese oxide pigments preferably have a perovskite crystal structure or an orthorhombic crystal structure. By using the rare earth manganese oxide pigments, a very high infrared reflectance can be obtained, and the heat generation characteristics can be reduced. Moreover, since the pigments do not contain cobalt materials, hexavalent chromium dissolution will not occur even in acidic solutions such as acid rain.

[0058] The pigment content in the material for forming the shielding layer can be appropriately set, but from the viewpoint of obtaining the desired hue, it is preferably 0.1% by mass or more, more preferably 1% by mass or more, further preferably 2% by mass or more, and particularly preferably 5% by mass or more. In addition, 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, further preferably 25% by mass or less, and particularly preferably 15% by mass or less.

[0059] Examples of the organic carrier for dispersing and suspending the above frit and pigment include vegetable oil, mineral oil, low molecular weight petroleum fraction, tridecanol, synthetic resin, natural resin, etc. As the conductive metal, for example, silver (silver particles) can be used. As the reducing agent, for example, ferrosilicon 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 having a group affinity for the pigment and may also contain a solvent (e.g., xylene, butyl acetate, methoxypropyl acetate) as required. As the dispersing surfactant, conventionally known surfactants can be appropriately used. For example, Disperbyk 162 (trade name, produced by BYK Chemie) can be used. The fluidity modifier is used to adjust the viscosity. Conventionally known fluidity modifiers can be appropriately used. For example, the Viscobyk series (produced by BYK Chemie) can be used. The flow aid is an additive for adjusting the viscosity and fluidity. Conventionally known flow aids can be used. For example, Additol VXW6388 (trade name, produced 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 blocker can be used. In addition, the compounding amount of these additives can be appropriately set and is not particularly limited.

[0060] The composition of the shielding layer (the overall shielding layer including frit, pigment, additives, etc.) is expressed in mass% based on oxides and can be, for example, 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 to 8 mass %.

[0061] The thickness of the shielding layer affects the ultraviolet transmittance, acid resistance, weather resistance, concealment, glass strength, and cost. From the viewpoints of ultraviolet 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).

[0062] 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 (with the material for forming the shielding layer) 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).

[0063] <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 on a glass substrate by dry coating. And, the total Ar amount in the silicon oxide-containing layer is 52.0 nm·atomic % or less. Regarding the Ar removal amount, as described above, the description thereof is omitted.

[0064] 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.

[0065] The PVD method is mainly a method in which, in a high vacuum (10 -1 to 10 -5 Pa) state, a film-forming substance for forming a thin 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 a 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 melt and evaporate or sublime, and the evaporated or sublimed particles (atoms and molecules) are attached and deposited on the surface of a substrate to form a thin film. In addition, sputtering refers to a technique in which inert gas and reactive gas (mainly Ar, O2, N2) are introduced into a vacuum, a negative voltage is applied to a target (e.g., a plate-shaped film-forming material) to generate glow discharge, inert gas atoms are ionized, and gas ions collide with the surface of the target at high speed and beat violently, causing particles (atoms and molecules) of the film-forming material constituting the target to pop out violently, and then adhering and accumulating on the surface of the substrate to form a thin 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 accommodated.

[0066] On the other hand, the CVD method is a method in which gaseous raw materials are fed in a state of atmospheric pressure to medium vacuum (100 to 10 -1 Pa), and energy such as heat, plasma, and light is imparted to excite and promote a chemical reaction to synthesize a thin film or fine particles, which are adsorbed and accumulated on the surface of the substrate.

[0067] 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 exhibiting 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 for forming each film, a conventionally well-known method can be appropriately used.

[0068] 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).

[0069] In addition, the above substrate preparation step (substrate production 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 a dielectric layer is provided between the glass substrate and the functional layer, a step of forming a dielectric layer on the above glass substrate (dielectric layer formation step) may be provided 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 for forming each layer may be provided.

[0070] In addition, in the glass article obtained by the present manufacturing method, a shielding layer may be formed on the above silicon oxide-containing layer (shielding layer formation step) to manufacture a glass article having a shielding layer (manufacturing method of a glass article having a shielding layer).

[0071] The above-mentioned shielding layer forming process may include the following processes, for example. · A process of preparing a material for forming a shielding layer (shielding layer forming material preparation process). · A process of coating the above-mentioned material for forming a shielding layer on the above-mentioned silicon oxide-containing layer (coating process). · A process of sintering the above-mentioned material for forming a shielding layer coated on the above-mentioned silicon oxide-containing layer (sintering process).

