Glass articles

Abstract

Provided is a glass article that has excellent heat resistance and is less susceptible to separation of layers disposed on a glass substrate and formation of cracks therein even after a long time from molding at a high temperature.　This glass article has a carbon-doped silicon oxide layer (2), a transparent conductive oxide layer (3), and a shielding layer (4) in the stated order on a glass substrate (1). The ratio C / Si in atomic percentages of carbon to silicon in the carbon-doped silicon oxide layer (2) is 0.1-0.5. The linear expansion coefficient αSh of the shielding layer is 7.7×10-3 / K or less.

Description

[Technical Field]

[0001] The present invention relates to a glazing article, particularly a glazing article for a vehicle. [Background technology]

[0002] BACKGROUND ART Glass articles such as window glass for vehicles and buildings are given desired properties by coating the surface of the glass substrate with various materials depending on the application.

[0003] Patent Document 1 discloses a glass article for a vehicle in which a base layer, a transparent conductive oxide layer, and a peripheral obscuration band (shielding layer) to which a black pigment or the like is applied are arranged on a glass substrate.

[0004] Typically, a base layer (e.g., a SnO2 layer) formed on a glass substrate can function as an alkali diffusion barrier layer that prevents alkali metal ions, such as sodium ions, from migrating from the glass substrate to the surface layer. It is also known to use a carbon-doped silicon oxide layer (hereinafter also referred to as an "SiOC layer"), which has excellent alkali diffusion barrier properties, as a base layer instead of a conventional base layer such as a SnO2 layer. Transparent conductive oxide layers (e.g., doped tin oxide layers) are known to have low-E (low emissivity) properties that can reduce the radiant heat of sunlight, and can improve the thermal insulation and heat shielding properties of glass articles. Furthermore, a shielding layer is usually provided on the peripheral edge of a glass article for a vehicle (for example, a window glass for an automobile) for the purposes of preventing deterioration of the adhesive due to sunlight, improving the design, and the like. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Special Publication No. 2019-533630 Summary of the Invention [Problem to be solved by the invention]

[0006] When a glass article having the configuration described in Patent Document 1 is molded at a high temperature (e.g., 600°C or higher) depending on the desired application, each layer (e.g., a base layer or a shielding layer) disposed on the glass substrate may peel off or cracks may occur. Furthermore, even if these phenomena are not observed immediately after molding at a high temperature, these phenomena may occur after a certain period of time has passed.

[0007] The present invention has been made to solve the above-mentioned problems, and aims to provide a glass article having excellent heat resistance that can suppress peeling and cracking of each layer arranged on a glass substrate even after a long period of time has passed since molding at high temperatures. [Means for solving the problem]

[0008] The present invention provides a glass article having the following configurations [1] to [9]. [1] A glass substrate is provided with a carbon-doped silicon oxide layer, a transparent conductive oxide layer, and a shielding layer in this order, wherein the ratio of the atomic composition percentage of carbon to silicon in the carbon-doped silicon oxide layer, C / Si, is 0.1 or more and 0.5 or less, and the linear expansion coefficient α of the shielding layer is Sh is 7.7 x 10 -3 / K or less. [2] The glass article according to [1], wherein the shielding layer contains a crystalline component and a pigment, and the crystallinity value, expressed as a CPS ratio of the crystalline component to the pigment in X-ray diffraction measurement data of the shielding layer, is 7 or more and 33 or less. [3] The glass article according to [1] or [2], wherein the shielding layer contains a crystalline component and a pigment, and the C / Si ratio of the carbon-doped silicon oxide layer to a crystallinity value expressed as a CPS ratio of the crystalline component to the pigment in X-ray diffraction measurement data of the shielding layer is 0.005 or more and 0.04 or less. [4] The linear expansion coefficient α of the carbon-added silicon oxide layer Si But 0.6×10 -6 / K or higher, 4.0×10-6 The glass article according to any one of [1] to [3], wherein the glass article has a temperature of 100°C or less. [5] The linear expansion coefficient α of the carbon-added silicon oxide layer Si But 2.9 x 10 -6 / K or less. [6] Thickness t of the glass substrate g The glass article according to any one of [1] to [5], wherein the thickness is 2.0 mm or more and 3.5 mm or less. [7] The thickness t of the carbon-doped silicon oxide layer Si The glass article according to any one of [1] to [6], wherein the average particle size is 30 nm or more and 150 nm or less. [8] The glass article according to any one of [1] to [7], wherein the transparent conductive oxide layer includes at least one of a fluorine-doped tin oxide layer and an antimony-doped tin oxide layer. [9] The glass article according to any one of [1] to [8], which is used as a window glass for an automobile. [Effects of the Invention]

[0009] The present invention provides a glass article having excellent heat resistance, which can suppress peeling and cracking of each layer disposed on a glass substrate even after a long period of time has passed since molding at high temperatures. [Brief explanation of the drawings]

[0010] [Figure 1A] 1 is a schematic cross-sectional view of one embodiment of a glass article according to the present invention. [Figure 1B] FIG. 1 is a schematic plan view of one embodiment of a glass article according to the present invention. [Figure 2A] FIG. 1 is a schematic cross-sectional view illustrating one embodiment of a glass article according to the present invention, showing a case in which the transparent conductive oxide layer is composed of a single layer. [Figure 2B] FIG. 1 is a schematic cross-sectional view illustrating one embodiment of a glass article according to the present invention, showing a case in which the transparent conductive oxide layer is composed of two layers. DETAILED DESCRIPTION OF THE INVENTION

[0011] In this specification, the use of "to" to indicate a range of values ​​means that the values ​​before and after it are included as the lower and upper limits. In addition, hereinafter, the term "SiOC layer" simply means that the layer contains silicon atoms (Si), oxygen atoms (O), and carbon atoms (C), and does not indicate that the composition ratio of these atoms (elements) is 1:1:1.

[0012] As described above, when a glass article having the configuration described in Patent Document 1 is formed at a high temperature, peeling or cracking may occur at the interface between each layer disposed on the glass substrate, for example, between the glass substrate and the base layer. Even if such a phenomenon is not observed immediately after forming, it may occur after a certain period of time. Furthermore, when the glass article is used as a glass article for a vehicle, cracking or peeling may occur not only in the center of the glass substrate but also in the edge portion of the periphery of the glass substrate where the shielding layer is provided. This tendency is particularly pronounced when an SiOC layer with excellent alkali diffusion prevention function is used as the base layer.

[0013] The inventors speculated that the occurrence of these peeling and cracks during the heat-molding (and subsequent cooling, if necessary) operation or after a certain period of time was due to the low adhesion between the glass substrate and the base layer or the shrinkage force of the shielding layer. In particular, when a SiOC layer is used as the base layer, there is a possibility that the SiOC may thermally decompose during molding at high temperatures, which is thought to further reduce the adhesion at the interface between the glass substrate and the base layer, resulting in peeling or cracks.

[0014] Based on these assumptions, the present inventors have conducted various studies and found that the occurrence of peeling or cracking during hot forming or after a certain period of time can be suppressed by setting the composition ratio of carbon to silicon (C / Si (at %)) in the SiOC layer within a specific range and further setting the linear expansion coefficient of the shielding layer to a specific value or less, thereby arriving at the present invention.

