Method for producing resin layer-attached glass plate, resin layer-attached glass plate, glass plate, photovoltaic module, and method for producing photovoltaic module

Abstract

To provide a method for producing a resin layer-attached glass plate by which the resin layer-attached glass plate is obtained with excellent resistance to falling objects.SOLUTION: The method for producing a resin layer-attached glass plate includes performing etching and cleaning on at least one surface of a glass plate, and then forming a resin layer on the one surface without substantially increasing scratches on the one surface.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a method for producing a glass plate with a resin layer. The present invention also relates to a glass plate with a resin layer and a glass plate. The present invention also relates to a photovoltaic module and a method for manufacturing a photovoltaic module. [Background technology]

[0002] In recent years, cover glass has been used for the purpose of protecting and enhancing the aesthetic appearance of display devices such as mobile phones, smartphones, and tablet terminals. Cover glass for these applications is required to have excellent strength to prevent breakage due to impact, etc. The cover glass described above may also be used to protect photovoltaic power generation modules, various sensors, and the like.

[0003] On the other hand, etching is known as a technique for thinning a glass plate. For example, Patent Document 1 discloses a method of etching the surface of a glass plate using an etching solution containing hydrofluoric acid. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 2017-081767 Summary of the Invention [Problem to be solved by the invention]

[0005] The present inventors have studied the etching of glass plates described in Patent Document 1 and the like, and have obtained glass plates with resin layers. As a result, they have found that there is room for improvement in the resistance of the obtained glass plates with resin layers to falling objects such as hail.

[0006] The present invention has been made in view of the above-mentioned problems, and an object of the present invention is to provide a method for producing a resin layer-coated glass sheet that can produce a resin layer-coated glass sheet that has excellent resistance to falling objects. Another object of the present invention is to provide a glass plate with a resin layer. Another object of the present invention is to provide a glass plate. Another object of the present invention is to provide a photovoltaic power generation module and a method for manufacturing the photovoltaic power generation module. [Means for solving the problem]

[0007] As a result of intensive research into the above-mentioned problems, the present inventors have found that if a resin layer is formed on the surface of an etched glass plate without substantially increasing scratches on one side, a glass plate with a resin layer having excellent resistance to falling objects can be obtained, and have arrived at the present invention. That is, the inventors have found that the above problems can be solved by the following configuration.

[0008] [1] A method for producing a glass plate with a resin layer, comprising: etching and cleaning at least one surface of a glass plate; and then forming a resin layer on the one surface without substantially increasing scratches on the one surface. [2] The method for producing a glass plate with a resin layer according to [1], wherein the resin layer is formed on the one surface without touching anything other than the resin layer. [3] The method for producing a resin layer-attached glass plate according to [1] or [2], wherein the glass plate is chemically strengthened glass or physically strengthened glass. [4] The method for producing a resin layer-attached glass plate according to [1] or [2], wherein etching is carried out on only one surface of the glass plate. [5] A glass plate with a resin layer, comprising a glass plate and a resin layer, The increase in the number density of recesses on at least one surface of the glass plate before and after the etching test is 10 / cm 2 The following is a glass plate with a resin layer. The etching test involves immersing a glass plate in an etching solution containing 5% by mass of hydrogen fluoride, 15% by mass of hydrogen chloride, and 80% by mass of water at a temperature of 25°C for 10 minutes. [6] The glass plate with a resin layer according to [5], wherein the glass plate is chemically strengthened glass or physically strengthened glass. [7] The glass plate with a resin layer according to [6], which satisfies at least one of the following requirements 1 and 2: Requirement 1: The depth of the compressive stress layer on one surface of the glass plate is smaller than the depth of the compressive stress layer on the other surface of the glass plate. Requirement 2: The compressive stress on the one surface side of the glass plate is smaller than the compressive stress on the other surface side of the glass plate. [8] A glass plate, wherein recesses having a diameter of 1 to 100 μm and a depth of 0.01 to 10 μm are formed at a rate of 0.1 / cm on at least one surface of the glass plate. 2 A glass plate having the above. [9] The increase in the number density of recesses on at least one surface of the glass plate before and after the etching test is 10 / cm 2 The glass plate according to [8], which is: The etching test involves immersing a glass plate in an etching solution containing 5% by mass of hydrogen fluoride, 15% by mass of hydrogen chloride, and 80% by mass of water at a temperature of 25°C for 10 minutes.