[0072] This manufacturing method may also include the following processes. · A process of heating and shaping a glass substrate on which a dielectric layer, a functional layer, a silicon oxide-containing layer, and an optional shielding layer are sequentially arranged into a desired shape as needed (heating and shaping process). · A process of cooling the above-mentioned glass substrate after heating and shaping (cooling process). These processes may be carried out sequentially, or multiple processes (such as the shielding layer forming process (specifically, the sintering process) and the heating and shaping process) may be carried out simultaneously. The following will explain this manufacturing method in detail.

[0073] First, prepare a glass substrate (glass plate), for example, in a rectangular shape (substrate preparation process). At this time, a commercially available product may be purchased and used as the glass substrate, or it may be manufactured by, for example, the following method. That is, heat a glass raw material with a blended 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 (molten process), form it into a plate-shaped glass ribbon, and perform slow cooling (slow cooling process) to obtain a glass substrate. At this time, processing (such as SO2 treatment or cleaning treatment) may also be performed on the obtained glass ribbon. In addition, the shaping of the glass substrate may be carried out in any one of the above-mentioned molten process and slow cooling process. Moreover, when manufacturing the glass substrate, it may be appropriately cut into a desired size. For example, when manufacturing vehicle glass into a front windshield for an automobile, prepare a glass substrate of (500 - 1300 mm) × (1200 - 1700 mm) × (1.6 - 2.5 mm). The glass substrate may be a single piece or a laminated glass formed by pasting two or more pieces of glass.

[0074] 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 may 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.

[0075] Here, from the viewpoints of improving the film density of the formed silicon oxide-containing layer and easily suppressing the total amount of Ar and the total amount of H in the silicon oxide-containing layer within the above-specified ranges, the formation conditions of the silicon oxide-containing layer are preferably as follows. From the above viewpoints, when sputtering the silicon oxide-containing layer (e.g., SiO x layer), the power density is preferably 7.5 W / cm 2 or more, more preferably 8.7 W / cm 2 or more, and further preferably 8.8 W / cm 2 or more. In addition, from the same viewpoints, the power density is preferably 9.6 W / cm 2 or less, more preferably 9.4 W / cm 2 or less, and further preferably 9.0 W / cm 2 or less. 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. 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 above viewpoints, the power density is preferably 7.7 W / cm 2 or more, more preferably 8.0 W / cm 2 or more. In addition, from the same viewpoints, the power density is preferably 10.2 W / cm 2 or less, more preferably 9.4 W / cm 2 or less, and further preferably 9.2 W / cm 2 or less. From the above viewpoints, when sputtering the silicon oxide-containing layer (doped or undoped SiO x layer), the process gas pressure is preferably 1.0 mTorr or more. In addition, from the viewpoint of heat resistance, when sputtering the silicon oxide-containing layer (e.g., SiO x layer), the process gas pressure is preferably 3.0 mTorr or less, more preferably 2.5 mTorr or less, and further preferably 2.0 mTorr or less. 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 viewpoints, the process gas pressure is more preferably 3.0 mTorr or less, more preferably 2.8 mTorr or less, and further preferably 2.5 mTorr or less. Thereby, a low-emissivity coating film having a good sheet resistance (Ω / □) can be obtained after firing. From the above viewpoints, when sputtering the silicon oxide-containing layer (e.g., SiO xWhen forming the silicon oxide-containing layer, the average O2 composition ratio in the process gas is preferably 80% by volume or more, more preferably 90% by volume or more. Additionally, this average O2 composition ratio can be 100% by volume, and in this case, the formation of voids can also be suppressed, and a glass article with excellent anti-whitening property can be provided. Here, when the silicon oxide-containing layer is a SiO layer doped with other elements (such as Zr, etc.) x in this case, from the above viewpoints, the average O2 composition ratio in the above process gas is preferably 38% by volume or more, more preferably 50% by volume or more. Additionally, from the same viewpoints, this average O2 composition ratio is preferably 90% by volume or less, more preferably 85% by volume or less. In summary, a glass article can be obtained in which a dielectric layer, a functional layer, and a silicon oxide-containing layer are sequentially disposed on a glass substrate. Additionally, the dielectric layer may or may not be formed.

[0076] Additionally, for the obtained glass article, a frame-shaped shielding layer (shielding layer forming step) can be formed on at least a part of the silicon oxide-containing layer (the uppermost layer), for example, on the peripheral portion of the silicon oxide-containing layer. Specifically, a material for forming the shielding layer (such as 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. As the coating method of the material for forming the shielding layer, there is no particular limitation, and for example, a screen printing method, an inkjet method, an electroprinting method, etc. can be used. Specifically, it is preferably printed on this glass substrate with a screen of #150 to #250 mesh.