[0015] Hereinafter, an embodiment of a glass article according to the present invention (hereinafter also referred to as "the present glass article") will be described in detail with reference to the drawings, but the present invention is not limited to this embodiment.

[0016] <Glass articles> The present glass article can be suitably used as glass for vehicles such as automobiles, particularly as automobile window glass, and can be used in any position of the front, rear, side, or ceiling of the vehicle body. The present glass article can also be used without restriction for applications other than vehicles, such as buildings. The present glass article only needs to have the following configuration in at least a portion thereof, and may be used, for example, as a single glass including one glass substrate, or as a laminated glass including multiple glass substrates. The method for producing the present glass article is not particularly limited, but as described below, it can be produced, for example, using a conventionally known float method.

[0017] As shown in FIG. 1A, the present glass article has a glass substrate 1 on which a carbon-doped silicon oxide layer (SiOC layer) 2, a transparent conductive oxide (TCO) layer (hereinafter also referred to as "TCO layer") 3, and a shielding layer 4 are stacked in this order. As described above, these layers may be stacked sequentially on at least a portion of one side of the glass substrate, and these layers may or may not be stacked over the entire glass substrate constituting the glass article. For example, the SiOC layer 2 and the TCO layer 3 may be stacked in this order over the entire glass substrate, and as shown in FIG. 1B, a frame-shaped shielding layer 4 may be placed on the TCO layer at a position that corresponds to the periphery of the glass substrate. Furthermore, other layers, such as a color-adjusting layer for adjusting the color tone, may be present between the layers as long as the effects of the present invention can be obtained. However, from the viewpoint of heat resistance, the present glass article is preferably composed of a glass substrate 1, an SiOC layer 2, a TCO layer 3, and a shielding layer 4. 1A and 1B are schematic diagrams of one embodiment of the glass article, with FIG. 1A showing a schematic cross-sectional view thereof and FIG. 1B showing a schematic plan view thereof as viewed from the shielding layer 4 side.

[0018] In the glass article, the composition ratio (C / Si) expressed as the ratio of the atomic composition percentage (at%) of carbon to silicon in the SiOC layer, i.e., the C (at%) / Si (at%) of the SiOC layer, is 0.1 or more and 0.5 or less. In addition, the linear expansion coefficient (thermal expansion coefficient) α of the shielding layer is Sh is 7.7 x 10 -3 / K or less.

[0019] The glass article thus provided with a SiOC layer having a specific C / Si ratio and a shielding layer having a specific linear expansion coefficient has excellent heat resistance, excellent adhesion between the glass substrate and the base layer, and can suppress peeling or cracking due to the shrinkage force of the shielding layer. Therefore, even when the glass article is formed into a curved shape for use in a vehicle at a high temperature (e.g., 600 to 750°C), peeling or cracking of the layers on the glass substrate can be easily avoided.

[0020] [Glass substrate] The glass substrate (glass plate) can be any conventionally known glass substrate, such as heat-absorbing glass, clear glass, soda-lime glass, green glass, or UV-green glass. However, when the glass article is used as vehicle glass, the glass substrate is required to have a visible light transmittance that complies with the safety standards of the country in which the vehicle is used, and when used for other purposes, it is required to have the properties required for that purpose. Therefore, it is preferable to appropriately adjust the composition of the glass substrate so that the required properties can be achieved. Examples of the composition of the glass substrate include the following. The composition of the glass substrate can be determined by X-ray fluorescence analysis. SiO2: 70~73% by mass, Al2O3: 0.6~2.4% by mass, CaO: 7~12% by mass, MgO: 1.0~4.5% by mass, RO: 13 to 15 mass% (R is an alkali metal, for example, Na or K), Total iron oxide converted to Fe2O3 (T-Fe2O3): 0-0.14 mass%.

[0021] The glass substrate may be substantially transparent or may be tinted, i.e., colored. The shape of the glass substrate is not particularly limited as long as it can be formed into a shape according to the desired application, and can be, for example, rectangular. The formed shape of the present glass article can be a curved shape, and the form of the curve is not particularly limited, and can be, for example, a shape curved in the vertical direction of the paper surface shown in FIG. 1A. The present glass article includes both a glass substrate having an SiOC layer, a TCO layer, and a shielding layer disposed thereon before being formed, and a glass substrate after being formed into a desired shape. Therefore, the glass substrate of the present glass article may be, for example, a rectangular glass substrate before being formed, or a curved glass substrate after being formed.

[0022] Glass substrate thickness t gis not particularly limited, but is preferably 1.0 mm or more, more preferably 1.5 mm or more, and even more preferably 2.0 mm or more. g is preferably 6.0 mm or less, more preferably 5.0 mm or less, and even more preferably 3.5 mm or less. From the viewpoint of suppressing layer peeling and cracking, the thickness of the glass substrate is generally considered to be about 4.0 to 5.0 mm. However, since the present glass article has excellent heat resistance, it is possible to use a glass substrate having a thickness thinner than usual, for example, a thickness t g The glass article can be easily formed even when the thickness is 2.0 to 3.5 mm, and even when formed at high temperatures, deterioration or peeling of each layer on the glass substrate can be suppressed. Therefore, the glass article can be suitably used not only as a single glass but also as a laminated glass, and can be used for a variety of purposes.

[0023] Linear expansion coefficient α of glass substrate g can be appropriately set by changing the composition. However, from the viewpoint of suppressing peeling of the base layer (SiOC layer) during hot molding, -6 / K~10×10 -6 From the same viewpoint, it is preferable to set α g is 1.0 x 10 -6 / K~7.0×10 -6 / K, and 1.0 × 10 -6 / K~4.0×10 -6 In this case, it is more preferable to set the linear expansion coefficient α of the glass substrate to 0.5 K / K in order to prevent layer peeling. g is the linear expansion coefficient α of the base layer at the molding temperature (for example, 600 to 750°C). Si It is preferable to set the difference between the α of the glass substrate and the α of the glass substrate so as to be as small as possible. g can be measured by the method described below.

[0024] The glass substrate can be produced by any conventional method (for example, a float method, a fusion method, or a roll-out method), and the production method is not particularly limited. Note that commercially available glass substrates may also be used.

[0025] [SiOC layer] In this glass article, a carbon-doped silicon oxide layer (SiOC layer) (SiOC film) is used as a base layer disposed between the glass substrate and the TCO layer. Although there are no particular limitations on the method for laminating the SiOC layer on the glass substrate, it is preferable to use online coating, more specifically, online CVD (Chemical Vapor Deposition), which is a film formation method performed during the manufacturing process of the glass article. The SiOC layer is preferably used because it has a superior alkali diffusion prevention function as well as superior durability and suppression of void defects compared to conventional base layers such as an SnO2 layer.

[0026] In the present glass article, the SiOC layer may be provided on at least a portion of one surface of the glass substrate. Therefore, the SiOC layer may be in contact with the glass substrate, or another layer may be disposed between the glass substrate and the SiOC layer, so that the glass substrate and the SiOC layer are not in direct contact with each other. However, from the viewpoint of suppressing layer peeling and cracking, it is preferable that the other layer disposed between the glass substrate and the SiOC layer has a linear expansion coefficient close to that of the glass substrate or the SiOC layer (i.e., the difference between the two is small).