[10] The glass plate according to [8], which is chemically strengthened glass or physically strengthened glass.

[11] The glass plate according to

[10] , which satisfies at least one of the following requirements 1 and 2:

[12] In mole percent based on oxides, SiO2 52-75%, Al2O3 0-20%, The glass plate according to any one of [8] to

[11] , containing 1 to 20% of Na2O. Requirement 1: The depth of the compressive stress layer on one surface of the glass plate is smaller than the depth of the compressive stress layer on the other surface of the glass plate. Requirement 2: The compressive stress on the one surface side of the glass plate is smaller than the compressive stress on the other surface side of the glass plate.

[13] A photovoltaic module comprising the glass plate according to any one of [8] to

[12] and a photovoltaic substrate, The increase in the number density of the recesses before and after the etching test on the glass plate was 10 / cm 2 A photovoltaic module, wherein a surface that is:

[14] A photovoltaic module having a glass plate and a photovoltaic substrate, wherein the glass plate is physically tempered glass, and recesses each having a diameter of 1 to 100 μm and a depth of 0.01 to 10 μm are formed at a rate of 0.1 / cm on the surface of the glass plate facing the photovoltaic substrate. 2 A solar power generation module having the above.

[15] A photovoltaic module including a photovoltaic substrate having a light-receiving surface and a back surface opposite to the light-receiving surface, and a light-receiving surface-side glass plate disposed on the light-receiving surface side of the photovoltaic substrate, A photovoltaic module in which the light-receiving side glass plate satisfies one or more of the following requirements A1, A2, and A3. Requirement A1: The compressive stress layer depth on the photovoltaic substrate side of the light-receiving surface glass plate is smaller than the compressive stress layer depth on the side of the light-receiving surface glass plate opposite to the photovoltaic substrate side. Requirement A2: The compressive stress on the photovoltaic substrate side of the light-receiving surface glass plate is smaller than the compressive stress on the side of the light-receiving surface glass plate opposite to the photovoltaic substrate side. Requirement A3: The light-receiving surface glass plate is warped convexly on the side opposite to the photovoltaic power generation substrate side.

[16] The photovoltaic module according to

[15] , wherein the light-receiving surface glass plate has a stepped portion where the thickness of the light-receiving surface glass plate is thinner in at least a part of the periphery of the light-receiving surface glass plate on the surface opposite to the photovoltaic substrate side.

[17] A method for manufacturing a photovoltaic module, comprising etching and cleaning at least one surface of a glass plate, and arranging a photovoltaic substrate on the one surface.

[18] A method for manufacturing a photovoltaic module, comprising: arranging a light-receiving surface-side glass plate on the light-receiving surface side of a photovoltaic substrate having a light-receiving surface and a back surface opposite to the light-receiving surface; and arranging a back surface-side glass plate on the back surface side to obtain a photovoltaic module, The method for manufacturing a photovoltaic module includes etching and cleaning at least one of the photovoltaic substrate side of the light-receiving side glass plate and the side of the back side glass plate opposite to the photovoltaic substrate side.

[19] The method for manufacturing a photovoltaic module according to

[18] , wherein the rear surface glass plate having the hole is etched and cleaned. [Effects of the Invention]

[0009] According to the present invention, it is possible to provide a method for producing a resin layer-coated glass plate that can produce a resin layer-coated glass plate that has excellent resistance to falling objects. Furthermore, the present invention can provide a glass plate with a resin layer. The present invention also provides a glass plate. The present invention also provides a photovoltaic power generation module and a method for manufacturing the photovoltaic power generation module. [Brief explanation of the drawings]