[0077] Additionally, a commercially available product can be used as the material for forming the shielding layer, or it can be prepared separately (shielding layer forming material preparation step). 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.

[0078] Then, using a firing furnace such as a conveyor-type IR furnace, the obtained glass substrate is heated to a specified temperature to sinter the material for forming the shielding layer on this 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). Additionally, the firing speed (conveyor speed) is also not particularly limited, and it is preferably 5 to 30 mm / s. Furthermore, 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 this glass substrate.

[0079] In addition, in order to make the frit in the material for forming the shielding layer exhibit various characteristics, one type of frit can be used, or two or more types of frits can be used in combination. Two or more types of frits having the same composition but different particle sizes can also be used in combination as appropriate. From the viewpoint of reducing the porosity, the melting point of the 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 frit is preferably 700 °C or lower, more preferably 680 °C or lower. When two or more types of frits are used in combination, it is preferable that the softening point of one or more of the frits is within the above range, and it is more preferable that the softening points of all the frits are within the above range.

[0080] Subsequently, the glass substrate on which the coating film and the shielding layer are sequentially disposed is heated and formed into a desired shape (heating and forming step), and a cooling operation (cooling step) is performed as needed. In addition, the glass substrate may be formed into a desired shape by performing self-weight bending forming or pressure bending forming while maintaining the glass substrate at the heating temperature in the above-mentioned sintering step. That is, the heating and forming step and the above-mentioned sintering step can be performed simultaneously. In the pressure bending forming, for example, according to the shape of the automotive window glass desired, the glass plate is bent by a pressing device (hot pressing device). In the self-weight bending forming, the glass substrate is bent by a self-weight bending device. Air cooling strengthening or the like can also be performed according to the safety standards required for the automotive window glass.

[0081] The glass article thus obtained has excellent durability, can suppress the occurrence of whitening, and has an excellent appearance. Examples

[0082] The present invention will be described in more detail below with reference to a plurality of examples, but the present disclosure is not limited to these examples. Among them, Examples 1 to 6 are examples of the glass article, and Examples 7 to 8 are comparative examples.

[0083] [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 having a thickness of 2.1 mm (product name: FGY1, manufactured by AGC Inc.) was prepared. Next, by sputtering, a zirconium-doped titanium oxide layer containing zirconium oxide was formed as a first dielectric layer on the surface of the glass substrate. In the film formation, a zirconium-doped titanium dioxide target having a zirconium oxide content of 35% by mass 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 a second dielectric layer. In the optical simulation based on spectroscopic measurement, the film thickness was 35 nm. Subsequently, an ITO (indium tin oxide) layer is formed as a functional layer by sputtering. An indium tin oxide target doped with 10 mass% of tin oxide is used for film formation, and film formation is carried out with a mixed gas having an average oxygen ratio O2 / (O2 + Ar) of 0.2 vol%. In an optical simulation based on spectroscopic measurement, the film thickness is 120 nm. Subsequently, a first silicon oxide-containing layer (SiO x ) is formed by film formation. A silicon target is used, and a mixed gas having an average oxygen ratio O2 / (O2 + Ar) of 80 vol% is applied at a pressure of 2.0 mTorr with a power of 48.9 kW (power density: 9.6 W / cm 2 ) for film formation. In an optical simulation based on spectroscopic measurement, the film thickness is 80 nm. After that, a silicon oxide-containing layer containing zirconium (SiO x :Zr) is formed as a second silicon oxide-containing layer by sputtering on the surface of the obtained glass substrate. A silicon oxide target doped with 10 mass% of zirconium is used for film formation, and a mixed gas having an average oxygen ratio O2 / (O2 + Ar) of 52 vol% is applied at a pressure of 3.0 mTorr with a power of 48.0 kW (power density: 9.4 W / cm 2 ) for film formation. In an optical simulation based on spectroscopic measurement, the film thickness is 25 nm. Through the above steps, a glass substrate with a coated film is obtained. In addition, when forming each layer by film formation, Ar or O2 or a mixed gas thereof is used in the absence of specific description. The following physical property values of the obtained glass article are measured, and then evaluation is carried out based on the evaluation method described below.