[0027] In the present glass article, the composition ratio (C / Si) of carbon atoms (C) to silicon atoms (Si) in the SiOC layer is 0.1 or more and 0.5 or less. When the composition ratio is 0.1 or more, the alkali diffusion prevention function of the SiOC layer can be improved. When the composition ratio is 0.5 or less, the heat resistance of the SiOC layer can be improved, and the thermal decomposition of SiOC and the generation of CO gas can be prevented during heat forming of the present glass article (for example, at high temperatures: 600°C or higher). As a result, the present glass article can be formed at high temperatures and can be used for a wide variety of applications, including automotive window glass. Furthermore, from the viewpoint of maintaining the alkali diffusion prevention function of the SiOC layer, the C / Si ratio in the SiOC layer is preferably 0.15 or more, more preferably 0.25 or more. Furthermore, from the viewpoint of the heat resistance of the SiOC layer, the C / Si ratio in the SiOC layer is preferably 0.40 or less, more preferably 0.30 or less.

[0028] The at% ratio (O / Si) of oxygen atoms (O) to silicon atoms (Si) in the SiOC layer is not particularly limited, but from the viewpoint of heat resistance, it is preferably 1.2 or more, more preferably 1.5 or more. Furthermore, from the viewpoint of maintaining the alkali diffusion prevention function, O / Si is preferably 3.0 or less, more preferably 2.5 or less.

[0029] The atomic composition percentage of oxygen atoms (O) in the SiOC layer is preferably 45 at% or more, more preferably 50 at% or more, and even more preferably 55 at% or more. If the at% of oxygen atoms is equal to or greater than these lower limits, the heat resistance of the SiOC layer can be further improved. Furthermore, the at% of oxygen atoms in the SiOC layer is preferably 70 at% or less, more preferably 65 at% or less, and even more preferably 62 at% or less. If the at% of oxygen atoms is equal to or less than these upper limits, the SiOC layer can easily be provided with excellent alkali diffusion prevention properties.

[0030] The atomic composition percentage of carbon atoms (C) in the SiOC layer is preferably 2 at% or more, more preferably 3 at% or more, and even more preferably 4 at% or more. The at% of carbon atoms in the SiOC layer is preferably 20 at% or less, more preferably 15 at% or less, and even more preferably 10 at% or less. When the at% of carbon atoms is equal to or greater than these lower limits, the SiOC layer can be easily endowed with excellent alkali diffusion prevention properties. When the at% of carbon atoms is equal to or less than these upper limits, the heat resistance of the SiOC layer can be further improved.

[0031] The atomic composition percentage of silicon atoms (Si) in the SiOC layer is preferably 20 at% or more, more preferably 23 at% or more, and even more preferably 25 at% or more. The at% of silicon atoms in the SiOC layer is preferably 35 at% or less, more preferably 34 at% or less, and even more preferably 32 at% or less. When the at% of silicon atoms is equal to or greater than these lower limits, the heat resistance and alkali diffusion prevention function of the SiOC layer can be further improved. When the at% of silicon atoms is equal to or less than these upper limits, the SiOC layer can easily be provided with excellent heat resistance and alkali diffusion prevention function.

[0032] In addition to the O, C, and Si atoms, the SiOC layer may contain, for example, atoms of Na, Ca, etc. The total at% of O, C, and Si atoms in the SiOC layer is preferably 85 to 99 at%, and more preferably 90 to 98 at%, from the viewpoint of imparting excellent heat resistance and alkali diffusion preventing function to the glass article.

[0033] The composition of the SiOC layer can be adjusted by changing the supply conditions of the source gas (mixture gas) during CVD. For example, the composition of the SiOC layer can be adjusted by increasing or decreasing the oxidation degree of the source gas (e.g., CO2 / SiH4, CO2 / C2H4), in other words, by increasing or decreasing the supply amount of CO2 gas used as the source gas. The atomic composition of the SiOC layer can also be measured using the method described below.

[0034] Linear expansion coefficient α of SiOC layer Si is 0.6 x 10 -6 / K or more is preferable, and 0.8×10 -6 / K or more is more preferable, and 1.0×10 -6 / K or more is more preferable. Si However, if the α of the SiOC layer is equal to or greater than these lower limit values, the base layer can be easily provided with an excellent alkali diffusion prevention function. Si is 4.0 x 10 -6 / K or less is preferable, and 3.5 × 10 -6 / K or less is more preferable, and 3.0×10 -6 / K or less is more preferable, and 2.9 × 10 -6 / K or less is particularly preferable. Si However, if the thickness is equal to or less than these upper limits, the heat resistance of the SiOC layer can be further improved, and the adhesive strength between the glass substrate and the base layer can be further improved. By appropriately adjusting the C / Si and O / Si ratio in the SiOC layer, the α Si The α of the SiOC layer can be adjusted. Si can be measured by the method described below.

[0035] The thickness of the SiOC layer t Si is not particularly limited and can be set appropriately, but from the viewpoint of achieving both heat resistance and alkali diffusion prevention function, it is preferably 30 nm or more, more preferably 35 nm or more, and even more preferably 40 nm or more. Si is preferably 150 nm or less, more preferably 120 nm or less, and even more preferably 100 nm or less.

[0036] [TCO layer] As described above, the transparent conductive oxide layer (TCO layer) used in the present glass article is known to have excellent Low-E performance and can include, for example, doped tin oxide, doped zinc oxide, and mixtures of two or more thereof. The TCO layer can also include alkali metal stannate (e.g., potassium, sodium, lithium, etc.), zinc stannate, cadmium stannate, and mixtures of two or more thereof. Among these, the TCO layer is preferably a doped tin oxide layer because it has excellent low-E performance. From the same viewpoint, the TCO layer is preferably a fluorine-doped tin oxide (F:SnO x ) layer and antimony-doped tin oxide (Sb:SnO x It is more preferable that the layer contains at least one of the following two layers: a layer having a thickness of 100 nm and a layer having a thickness of 100 nm; ... and a layer having a thickness of 100 nm; a layer

[0037] The TCO layer is F:SnO as shown in Figure 2A. x The glass article may be composed of a single TCO layer 3 consisting of a single layer. In this way, the glass article having a configuration consisting of a single TCO layer can have a visible light transmittance Tv of 80% or more (e.g., 83%) in accordance with ISO 9050 and JIS-R3106. Because the glass article having a TCO layer of this configuration has a high Tv, it can be used in the front or front side of an automobile body, specifically as a windshield or window glass next to the driver's seat or passenger seat.

[0038] As shown in FIGS. 1A and 2B, the TCO layer is a first TCO layer 3a made of Sb:SnO x layer and a second TCO layer 3b, F:SnO x The glass article may be composed of two or more layers including a TCO layer. In this way, the glass article having a configuration in which the TCO layer is composed of two or more layers can have a Tv of 25% or less (e.g., 18%). Because the glass article having a TCO layer of this configuration has a low Tv, it can be used as a windowpane for the rear side, ceiling, or rear of an automobile. 2A and 2B are schematic cross-sectional views illustrating an embodiment of the glass article, each showing a single TCO layer and a double TCO layer, respectively, and the shielding layer is omitted in FIGS.