[0010] [Figure 1] 1 is a cross-sectional view schematically illustrating an example of a glass plate with a resin layer. [Figure 2] 1 is a cross-sectional view showing an example of a photovoltaic power generation module of the present invention. [Figure 3] FIG. 4 is a cross-sectional view showing another example of a photovoltaic power generation module according to the present invention. [Figure 4] FIG. 10 is a cross-sectional view showing a modified example of another example of the photovoltaic power generation module. [Figure 5] FIG. 10 is a cross-sectional view of a photovoltaic power generation module that satisfies requirement A3. [Figure 6] FIG. 2 is a top view of a glass plate used in one embodiment of the photovoltaic module of the present invention. [Figure 7] 7 is a cross-sectional view taken along the line AA of the glass plate shown in FIG. 6. [Figure 8] FIG. 1 is a cross-sectional view schematically illustrating an embodiment in which a glass plate having a step portion is used as a light-receiving surface side glass plate of a photovoltaic module. [Figure 9] FIG. 10 is a cross-sectional schematic diagram of a modified example of an embodiment in which a glass plate having a step portion is used as a light-receiving surface side glass plate of a photovoltaic module. [Figure 10] FIG. 1 is a cross-sectional schematic diagram of an embodiment in which a glass plate having a step portion is used as a rear glass plate of a photovoltaic module. [Figure 11] FIG. 2 is a top view of a rear glass having a hole. [Figure 12] FIG. 1 is a schematic diagram of a ball drop strength tester used to evaluate strength against a falling object. [Figure 13] 1 is a photograph of an example of a sample that has developed a crack after being tested using a drop ball strength tester. [Figure 14] FIG. 10 is a schematic diagram of a microscope image of a recess after etching. DETAILED DESCRIPTION OF THE INVENTION

[0011] The chemically strengthened glass of the present invention will be described in detail below, but the present invention is not limited to the following embodiments and can be arbitrarily modified and implemented within the scope of the present invention. In this specification, glass compositions are expressed in mole percentages based on oxides, and mole % is sometimes simply referred to as %. Furthermore, the symbol "to" indicating a range of values ​​is used to mean that the values ​​before and after it are included as the lower and upper limits.

[0012] In this specification, "chemically strengthened glass" refers to glass after chemical strengthening treatment, and "glass for chemical strengthening" refers to glass before chemical strengthening treatment. In this specification, "physically strengthened glass" refers to glass that has been subjected to a physical strengthening treatment.

[0013] In this specification, the surface of a glass plate refers to either of the two main surfaces of the glass plate that have the largest area.

[0014] In the glass composition, "substantially not contained" means that the components are not contained except for unavoidable impurities contained in raw materials, etc., that is, they are not intentionally contained. Specifically, the content of components other than those described as the glass composition is preferably less than 0.1 mol%, more preferably 0.08 mol% or less, and even more preferably 0.05 mol% or less.

[0015] In this specification, the term "stress profile" refers to a pattern that expresses compressive stress values ​​as a function of depth from the glass surface. A negative compressive stress value indicates tensile stress. In this specification, the "stress profile" can be measured by a method using a combination of an optical waveguide surface stress meter and a scattered light photoelastic stress meter.

[0016] Optical waveguide surface stress meters can accurately measure the stress in glass in a short time. One example of an optical waveguide surface stress meter is the FSM-6000 manufactured by Orihara Seisakusho. However, in principle, optical waveguide surface stress meters can only measure stress when the refractive index decreases from the surface to the interior of the sample. In chemically strengthened glass, the layer obtained by replacing sodium ions inside the glass with external potassium ions has a refractive index that decreases from the surface to the interior of the sample, so stress can be measured with an optical waveguide surface stress meter. However, the stress in the layer obtained by replacing lithium ions inside the glass with external sodium ions cannot be accurately measured with an optical waveguide surface stress meter.

[0017] The method using a scattered light photoelastic stress meter can measure stress regardless of the refractive index distribution. An example of a scattered light photoelastic stress meter is the SLP2000 manufactured by Orihara Seisakusho. However, scattered light photoelastic stress meters are easily affected by surface scattering, and may not be able to accurately measure stress near the surface. For the above reasons, accurate stress measurement becomes possible by combining two types of measuring devices, an optical waveguide surface stress meter and a scattered light photoelastic stress meter.