[0084] [Examples 2, 3, 5, 7, and 8] In Examples 2 to 3, 5, 7 to 8, the power, power density, process gas pressure, and average oxygen ratio during sputtering of the first silicon oxide-containing layer and the second silicon oxide-containing layer are as shown in Table 1. Except for this, a glass article with a coated film is produced in the same manner as in Example 1, the following physical property values are measured, and then evaluation is carried out based on the evaluation method described below.

[0085] [Example 4] A glass article with a coated film is produced in the same manner as in Example 1, except that the first silicon oxide-containing layer and the second silicon oxide-containing layer are formed by film formation according to the following methods respectively, the following physical property values are measured, and then evaluation is carried out based on the evaluation method described below. That is, when forming the first silicon oxide-containing layer, a silicon target is used, and a gas with an average oxygen ratio of 100 vol% of O2 is applied at a pressure of 2.0 mTorr with a power of 45.0 kW (power density: 8.8 W / cm 2)Film formation is carried out. In the optical simulation based on spectroscopic measurement, the film thickness is 46 nm. Subsequently, when forming the second silicon oxide-containing layer, a silicon target is used, and a mixed gas with an average oxygen ratio O2 / (O2+Ar) of 80 vol% is used to apply a power of 45.0 kW at a pressure of 2.0 mTorr (power density: 8.8 W / cm 2 )Film formation is carried out. In the optical simulation based on spectroscopic measurement, the film thickness is 46 nm.

[0086] [Example 6] Except for not forming the second silicon oxide-containing layer and forming the first silicon oxide-containing layer by film formation according to the following method, a glass article with a coating film is produced in the same manner as in Example 1, the following physical property values are measured, and further evaluation is carried out based on the following evaluation method. That is, when forming the first silicon oxide-containing layer, a silicon target is used, and a gas with an average oxygen ratio of 100 vol% of O2 is used to apply a power of 45.0 kW at a pressure of 2.0 mTorr (power density: 8.8 W / cm 2 )Film formation is carried out. In the optical simulation based on spectroscopic measurement, the film thickness is 92 nm.

[0087] (Method for measuring physical property values) The measurement methods for the following physical property values of the obtained glass article are as follows.

[0088] [Total Ar amount in the silicon oxide-containing layer] The total Ar amount (nm·atomic%) in the silicon oxide-containing layer (the first and second silicon oxide-containing layers except for Example 6, and the first silicon oxide-containing layer in Example 6) in the obtained glass article is obtained according to the following method. The average Ar atomic concentration in each silicon oxide-containing layer is calculated through the following steps (I) to (II). I) Using a Rutherford backscattering spectrometry apparatus (manufactured by National Electrostatics Corporation, Pelletron 3SDH (trade name)), 2300 keV He ++ ions are incident at two conditions of an incident angle of 0° and -35°, and the obtained values are used to obtain a composition depth curve including the Ar atomic concentration [atomic%] in the silicon oxide-containing film through simulation fitting. Here, the first order of the depth curve is in the range of 1 to 3 nm. II) In the Ar atom concentration depth profile of 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 portion, and this is the portion where the Ar atom concentration is read. When there are multiple consecutive measurement points within the range of the average value ± 0.05 atomic %, the average value of all corresponding measurement points is used as the average Ar atom concentration of this layer. Additionally, when there are multiple discontinuous flat portions in one layer, for each flat portion, 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 portions 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 portion to calculate the average Ar atom concentration is the portion where the atomic concentration 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 is half of the atomic concentration of the element closest to the flat portion of the silicon oxide-containing film. When there is no flat portion, the portion that is half of the maximum atomic concentration value of this element is used as the boundary between the two layers, and the average Ar atom concentration inside the boundary is calculated. The value obtained by multiplying the calculated average Ar atom concentration by the film thickness of the silicon oxide-containing layer is the Ar amount [nm·atomic %]. When the silicon oxide-containing layer is a single layer, the value obtained from this calculation is the total Ar amount. When the silicon oxide-containing layer is a multi-layer, the sum of the Ar amounts of each layer is the total Ar amount. Here, Figure 2 An example of the curve of each atomic concentration in the depth direction measured by the Rutherford backscattering spectrometry (RBS) device in Example 1 above is shown. By using RBS in this way, the composition ratio and average Ar atom concentration of each silicon oxide-containing layer in the depth direction can be obtained.