[0039] The thickness of the TCO layer is not particularly limited, but from the viewpoint of imparting excellent Low-E performance, the total thickness t TCO From the same viewpoint, F:SnO x The thickness of the layer is preferably 100 to 500 nm, more preferably 150 to 350 nm. x The thickness of the layer is preferably 250 to 500 nm, more preferably 300 to 450 nm.

[0040] Although the method for laminating a TCO layer on a SiOC layer is not particularly limited, it is preferable to use online coating, more specifically, online CVD, in which film formation is performed during the manufacturing process of a glass article. In addition, in this glass article, it is sufficient that the TCO layer is provided on at least a portion of the SiOC layer. Therefore, the TCO layer (in the case of a multi-layer structure, the TCO layer closest to the glass substrate) may be in contact with the SiOC layer, or another layer may be disposed between the SiOC layer and the TCO layer so that the SiOC layer and the TCO layer are not in direct contact with each other. However, from the viewpoint of suppressing layer peeling and cracking, it is preferable to use another layer disposed between the SiOC layer and the TCO layer whose linear expansion coefficient is close to that of the SiOC layer and the TCO layer.

[0041] Linear expansion coefficient α of the TCO layer TCO can be appropriately set and is not particularly limited, but from the viewpoint of suppressing peeling of each layer on the glass substrate, α of the SiOC layer is Si It is preferable that the difference between the α of the TCO layer and the α of the TCO layer is small, and for example, it is preferable that the difference is in the following range. TCO is 1.0 x 10 -6 / K or higher, 9.0×10-6 / K or less, and the present glass article preferably has, for example, a linear expansion coefficient α TCO But 4.0×10 -6 In the case where the TCO layer is composed of multiple layers, all of the multiple TCO layers may satisfy the above-mentioned range of linear expansion coefficients, but it is preferable that at least the linear expansion coefficient of the TCO layer closest to the glass substrate, in other words, the TCO layer closest to the SiOC layer, is within the above-mentioned range. TCO can be measured by the method described below.

[0042] [Shielding layer] The shielding layer may be disposed on at least a portion of one side of the glass substrate, specifically on at least a portion of the TCO layer, but when the glass article is used as a glass article for a vehicle, it is preferably disposed so as to cover the peripheral portion of the glass substrate, so that attachment members to the vehicle body, terminals of electrical equipment, etc., are not visible from outside the vehicle. The shielding layer may have various shapes, such as a frame shape, a strip shape, or a dot shape. In FIG. 1B, a frame-shaped shielding layer 4 is provided on the peripheral edge of the glass substrate, more specifically, on the peripheral edge of the TCO layer 3. The shielding layer may be provided, for example, to cover a specific region from the edge of the glass substrate. More specifically, the shielding layer may cover a portion of the glass substrate within at least 30 mm (for example, within 50 mm) from the edge.

[0043] The shielding layer preferably contains a crystalline component and a pigment, and the crystallinity value of the shielding layer, expressed as the ratio of the diffraction intensity of the crystalline component to that of the pigment in counts per second (CPS) in X-ray diffraction measurement data, is 7 or more and 33 or less. The crystalline component of the shielding layer can provide advantageous non-adhesive properties and excellent mold releasability in compression-bending molding operations such as those performed in the automotive glass industry. Note that the crystalline form (crystal structure) of the crystalline component when present in the shielding layer and the crystalline form measured by XRD may be different or the same. If the crystallinity value of the shielding layer, i.e., the CPS of the crystalline component / CPS of the pigment, is 7 or more, the crystallinity is further improved, the surface unevenness of the shielding layer becomes larger, and the releasability during molding can be further improved. From the same viewpoint, the crystallinity value of the shielding layer is more preferably 10 or more, and particularly preferably 11 or more. Furthermore, if the crystallinity value of the shielding layer is 33 or less, layer peeling on the glass substrate can be easily suppressed when molding the glass article at high temperatures. From the same viewpoint, the crystallinity value of the shielding layer is more preferably 20 or less, and particularly preferably less than 15 (for example, 14 or less). Note that when the shielding layer contains multiple types of crystalline components and pigments, the crystallinity values ​​of the CPS of the crystalline component and the CPS of the pigment are calculated using the total values ​​of the CPS of the multiple types, respectively.

[0044] The crystallinity value of the shielding layer can be adjusted by changing the raw materials (crystalline components and pigments) used for the shielding layer and the firing conditions for firing the shielding layer. Examples of firing conditions include the firing speed (transport speed) (mm / s) and firing temperature (°C) when transporting the workpiece (to which the shielding layer-forming material has been applied) in the automotive glass molding process, and the temperature profile when the firing temperature is changed during firing. Specifically, the crystallinity value can be increased by slowing down the firing speed of the shielding layer or increasing the firing temperature. Conversely, the crystallinity value can be decreased by increasing the firing speed of the shielding layer or decreasing the firing temperature. The firing conditions for the shielding layer can be set as appropriate, but for example, the firing speed can be 5 to 30 mm / s (preferably 10 to 25 mm / s) and the firing temperature can be 550 to 730°C (preferably 580 to 710°C, more preferably 680 to 710°C). Table 1 below shows an example of the relationship between the crystallinity value of the shielding layer and the firing rate and firing temperature of the shielding layer.

[0045] [Table 1]

[0046] The shielding layer (e.g., black ceramic layer) can be formed by coating a shielding layer-forming material (ceramic paste) on a glass substrate, more specifically, on a desired position (e.g., on the periphery) on the TCO layer, and heating it at a high temperature to sinter it. The shielding layer-forming material before firing contains at least a frit (corresponding to the crystalline component when made into the shielding layer) and a pigment (for example, a heat-resistant black pigment), and may further contain, as necessary, an (organic) vehicle for dispersing the pigment, a conductive metal, a reducing agent, a dispersing surfactant, a flowability modifier, a flowability aid, an adhesion promoter, a stabilizer, a colorant, etc. Note that commercially available products can also be used as the shielding layer-forming material. An example of a commercially available shielding layer-forming material is product name: 14501 (manufactured by Ferro).

[0047] The frit may contain one or more (solid) crystalline substances such as zinc borate, zinc silicate, aluminum silicate, zinc titanate, and bismuth silicate. The frit may also contain one or more other components such as SiO2, Bi2O3, Cs2O, Na2O, B2O3, ZnO, TiO2, La2O3, Nb2O5, MnO2, CeO2, MoO3, WO3, F, Al2O3, and BaO. The frit may have a linear expansion coefficient α of the shielding layer. sh However, the values ​​of the components can be appropriately selected within a range that satisfies the predetermined values ​​described below, and the blending ratio is also arbitrary. Note that frits having a high melting point range are known to have excellent chemical resistance and a relatively low coefficient of thermal expansion.

[0048] When the frit is used to form the shielding layer, it may or may not have a crystalline form different from that of the raw material (shielding layer forming material) before firing. The crystalline component of the shielding layer may be composed of one type of frit, or may be composed of multiple types of frits fused together by firing, for example. In the examples described below, Bi4(SiO4)3 is observed as the crystalline component in the X-ray diffraction measurement data.