[0018] In this specification, the compressive stress layer depth is the depth at which the compressive stress value becomes zero.

[0019] <Method of manufacturing a glass plate with a resin layer> The method for producing a resin layer-attached glass plate of the present invention involves etching and cleaning at least one surface of a glass plate, and then forming the resin layer without substantially increasing scratches on the one surface. The mechanism by which a resin layer-coated glass having excellent resistance to falling objects can be obtained by the method for producing a resin layer-coated glass plate of the present invention is not entirely clear, but the present inventors speculate as follows. In the method for producing a glass plate with a resin layer of the present invention, etching and cleaning are performed. It is believed that etching changes the shape of scratches present in the glass plate, making it less likely that breakage will occur originating from the scratches. Here, in the method for producing a glass plate with a resin layer of the present invention, a resin layer is formed on the surface that has been etched and cleaned without substantially increasing the number of scratches. This maintains the shape of the scratches changed by etching, and further, new scratches are not formed during the formation of the resin layer or in subsequent steps, so it is believed that a state in which breakage is less likely to occur is maintained. As a result, according to the method for producing a glass plate with a resin layer of the present invention, it is possible to obtain glass with a resin layer (see FIG. 1) that has excellent resistance to falling objects.

[0020] Hereinafter, the step of etching and cleaning at least one surface of a glass plate will also be referred to as an “etching step.” Furthermore, the step of forming the resin layer on one surface will also be referred to as a “resin layer forming step.” In the following description, scratches on a glass plate include scratches that are visible to the naked eye and scratches that are not visible to the naked eye (also called "latent scratches"). The method for producing a resin layer-attached glass plate of the present invention will be described below.

[0021] [Etching process] In the method for producing a resin layer-attached glass plate of the present invention, an etching step is carried out in which etching and cleaning are carried out on at least one surface of the glass plate. The glass plate to be subjected to the etching step is not particularly limited, and various glass plates can be used. For example, the type of glass plate is not particularly limited, and it may be figured glass or float glass. It may also be glass obtained by the fusion method or flat glass obtained by the roll-out method. The glass plate may be tempered glass. That is, the glass plate may be chemically tempered glass or physically tempered glass. Examples of the glass plate include a glass plate obtained by subjecting patterned glass to a physical tempering treatment, a glass plate obtained by subjecting patterned glass to a chemical tempering treatment, a glass plate obtained by subjecting float glass to a physical tempering treatment, and a glass plate obtained by subjecting float glass to a chemical tempering treatment. An example of a glass plate to be subjected to the etching step will be described in detail below.

[0022] An example of the chemically strengthened glass is glass obtained by chemically strengthening a glass plate. Chemical strengthening methods include, for example, ion exchange. In the ion exchange method, glass is immersed in a treatment liquid (e.g., a molten salt containing at least one of potassium nitrate and sodium nitrate) to exchange ions with small ionic radii (e.g., Li ions and Na ions) contained in the glass for ions with larger ionic radii (e.g., Na ions and K ions), thereby generating compressive stress on the glass surface. The compressive stress is generated uniformly across the entire surface of the glass, forming a compressive stress layer of uniform depth across the entire surface of the glass.

[0023] The magnitude of the compressive stress on the glass surface (hereinafter referred to as surface compressive stress) and the depth of the compressive stress layer formed on the glass surface can be adjusted by the glass composition, the concentration of the treatment solution, the chemical strengthening treatment time, and the chemical strengthening treatment temperature, respectively. The surface compressive stress is, for example, 200 MPa or more, preferably 400 MPa or more, and more preferably 500 MPa or more. On the other hand, the surface compressive stress is, for example, 1200 MPa or less, preferably 900 MPa or less, and more preferably 800 MPa or less. The depth of the compressive stress layer is, for example, 2 μm or more, preferably 3 μm or more, and more preferably 5 μm or more. On the other hand, the depth of the compressive stress layer is, for example, 100 μm or less, preferably 60 μm or less, and more preferably 40 μm or less.