[0089] [Total H amount in the silicon oxide-containing layer] The total H amount (nm / cm 3 ) in the silicon oxide-containing layer (the first and second silicon oxide-containing layers except for Example 6, and the first silicon oxide-containing layer in Example 6) of the obtained glass article is obtained in the following order (I) to (III). (I) In order to remove the organic contamination on the surface of the measurement sample (silicon oxide-containing layer), ultraviolet (UV) ozone treatment is performed. The UV ozone treatment uses an ultraviolet irradiation device with the trade name: PL30 - 200 (manufactured by SEN ENGINEERING Co., Ltd.), and the power supply for the ultraviolet irradiation device uses the trade name: UB201D - 20. The treatment conditions are ultraviolet wavelength: 254 nm, treatment time: 10 minutes. (II) Use H below 1% + Inject silicon oxide as a standard sample for quantification, and measure the H concentration and the average H / Si intensity ratio in the standard sample using a secondary ion mass spectrometry apparatus. The analysis conditions are as follows. Apparatus: Manufactured by ULVAC, Inc., Trade name: PHIADEPT1010, Primary ion species: Cs + , Primary ion acceleration voltage: 2 kV, Primary ion current: 20 nA, Primary ion incident angle (angle from the perpendicular direction of the sample surface): 60°, Grating size: 400×400 μm 2 , Secondary ion polarity: negative. (III) Using a secondary ion mass spectrometry apparatus, measure the average H / Si intensity ratio in the sample to be measured under the same conditions as the above analysis conditions. Then, calculate the relative sensitivity coefficient of the above standard sample for quantification according to JIS K0163:2010, and convert the average H / Si intensity ratio in the sample to be measured into an H concentration. The value obtained by multiplying the obtained H concentration by the film thickness of the silicon oxide-containing layer is defined as the H amount [nm / cm 3 . In the case where there are multiple silicon oxide-containing layers, the sum of the H amounts of each layer obtained is the total H amount. Here, Figure 3 , Figure 4 and Figure 5 respectively show the curves of the relationship between the secondary ion intensity (cps) of the sample constituent elements measured by the secondary ion mass spectrometry apparatus and the sputtering time (sec) in Example 1, Example 7, and Example 6. In addition, the range for calculating the H / Si intensity ratio is defined by the curve of the metal element with the largest intensity change among those not present in the adjacent layer. Specifically, as shown in the curve of Example 1, Figure 3 when the (90Zr + 16O)-secondary ion curve in the outermost silicon oxide-containing layer containing zirconia has a flat portion, the H / Si intensity ratio in the steady stagnation region where the (90Zr + 16O)-secondary ion intensity sharply rises and ends, that is, the region before the intensity starts to sharply decline, is used as the H / Si intensity ratio of this layer. Specifically, for the silicon oxide-containing layer containing zirconia, Figure 3The H / Si intensity ratio within the range indicated by symbol A in [description] is taken as the H / Si intensity ratio of the silicon oxide-containing layer. Additionally, for a silicon oxide-containing layer that mainly contains no metal elements other than Si, the H / Si intensity ratio within the range from the region where the (90Zr + 16O)-secondary ion intensity sharply drops to the region before the (120Sn + 16O)-secondary ion intensity starts to rise ( Figure 3 the range indicated by symbol B in [description]) is taken as the H / Si intensity ratio of the silicon oxide-containing layer. As shown in the graph of Example 7, namely Figure 4 when there is no stable stagnant region in the (90Zr + 16O)-secondary ion intensity curve of the outermost zirconia-doped silicon oxide-containing layer in the zirconia-containing silicon oxide-containing layer, the H / Si intensity ratio within the range from the region where the (90Zr + 16O)-secondary ion intensity sharply rises to the region before the intensity starts to sharply drop ( Figure 4 the range indicated by symbol A in [description]) is taken as the H / Si intensity ratio of the Zr-doped silicon oxide-containing layer. Additionally, for a silicon oxide-containing layer that mainly contains no metal elements other than Si, the H / Si intensity ratio within the range indicated by symbol B in [description] is calculated in the same manner as in Example 1. Figure 4 As shown in the graph of Example 6, namely Figure 5 when the silicon oxide layer that mainly contains no metal elements other than Si is the outermost layer, the H / Si intensity ratio within the range from the region where the sharp rise of the 30Si-secondary ion intensity ends to the region before the (120Sn + 16O)-secondary ion intensity starts to rise ( Figure 5 the range indicated by symbol B in [description]) is taken as the H / Si intensity ratio of this layer. In addition, for each measurement sample, the H / Si intensity ratio is calculated 3 times, and their average value is taken as the average H / Si intensity ratio. Furthermore, in Table 1, for example, the total H amount [nm / cm 3 “5.63E+23” means “5.63×10 23 ”.