[0049] The frit can be produced by a conventionally known method. For example, starting materials according to the desired composition are mixed, melted at a desired temperature for a desired time, and cooled with water or the like as needed to produce a frit having the desired composition. The frit can be crushed to a desired particle size (e.g., 1 to 8 μm) using a known crushing technique, as needed. Commercially available frits can also be used.

[0050] The content of frit in the material for forming the shielding layer can be appropriately set within a range that satisfies the above crystallinity value when fired. However, from the viewpoint of facilitating adjustment of the crystallinity value of the shielding layer, the content of frit is preferably 60 to 99 mass%, more preferably 65 to 95 mass%, and even more preferably 70 to 85 mass%.

[0051] The pigments may be any conventional pigment, including those derived from one or more inorganic composite pigments such as corundum-hematite, olivine, princerite, pyrite, rutile, and spinel. Examples of pigments that can be used include 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). These black spinel pigments are suitable for use in the automotive industry, while other metal oxide pigments producing other colors can be used in other industries, such as construction, household appliances, and beverages.

[0052] In the spinel structure, X is usually O, which has almost the same ionic radius. 2- or F -A common pigment structure has the general formula AB2X4, where A and B represent tetrahedral and octahedral sites in a standard spinel lattice. Spinel structures can be formed from many different elements, including first-row transition elements, and are therefore the structure of many inorganic pigments. Most spinel compounds have a cubic space group, but distorted spinel structures can adopt tetragonal and sometimes orthorhombic phases.

[0053] More specific examples of metal oxide pigments include CuO·CrO3, CuCr2O4, (Co,Fe)(Fe,Cr)2O4, MnCr2O4, NiMnCrFe, CuCrMnO, and pigments modified with a modifying agent. Here, the performance of the pigment can be determined by the raw materials, synthesis techniques and conditions, and post-calcination treatment. The pigment may be synthesized by a conventionally known method, for example, the method described in JP-A-2019-509959, or a commercially available product may be purchased. However, the α of the shielding layer sh The composition is adjusted so that the value is equal to or less than a predetermined value. The desired pigment can be formed, for example, by combining fine metal oxides or salts containing the desired metal and calcining them. The size of the fine metal oxide particles can be appropriately set, but is preferably 1 nm to 10 μm, more preferably 10 nm to 1 μm, and even more preferably 50 to 500 nm.

[0054] Furthermore, rare earth manganese oxide pigments can also be used. For example, (YxMn)Oy, (LaxMn)Oy, (CexMn)Oy, (PrxMn)Oy, and (NdxMn)Oy can be used. In the above chemical formula, x is preferably 0.01 to 99, more preferably 0.08 to 12, and even more preferably 0.25 to 4. Furthermore, in the above chemical formula, y represents the number of oxygen atoms required to maintain electrical neutrality, and is preferably x+1 to 2x+2. Specific examples of such pigments include CeMnO3, PrMnO3, and NdMnO3, as well as pigments modified with a modifying agent. The rare earth manganese oxide pigment preferably has a perovskite crystal structure or an orthorhombic crystal structure. The use of rare earth manganese oxide pigments can achieve high infrared reflectance and reduced heat generation. Furthermore, the pigment does not contain cobalt material, and hexavalent chromium is not produced and eluted even in acidic solutions such as acid rain.

[0055] The content of the pigment in the material for forming the shielding layer can be appropriately set within a range that satisfies the above crystallinity value when fired. However, from the viewpoint of facilitating adjustment of the crystallinity value of the shielding layer, the content of the pigment is preferably 0.1 to 50 mass%, more preferably 1 to 25 mass%, and even more preferably 2 to 25 mass%.

[0056] Examples of organic vehicles for dispersing and suspending the frit and pigment include vegetable oils, mineral oils, low molecular weight petroleum fractions, tridecyl alcohol, synthetic resins, and natural resins. 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 a role in helping the pigment to be wetted when an inert inorganic fine particle pigment is used. The dispersing surfactant usually contains a block copolymer having a group having affinity for the pigment, and further contains a solvent (e.g., xylene, butyl acetate, methoxypropyl acetate) as needed. Any conventionally known dispersing surfactant can be used as appropriate, for example, Disperbyk 162 (trade name, manufactured by BykChemie). The flow modifier is used to adjust the viscosity, and any known flow modifier can be used as appropriate, for example, Viscobyk series (manufactured by BykChemie). The flow aid is an additive used to adjust viscosity and flowability, and conventionally known ones can be used, for example, Additol VXW6388 (trade name, manufactured by UCB Surface Specialty). The adhesion promoter is used to improve compatibility with the layer (TCO layer) on which the shielding layer is to be formed, and can be appropriately selected depending on the composition of the TCO layer to be used. As the stabilizer, for example, a light stabilizer or a UV blocking agent can be used. The amounts of these additives to be added can be set appropriately and are not particularly limited.

[0057] Linear expansion coefficient α of the shielding layer sh is 7.7 x 10 -3 / K or less. α of the shielding layer sh By making the α of the shielding layer equal to or less than this value, the peeling force due to the shrinkage of the shielding layer during high-temperature molding and cooling can be easily suppressed, and peeling of the layer from the glass substrate can be easily prevented. sh is 7.5 x 10 -3 / K or less. sh The smaller the α of the shielding layer, the better, but it is more preferable that the difference between the α of the shielding layer and the linear expansion coefficient of the TCO layer provided below the shielding layer is as small as possible. sh can be measured by the method described below.

[0058] The ratio of C / Si in the SiOC layer to the crystallinity value of the shielding layer {(C / Si in the SiOC layer) / (crystallinity value of the shielding layer)} is preferably 0.005 or more and 0.04 or less. If this ratio is 0.04 or less, it is easy to achieve both excellent mold releasability during molding and excellent heat resistance of the SiOC layer. From the same viewpoint, this ratio is more preferably 0.03 or less, and even more preferably 0.02 or less. Furthermore, if the ratio is 0.005 or more, the SiOC layer exhibits an excellent alkali diffusion preventing function and can easily suppress layer peeling on the glass substrate when the glass article is molded at high temperature. From the same viewpoint, the ratio is more preferably 0.008 or more, and even more preferably 0.010 or more.

[0059] Shielding layer thickness t sh The thickness can be set appropriately, but is preferably 8 μm or more and 20 μm or less, and more preferably 10 μm or more and 15 μm or less, from the viewpoint of excellent light resistance and ability to conceal excess adhesive.

[0060] <Method of manufacturing glass articles> The method for producing the present glass article is not particularly limited, but it can be produced, for example, by a production method including the following steps. · The process of preparing a glass substrate (substrate preparation process). A process for forming an SiOC layer on a glass substrate (SiOC layer formation process). A process of forming a TCO layer on the SiOC layer (TCO layer formation process). A process of forming a shielding layer on the TCO layer (shielding layer forming process).

[0061] The substrate preparation step (substrate manufacturing step) can include a step of melting glass raw materials and pouring the melted glass raw materials into a tin bath (melting step), and a step of slowly cooling the molten glass raw materials (slow cooling step).

[0062] The TCO layer forming step can include, for example, the following steps. A step of forming a first TCO layer on the SiOC layer (first TCO layer forming step). A step of forming a second TCO layer on the first TCO layer (second TCO layer forming step).