[0024] The chemically strengthened glass is not limited as long as it is ion-exchangeable, and examples thereof include aluminosilicate glass, soda glass, soda-lime glass, and lithium silicate glass that have been subjected to chemical strengthening treatment.

[0025] The physically strengthened glass may have a glass transition temperature of 500°C or higher and an average expansion coefficient α 50~350 is 70 x 10 -7 / ° C. An example of glass having the above properties is soda lime glass. Thermal tempering refers to a process in which a uniformly heated glass sheet is rapidly cooled from a temperature near its softening point, and compressive stress is generated on the glass surface due to the temperature difference between the surface and the interior of the glass. A typical thermal tempering process involves producing glass sheets by the float method or other methods, heating the cut glass sheets to a temperature near its softening point or yield point, and then spraying a coolant onto the surface to rapidly cool them, a process known as air-cooling tempering. Compressive stress is generated uniformly across the entire surface of the glass, and a compressive stress layer of uniform depth is formed across the entire surface of the glass. Thermal tempering is more suitable for tempering thick glass sheets than chemical tempering.

[0026] The float glass refers to glass formed by the float method. As described above, the float glass may be subjected to a physical or chemical strengthening treatment.

[0027] The patterned glass refers to glass formed by pressing a roll mold against glass by a roll-out method. The pattern on the surface of the patterned glass is not particularly limited, and may have any known pattern. As described above, the patterned glass may be subjected to a physical or chemical strengthening treatment. In physically strengthened glass and chemically strengthened glass, increasing the compressive stress can make the surface more scratch-resistant. In addition, increasing the depth of the compressive stress layer can make the glass scratch-resistant to a greater extent.

[0028] The composition of the glass plate is not particularly limited, but may be, for example, the following in mole percent on an oxide basis: SiO2 52-75%, Al2O3 0-20%, A glass plate having a composition containing 1 to 20% of Na2O is preferred. A more preferred composition of the glass plate will be described below.

[0029] One of the more preferable embodiments of the composition of the glass plate is, in mole percent on an oxide basis, SiO2 52-75%, Al2O3 0-20%, Li2O 0-18%, Na2O 1-20%, K2O 0-5%, MgO 0-20%, CaO 0-20%, SrO 0-20%, BaO 0-20%, ZnO 0-10% TiO2 0-1% ZrO2 0-8%, Contains 0-5% Y2O3. One of the more preferred embodiments of the glass composition (first glass composition) will be described below.

[0030] SiO2 is a component that forms the network structure of glass. It is also a component that increases chemical durability. The SiO2 content is preferably 52% or more, more preferably 56% or more, even more preferably 60% or more, and particularly preferably 64% or more. On the other hand, to improve meltability, the SiO2 content is preferably 75% or less, more preferably 73% or less, even more preferably 71% or less, and particularly preferably 69% or less.

[0031] Al2O3 is a component that can increase the surface compressive stress due to chemical strengthening. The Al2O3 content is preferably 1% or more, more preferably 2% or more, even more preferably 4% or more, and particularly preferably 6% or more. On the other hand, the Al2O3 content is preferably 20% or less, more preferably 18% or less, further preferably 17% or less, further preferably 16% or less, and most preferably 15% or less, in order to prevent the devitrification temperature of the glass from becoming too high.

[0032] Na2O is a component that improves the meltability of glass and forms surface compressive stress by ion exchange. The Na2O content is preferably 1% or more, more preferably 2% or more, and particularly preferably 4% or more. If the Na2O content is too high, the chemical strengthening properties will decrease, so the Na2O content is preferably 20% or less, more preferably 18% or less, particularly preferably 16% or less, and most preferably 14% or less.

[0033] Like NaO, KO is a component that lowers the melting temperature of glass and forms surface compressive stress through ion exchange. When KO is contained, its content is preferably 0% or more, more preferably 0.1% or more, even more preferably 0.3% or more, even more preferably 0.4% or more, and particularly preferably 0.5% or more. If the KO content is too high, the chemical strengthening properties or chemical durability will decrease, so the content is preferably 5% or less, more preferably 4.8% or less, even more preferably 4.5% or less, particularly preferably 4.2% or less, and most preferably 4.0% or less.