[0090] [Sheet Resistance] Using a firing furnace (IR furnace), the above glass substrate is heated at a rate of 3°C / second to a firing temperature of 650°C. After reaching the firing temperature, it is maintained at the firing temperature, and the total firing (heating) time is 240 seconds for firing. Using a non-contact surface resistance measuring instrument (manufactured by NAGY Corporation: PULS), the sheet resistance of the fired glass substrate is measured. The measurement results are shown in Table 1.

[0091] <Evaluation Method> The obtained glass articles are evaluated using the following evaluation method.

[0092] [Evaluation of resistance to whitening] On the above-mentioned glass substrate, specifically on the peripheral portion of the coating film (the uppermost silicon oxide-containing layer), a masking layer A or B having the elemental composition (mass %) shown in Table 2 is formed. Specifically, the materials for forming the masking layer having this elemental composition are respectively printed on the peripheral portion of the coating film by a screen printing method with a mesh size of #150 to #250 and dried. Then, firing is carried out in a firing furnace (IR furnace) under the following firing conditions to sinter the material for forming the masking layer on this glass substrate, and a frame-shaped masking layer A or B as shown in Figure 1C is formed. The thickness of both masking layers is 15 μm. Among them, when sintering the masking layer A or B on the glass substrate, bending forming is carried out simultaneously to produce a bent 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 produced. ·Firing conditions Firing temperature: 650, 660 °C or 670 °C. Temperature rising condition: The temperature is raised to the firing temperature (650 - 670 °C) at a rate of 3 °C / second, and after reaching the firing temperature, it is maintained at the firing temperature. The total firing (heating) time is 240 seconds. In addition, the specific elemental composition (mass %) of the masking layer A described 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 described 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 glass articles to which the masking layer A or B is applied for each example), 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 the firing temperature: 650 °C to 670 °C are all black, and the desired appearance is obtained. A: The colors of the masking layers are all black under the conditions of the 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 the 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.

[0093] [Shielding layer composition] In the above evaluation of whitening resistance, 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, the trade name: TM4000Plus manufactured by Hitachi, Ltd. is used as the scanning electron microscope (SEM), and the trade name: AZtecOne of Oxford Instruments is used as the EDX. The measurement results are shown in Table 2.

[0094] [SiO2 content] In the above evaluation of whitening resistance, 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.

[0095] [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.

[0096] Table 1 Table 2

[0097] In summary, this glass article with a silica-containing layer having a specific total Ar amount has excellent whitening resistance regardless of the type of shielding layer used, can suppress the occurrence of whitening caused by voids, and has an excellent appearance.

[0098] This application claims priority based on Japanese Patent Application No. 2022-199456 filed on December 14, 2022, and Japanese Patent Application No. 2023-019959 filed on February 13, 2023, and the entire disclosures thereof are incorporated herein by reference. Symbol description

[0099] 1 Glass substrate 2 Dielectric layer 3 Functional layer 4 Silica-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 total Ar amount in the silicon oxide-containing layer is 52.0 nm·atomic% or less.

2. The glass article according to claim 1, wherein, The total Ar amount in the silicon oxide-containing layer is 19.0 nm·atomic% or less.

3. The glass article according to claim 1, wherein, The total amount of H in the silicon oxide-containing layer is 5.7×10 23 nm / cm 3 or less.

4. The glass article according to claim 3, wherein, The total amount of H in the silicon oxide-containing layer is 2.9×10 23 nm / cm 3 or less.

5. 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.

6. The glass article according to claim 3, 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.

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

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

9. 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 contains an oxide, nitride, or oxynitride of these elements.

10. 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 contains an oxide, nitride, or oxynitride of these elements.

11. The glass article according to any one of claims 1 to 10, wherein, It is used as automotive window glass.

12. 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 total Ar amount in the silicon oxide-containing layer is 52.0 nm·atomic% or less.

13. The manufacturing method of the glass article according to claim 12, wherein, The power density during sputtering of the silicon oxide-containing layer is 8.7 W / cm 2 or higher.

14. The manufacturing method of the glass article according to claim 12, wherein, The process gas pressure during sputtering of the silicon oxide-containing layer is 3.0 mTorr or less.

15. The method for manufacturing a glass article according to claim 12, wherein, The average O2 mixing ratio in the process gas during sputtering of the silicon oxide-containing layer is 80 vol% or more.

16. The manufacturing method of the glass article according to claim 15, wherein, The average O2 mixing ratio in the process gas during sputtering of the silicon oxide-containing layer is 90 vol% or more.

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