[0063] The shielding layer forming step can include, for example, the following steps. A step of preparing a material for forming a shielding layer (a step of preparing a material for forming a shielding layer). A step of applying the material for forming the shielding layer onto the TCO layer (application step). A step of sintering the material for forming the shielding layer applied onto the TCO layer (sintering step).

[0064] The above manufacturing method may also include the following steps. A step of heat-forming the glass substrate on which the SiOC layer, the TCO layer, and the shielding layer are arranged in this order into a desired shape (heat-forming step). A step of cooling the heated and formed glass substrate (cooling step). These steps may be performed sequentially, or multiple steps (for example, a substrate preparation step (specifically, a melting step) and a SiOC layer formation step, or a shielding layer formation step (specifically, a sintering step) and a heat molding step) may be performed in parallel. The above manufacturing method will be described in detail below.

[0065] First, for example, a rectangular glass substrate (glass plate) is prepared (substrate preparation step). In this case, a commercially available glass substrate may be used, but it can also be prepared, for example, by the following method. That is, glass raw materials blended to obtain a desired glass composition are heated at a predetermined temperature to obtain molten glass. Next, the obtained molten glass is poured into a tin bath filled with molten tin (melting step), and a plate-shaped glass ribbon is formed. The glass ribbon is then slowly cooled (slow cooling step) to obtain a glass substrate. At this time, the obtained glass ribbon may be subjected to processing treatment (for example, SO2 treatment or cleaning treatment). The glass substrate can be formed in either the melting step or the slow cooling step. Furthermore, when preparing the glass substrate, it can be cut to a desired size as appropriate.

[0066] Next, a SiOC layer is formed on at least a portion of one surface of the glass substrate, for example, on the entire one surface of the glass substrate (SiOC layer formation process). As described above, the SiOC layer is preferably formed using the online CVD method, in which a film is formed directly on a glass substrate on a float line. Specifically, the SiOC layer is formed by spraying a mixed source gas at atmospheric pressure (1013 hPa) onto a glass substrate heated to a predetermined temperature. In this case, a mixed gas of silane gas, ethylene gas, carbon dioxide gas, and nitrogen gas can be used as the source gas. The composition of the SiOC layer to be formed can be adjusted by changing the blending ratio of the source gas. Note that the formation of the SiOC layer using the online CVD method can be performed in parallel with the melting process when preparing the glass substrate. That is, the SiOC layer may be formed by spraying the source gas onto the glass surface of molten glass poured into a tin bath during the melting process. In this way, the formation of the layer using the online CVD method can be performed in parallel with the glass substrate preparation process.

[0067] Next, a TCO layer is formed on at least a portion of the SiOC layer, for example, on the entire surface of the SiOC layer (TCO layer forming step). At this time, if the TCO layer is composed of two or more layers, these layers are formed sequentially. For example, if the TCO layer is composed of a first TCO layer and a second TCO layer, the first TCO layer is formed on the SiOC layer (first TCO layer forming step), and then the second TCO layer is formed on the first TCO layer (second TCO layer forming step). As described above, the TCO layer is preferably formed continuously after the SiOC layer is formed on the glass substrate using the online CVD method. Specifically, the TCO layer is formed by spraying a mixed gas of raw materials at normal pressure onto the glass substrate on which the SiOC layer has been formed and heated to a predetermined temperature. At this time, the TCO layer is formed using Sb:SnO x When forming a TCO layer, a mixed gas consisting of MBTC (monobutyltin trichloride) raw material, Sb raw material, HCl gas, and NHO3 gas can be used as the raw material gas. xWhen producing a TCO layer, a mixed gas consisting of MBTC raw material, F raw material (trifluoroacetic acid (TFA)), oxygen gas, and nitrogen gas can be used as the raw material gas. The composition of the TCO layer to be produced can be adjusted by changing the blending of the raw material gases.

[0068] Next, a frame-shaped shielding layer is formed on at least a portion of the TCO layer (when the TCO layer is composed of multiple layers, the outermost TCO layer), for example, on the periphery of the TCO layer (shielding layer forming step). Specifically, a shielding layer forming material (for example, ceramic color paste) is applied to at least a portion of the region of the glass substrate on which the SiOC layer and TCO layer have been formed (application step), and dried as necessary. The method for applying the shielding layer forming material is not particularly limited, but for example, a screen printing method or an inkjet method can be used. Specifically, it is preferable to print the material on the glass substrate using a #150 to #250 mesh screen.

[0069] The shielding layer-forming material may be a commercially available product or may be prepared separately (shielding layer-forming material preparation step). The shielding layer-forming material can be prepared, for example, by dispersing the desired frit and pigment described above in an organic vehicle.

[0070] Next, the obtained glass substrate is heated to a predetermined temperature using a firing furnace such as an IR furnace to sinter the shielding layer-forming material onto the glass substrate (sintering step). The heating (firing) temperature is not particularly limited, but is preferably 550 to 730°C. The firing speed (transport speed) is also not particularly limited, but is preferably 5 to 30 mm / s. By changing these firing conditions, the crystallinity value of the shielding layer to be produced can be adjusted. In this manner, a shielding layer is formed on the glass substrate.

[0071] Next, the glass substrate having the SiOC layer, the TCO layer, and the shielding layer arranged in this order is heated and formed into a desired shape (heat-forming step), and cooled as necessary (cooling step). Note that the glass substrate may be bent by gravity or press-bent into a desired shape while being maintained at the heating temperature in the sintering step. That is, the heat-forming step and the sintering step may be performed in parallel. In press bending, for example, a glass sheet is bent using a press (heat press) according to the desired shape of the automotive window glass. In gravity bending, the glass substrate is bent using a gravity bending device. Furthermore, air-cooling tempering or the like may be performed according to the safety standards required for automotive window glass.

[0072] The glass article obtained as described above has excellent heat resistance and can suppress peeling and cracking of each layer on the glass substrate. Furthermore, the glass article does not use whisker-like refractories, and can achieve both low-temperature sintering of the shielding layer-forming material and high plate strength of the glass article. [Example]

[0073] The present invention will be described in more detail below using several examples, but the present invention is not limited to these examples. Examples 1 to 3 are working examples related to the present glass article, and Examples 4 to 6 are comparative examples.

[0074] [Example 1] (Example 1-1) Preparation of glass substrate Glass raw materials SiO2, Al2O3, MgO, CaO, Na2O, and K2O were heated at temperatures between 1450 and 1700°C to obtain molten glass. The molten glass was then poured into a tin bath filled with molten tin to form a plate-shaped glass ribbon. The tin bath was filled with a mixed gas of H2 and N2, and the temperature was 950 to 1200°C on the upstream side and 500 to 950°C on the downstream side. The obtained glass ribbon was then slowly cooled, and SO2 treatment was simultaneously performed in a slow-cooling furnace. Specifically, a mixed gas of SO2 gas and air was sprayed onto the bottom surface of the glass ribbon (the surface that had been in contact with the tin bath). After the SO2 treatment, the obtained glass ribbon was washed with a mixture of calcium carbonate and water and a mixture of neutral detergent and water, respectively, to remove the sulfate protective layers attached to both sides of the glass ribbon. This resulted in a glass substrate. The glass substrate had a thickness of 2.1 mm. The composition of the prepared glass substrate is shown in the following Table 2. Here, since the composition is usually unstable near the surface of a glass substrate, the blending amount of each component shown in Table 2 indicates the mass percentage based on oxides at a depth of approximately 5000 nm from the surface of the glass substrate where the composition is stable.