[0034] The total content of Na2O and K2O (Na2O+K2O) is preferably 1% or more, and more preferably 2% or more, from the viewpoints of improving the meltability of glass raw materials and forming surface compressive stress by ion exchange.

[0035] Li2O is a component that forms surface compressive stress by ion exchange. When Li2O is contained, its content is preferably 1% or more, more preferably 2% or more, even more preferably 4% or more, and particularly preferably 5% or more. On the other hand, to stabilize the glass, the Li2O content is preferably 18% or less, more preferably 17% or less, even more preferably 16% or less, and most preferably 15% or less.

[0036] The ratio of the K2O content to the total content of Li2O, Na2O, and K2O (hereinafter referred to as R2O), K2O / R2O, is preferably 0.2 or less, as this improves chemical strengthening properties and chemical durability. K2O / R2O is more preferably 0.15 or less, and even more preferably 0.10 or less. R2O is preferably 10% or more, more preferably 12% or more, and even more preferably 15% or more. R2O is preferably 20% or less, and more preferably 18% or less.

[0037] MgO is a component that stabilizes glass and also increases mechanical strength and chemical resistance, so it is preferable to add it when the Al2O3 content is relatively low. The MgO content is preferably 1% or more, more preferably 2% or more, even more preferably 3% or more, and particularly preferably 4% or more. On the other hand, if too much MgO is added, the viscosity of the glass decreases, making devitrification or phase separation more likely to occur. The MgO content is preferably 20% or less, more preferably 19% or less, even more preferably 18% or less, and particularly preferably 17% or less.

[0038] CaO, SrO, BaO and ZnO are all components that improve the meltability of the glass and may be contained.

[0039] CaO is a component that improves the meltability of glass and improves the crushability of glass when chemically strengthened, and may be contained. When CaO is contained, the content is preferably 0.5% or more, more preferably 1% or more, even more preferably 2% or more, particularly preferably 3% or more, and most preferably 5% or more. On the other hand, if the CaO content exceeds 20%, the ion exchange performance is significantly reduced, so it is preferably 20% or less. The CaO content is more preferably 14% or less, and even more preferably 10% or less, 8% or less, 6% or less, 3% or less, and 1% or less in the following stepwise manner.

[0040] SrO is a component that improves the meltability of glass and improves the crushability of glass when chemically strengthened, and may be contained. When SrO is contained, the content is preferably 0.5% or more, more preferably 1% or more, even more preferably 2% or more, particularly preferably 3% or more, and most preferably 5% or more. On the other hand, if the SrO content exceeds 20%, the ion exchange performance is significantly reduced, so it is preferably 20% or less. The SrO content is more preferably 14% or less, and even more preferably 10% or less, 8% or less, 6% or less, 3% or less, and 1% or less in the following stepwise manner.

[0041] BaO is a component that improves the meltability of glass and improves the crushability of glass when chemically strengthened, and may be contained. When BaO is contained, the content is preferably 0.5% or more, more preferably 1% or more, even more preferably 2% or more, particularly preferably 3% or more, and most preferably 5% or more. On the other hand, if the BaO content exceeds 20%, the ion exchange performance is significantly reduced. The BaO content is preferably 20% or less, and more preferably 15% or less, 10% or less, 6% or less, 3% or less, and 1% or less in the following stepwise order.

[0042] ZnO is a component that improves the meltability of glass and may be contained. When ZnO is contained, the content is preferably 0.25% or more, and more preferably 0.5% or more. On the other hand, if the ZnO content exceeds 10%, the weather resistance of the glass will be significantly reduced. The ZnO content is more preferably 10% or less, and even more preferably 8% or less, 6% or less, 3% or less, and 1% or less in the following stepwise order.