[0075] [Table 2]

[0076] (Example 1-2) Fabrication of SiOC layer and TCO layer An online CVD apparatus was used to successively form a SiOC layer, a first TCO layer, and a second TCO layer on one side of the glass substrate. Specifically, a mixed gas composed of the following raw material gases was sprayed at atmospheric pressure onto one side of the glass substrate heated to 600 to 1100°C under the following SiOC layer deposition conditions to form a SiOC layer with the following thickness: ·SiOC layer deposition conditions Raw material gases: silane gas (0.585 kg / hr), ethylene gas (2.03 kg / hr), carbon dioxide gas (6.10 kg / hr), nitrogen gas (4.30 kg / hr). Glass substrate temperature: 600 to 1100°C. Film formation pressure: atmospheric pressure. SiOC layer thickness: 80 nm.

[0077] Next, under the following first TCO layer deposition conditions, a mixed gas composed of the following raw materials was sprayed at normal pressure onto the surface of the SiOC layer heated to 600 to 1100°C to form a first TCO layer (SnOx:Sb) with the following thickness. First TCO layer deposition conditions Raw materials: MBTC raw material (37.3 L / hr), Sb raw material (6.0 vol.%: ratio when MBTC raw material is 100 vol.%), HCl gas (7.17 kg / hr), NHO3 gas (38.9 L / hr). Glass substrate temperature: 600 to 1100°C. Film formation pressure: atmospheric pressure. Film thickness: 430nm.

[0078] Next, under the second TCO layer deposition conditions described below, a mixed gas composed of the following raw materials was sprayed at normal pressure onto the entire surface of the first TCO layer heated to 600 to 1100°C to form a second TCO layer (SnOx:F) with the following thickness. - Second TCO layer deposition conditions Raw materials: MBTC raw material (18.18 L / hr), F raw material (TFA) (7.08 L / hr), oxygen gas (24.43 Nm 3 / hr), nitrogen gas (20.28 Nm 3 / hr). Glass substrate temperature: 600 to 1100°C. Film formation pressure: atmospheric pressure. Film thickness: 200 nm.

[0079] (Example 1-3) Creating a shielding layer A shielding layer containing Bi4(SiO4)3 as a crystalline component and CuCrMnO spinel pigment as a pigment, as determined by XRD measurement data, was fabricated on the glass substrate, specifically, on the periphery of the second TCO layer. Specifically, a commercially available shielding layer material (product name: 14501, manufactured by Ferro) was printed on the periphery of the second TCO layer using a #150 to #250 mesh screen printing method and then dried. Subsequently, firing was performed using a firing furnace (IR furnace) under the following firing conditions to sinter the shielding layer material onto the glass substrate, forming a frame-shaped shielding layer as shown in Figure 1B. Firing conditions Firing temperature: 680~710℃, Firing speed (conveying speed): 5 to 30 mm / s. The thickness of the shielding layer was 15 μm. As a result, a glass substrate having a SiOC layer, a TCO layer, and a shielding layer laminated thereon was obtained.

[0080] <Evaluation method> The glass substrate prepared in Example 1 was evaluated using the following evaluation methods.

[0081] [Heat resistance evaluation (film peeling and crack occurrence evaluation)] In Example 1, when the shielding layer was sintered on the glass substrate at 680 to 710°C, press bending was also performed to produce curved automobile window glass. The obtained automobile window glass was placed in a high-temperature, high-humidity chamber (temperature of 80°C or higher, relative humidity of 95% or higher), and the presence or absence of film peeling and cracking was visually confirmed every 24 hours, and evaluation was performed based on the following evaluation criteria. The evaluation results are shown in Table 3 below. Evaluation criteria 4: No peeling or cracking occurred after 2000 hours. 3: No peeling or cracking occurred after 1500 hours. However, peeling and / or cracking occurred between 1500 and 2000 hours. 2: No peeling or cracking occurred after 1000 hours. However, peeling and / or cracking occurred between 1000 and 1500 hours. 1: Peeling and / or cracking occurs within 1000 hours.

[0082] <Physical property measurement method> The physical properties of the glass substrate were measured as follows.

[0083] [Linear expansion coefficient] The linear expansion coefficients of the glass substrate and each layer (here, the shielding layer) laminated on the glass substrate were measured by the following method. That is, the thermal expansion curve of the measurement object cut into a predetermined shape (for example, a 5 cm rod) was measured using an Orton dilatometer in the temperature range of 25 to 300°C, and the linear expansion coefficient was calculated based on these data. The measurement results for the shielding layer are shown in Table 3 below. Note that the α of the SiOC layer in Example 1 Si is 0.6 to 4.0 × 10 -6 / K range.

[0084] [C / Si] The element ratio of the SiOC layer was measured by ESCA (Electron Spectroscopy Chemical Analysis). The equipment used was a scanning X-ray photoelectron spectrometer (XPS) PHI Quantera II (product name) manufactured by ULVAC-PHI. sample The sample was cut to a size (several millimeters square) that fit on the table and placed in the device. Measurement conditions (analysis diameter: 100 μmφ, X-ray setting: 25 W, 15 kV, sputter setting: 2 kV (area of ​​2 mm × 2 mm), vacuum level during analysis: approximately 2 × 10 -7 The composition of the film was analyzed by repeatedly measuring while the film was being scraped off with a sputtering gun (used to scrape off films) and inputting a pressure of 100 Pa. The film composition in the SiOC layer was analyzed, and the C / Si value was calculated using the element ratio in the center of the SiOC layer. The calculated values ​​are shown in Table 3.

[0085] [Crystallinity value] The crystallinity of the shielding layer was calculated using XRD (X-ray Diffraction). The equipment used was a fully automatic multipurpose X-ray diffractionThe measurement sample was placed in the measuring device. sample The sample was cut to a size (several centimeters square) that could fit on the table, and placed inside the instrument. The measurement conditions (tube voltage 45 kV, tube current 200 mA) were entered, and measurements were performed using the 2θ / θ scan method with a measurement angle of 10° to 80°, a step of 0.02°, and a scan speed of 20° / min. The obtained x-axis 2θ / θ angle and y-axis CPS (counts per second) values ​​were used to calculate the crystallinity value of the shielding layer (CPS of the Bi4(SiO4)3 crystal phase / CPS of the Cu-Cr-Mn-O spinel pigment phase). The calculated crystallinity values ​​are shown in Table 3. The peak of the Bi4(SiO4)3 crystal phase was observed at 2θ / θ: 32.6°, and the peak of the Cu-Cr-Mn-O spinel pigment phase was observed at 2θ / θ: 35.8°. Crystallinity values ​​were not measured in Examples 5 and 6, which will be described later.

[0086] [(C / Si) / crystallinity value] The C / Si value obtained by the above measurement method was divided by the crystallinity value to calculate the C / Si ratio. The calculated values ​​are shown in Table 3.

[0087] [Example 2] Glass substrates having each layer were prepared in the same manner as in Example 1, except that the firing conditions for the material for forming a shielding film in the firing furnace were changed as follows, and evaluations were performed based on the evaluation methods described above, and each physical property value was measured. Firing conditions Firing temperature: 680℃, Firing speed: 10mm / s. In Example 2, the α of the SiOC layer Si is 0.6 to 4.0 × 10 -6 / K range.

[0088] [Example 3] Except for the following changes, glass substrates having each layer were prepared in the same manner as in Example 1, and evaluations were performed based on the above-mentioned evaluation methods to measure each physical property value. Specifically, in Example 3, the source gas used in the film formation conditions for the SiOC layer and the firing conditions for the shielding film-forming material in the firing furnace were changed as follows: ·SiOC layer deposition conditions Raw material gases: silane gas (0.335 kg / hr), ethylene gas (0.64 kg / hr), carbon dioxide gas (14.11 kg / hr), nitrogen gas (1.00 kg / hr). Firing conditions Firing temperature: 710℃, Firing speed: 25mm / s. In Example 3, the α of the SiOC layer Si is 0.6 to 4.0 × 10 -6 / K range.

[0089] [Example 4] Substrates having each layer were prepared in the same manner as in Example 1, except that the source gases used in the SiOC layer formation conditions, the first TCO layer formation conditions, and the second TCO layer formation conditions were changed as follows, and evaluations were performed based on the evaluation methods described above, and the physical properties were measured. ·SiOC layer deposition conditions Raw material gases: silane gas (0.335 kg / hr), ethylene gas (0.64 kg / hr), carbon dioxide gas (14.11 kg / hr), nitrogen gas (1.00 kg / hr). First TCO layer deposition conditions Raw materials: MBTC raw material (50.6L / hr), Sb raw material (6.0%), HCl gas (9.37kg / hr). - Second TCO layer deposition conditions Raw materials: MBTC raw material (17.93 L / hr), F raw material (TFA) (6.98 L / hr), oxygen gas (24.10 Nm 3 / hr), nitrogen gas (20.28 Nm 3 / hr).

[0090] [Example 5] Glass substrates having each layer were prepared in the same manner as in Example 1, except for the following changes, and evaluated based on the evaluation methods described above to measure each physical property value. Si is 0.6 to 4.0 × 10 -6 / K. Specifically, in Example 5, the material for forming the shielding layer used in Example 1 was changed to a product name: B9-71 manufactured by Ferro.

[0091] [Example 6] Glass substrates having each layer were prepared in the same manner as in Example 1, except for the following changes, and evaluations were performed based on the evaluation methods described above, and each physical property value was measured. Specifically, in Example 6, the source gases used in the film formation conditions for the SiOC layer were changed to silane gas (0.335 kg / hr), ethylene gas (0.64 kg / hr), carbon dioxide gas (14.11 kg / hr), and nitrogen gas (1.00 kg / hr). Also, in Example 6, the material for forming the shielding layer used in Example 1 was changed to a product name: B9-83, manufactured by Ferro. In Example 6, the α of the SiOC layer Si is 0.6 to 4.0 × 10 -6 / K range.

[0092] Table 3 shows the measurement results of the SiOC layer and the shielding layer of each example and the evaluation results based on the above-mentioned evaluation method.

[0093] [Table 3]

[0094] As shown in Table 3 above, when the C / Si of the SiOC layer is 0.1 to 0.5 and the α of the shielding layer is sh is 7.7 x 10 -3 It can be seen that the present glass articles having a temperature of 1 / K or less exhibit excellent heat resistance. Furthermore, the present glass articles obtained in Examples 1 to 3 also had excellent demolding properties.

[0095] This application claims priority based on Japanese Patent Application No. 2020-149056, filed on September 4, 2020, the disclosure of which is incorporated herein by reference in its entirety. [Explanation of symbols]

[0096] 1. Glass substrate 2. Carbon-doped silicon oxide layer (SiOC layer) 3 Transparent conductive oxide layer (TCO layer) 3a First TCO layer 3b Second TCO layer 4 Shielding layer

Claims

1. A carbon-doped silicon oxide layer, a transparent conductive oxide layer, and a shielding layer are provided on a glass substrate in this order; the ratio C / Si of the atomic composition percentage of carbon to silicon in the carbon-added silicon oxide layer is 0.1 or more and 0.5 or less; The linear expansion coefficient α of the shielding layer Ｓｈ is 7.7 x 10 －３ / K or less, the linear expansion coefficient α g of the glass substrate is 0.6×10 −6 / K or more and 10×10 −6 / K or less; the transparent conductive oxide layer includes at least one of a fluorine-doped tin oxide layer and an antimony-doped tin oxide layer; A glass article characterized by:

2. the shielding layer includes a crystalline component and a pigment; The glass article according to claim 1, wherein the crystallinity value represented by the CPS ratio of the crystalline component to the pigment in X-ray diffraction measurement data of the shielding layer is 7 or more and 33 or less.

3. the shielding layer includes a crystalline component and a pigment; The C / Si ratio of the carbon-added silicon oxide layer to the crystallinity value represented by the CPS ratio of the crystalline component to the pigment in the X-ray diffraction measurement data of the shielding layer is 0.005 or more and 0.04 or less. The glass article according to claim 1 or 2.

4. The linear expansion coefficient α of the carbon-added silicon oxide layer Ｓｉ But 0.6 x 10 －６ / K or more, 4.0×10 －６ The glass article according to any one of claims 1 to 3, wherein the glass article has a viscosity of 1 / 2K or less.

5. The linear expansion coefficient α of the carbon-added silicon oxide layer Ｓｉ But 2.9 x 10 －６ The glass article according to claim 4, wherein the viscosity is 1 / K or less.

6. A glass article according to any one of claims 1 to 5, wherein the ratio O / Si of the atomic composition percentage of oxygen to silicon in the carbon-doped silicon oxide layer is 1.2 or more and 3.0 or less.

7. The glass article according to claim 1, wherein the transparent conductive oxide layer has a linear expansion coefficient α TCO of 1.0×10 −6 / K or more and 9.0×10 −6 / K or less.

8. The thickness t of the glass substrate ｇ The glass article according to any one of claims 1 to 7, wherein the thickness is 2.0 mm or more and 3.5 mm or less.

9. The carbon-doped silicon oxide layer has a thickness t Ｓｉ The glass article according to any one of claims 1 to 8, wherein the average particle diameter is 30 nm or more and 150 nm or less.

10. The method of claim 1, wherein the thickness of the fluorine-doped tin oxide layer is 100 nm or more and 500 nm or less; 10. The glass article according to claim 1, wherein the antimony-doped tin oxide layer has a thickness of 250 nm or more and 500 nm or less.

11. The method of claim 10, wherein the thickness of the fluorine-doped tin oxide layer is 150 nm or more and 350 nm or less; 11. The glass article according to claim 10, wherein the antimony-doped tin oxide layer has a thickness of 300 nm or more and 450 nm or less.

12. The glass article according to any one of claims 1 to 11, wherein the thickness t sh of the shielding layer is 8 µm or more and 20 µm or less.

13. The glass article according to any one of claims 1 to 12, which is used as a window glass for an automobile.

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