[0043] ZrO2 is a component that enhances mechanical strength and chemical durability, and is preferably contained because it significantly improves CS. The ZrO2 content is preferably 0.5% or more, more preferably 0.7% or more, even more preferably 1.0% or more, particularly preferably 1.2% or more, and most preferably 1.5% or more. On the other hand, to suppress devitrification during melting, ZrO2 is preferably 8% or less, more preferably 7.5% or less, even more preferably 7% or less, and particularly preferably 6% or less. If the ZrO2 content is too high, the viscosity decreases due to an increase in the devitrification temperature. To suppress deterioration of formability due to such a decrease in viscosity, when the forming viscosity is low, the ZrO2 content is preferably 5% or less, more preferably 4.5% or less, and even more preferably 3.5% or less.

[0044] To improve chemical durability, ZrO2 / R2O is preferably 0.02 or more, more preferably 0.04 or more, even more preferably 0.06 or more, particularly preferably 0.08 or more, and most preferably 0.1 or more. ZrO2 / R2O is preferably 0.2 or less, more preferably 0.18 or less, even more preferably 0.16 or less, and particularly preferably 0.14 or less.

[0045] Although TiO2 is not essential, if it is contained, it is preferably 0.05% or more, more preferably 0.1% or more. On the other hand, in order to suppress devitrification during melting, the TiO2 content is preferably 1% or less, more preferably 0.5% or less, and even more preferably 0.3% or less.

[0046] Although SnO2 is not essential, when it is contained, it is preferably 0.5% or more, more preferably 1% or more, even more preferably 1.5% or more, and particularly preferably 2% or more. On the other hand, in order to suppress devitrification during melting, the content of SnO2 is preferably 4% or less, more preferably 3.5% or less, even more preferably 3% or less, and particularly preferably 2.5% or less.

[0047] Y2O3 is a component that, when chemically strengthened glass, has the effect of preventing fragments from scattering when the glass breaks, and may be contained. The Y2O3 content is preferably 0.3% or more, more preferably 0.5% or more, even more preferably 0.7% or more, and particularly preferably 1.0% or more. On the other hand, in order to suppress devitrification during melting, the Y2O3 content is preferably 5% or less, and more preferably 4% or less.

[0048] B2O3 is a component that improves the chipping resistance and meltability of glass, and may be contained. When B2O3 is contained, the content is preferably 0.5% or more, more preferably 1% or more, and even more preferably 2% or more, in order to improve meltability. On the other hand, if the B2O3 content is too high, striae may occur during melting, or phase separation may occur, which may lead to a deterioration in the quality of the glass for chemical strengthening, so the B2O3 content is preferably 10% or less. The B2O3 content is more preferably 8% or less, even more preferably 6% or less, and particularly preferably 4% or less.

[0049] La2O3, Nb2O5, and Ta2O5 are all components that, when chemically strengthened glass, make it less likely for glass to shatter when broken, and may be included to increase the refractive index. When these are included, the total content of La2O3, Nb2O5, and Ta2O5 (hereinafter, La2O3 + Nb2O5 + Ta2O5) is preferably 0.5% or more, more preferably 1% or more, even more preferably 1.5% or more, and particularly preferably 2% or more. Furthermore, to make the glass less susceptible to devitrification during melting, La2O3 + Nb2O5 + Ta2O5 is preferably 4% or less, more preferably 3% or less, even more preferably 2% or less, and particularly preferably 1% or less.

[0050] CeO2 may also be contained. CeO2 may oxidize the glass, thereby suppressing coloration. When CeO2 is contained, the content is preferably 0.03% or more, more preferably 0.05% or more, and even more preferably 0.07% or more. In order to increase transparency, the CeO2 content is preferably 1.5% or less, and more preferably 1.0% or less.

[0051] When chemically strengthened glass is used in a colored form, coloring components may be added to the glass within a range that does not impede the achievement of the desired chemical strengthening characteristics. Examples of coloring components include Co3O4, MnO2, Fe2O3, NiO, CuO, Cr2O3, V2O5, Bi2O3, SeO2, Er2O3, and Nd2O3.

[0052] The total content of coloring components is preferably in the range of 1% or less. If a higher visible light transmittance of the glass is desired, it is preferable that these components are substantially not contained.

[0053] To improve weather resistance against ultraviolet light irradiation, HfO2, Nb2O5, and Ti2O3 may be added. When added for the purpose of improving weather resistance against ultraviolet light irradiation, the total content of HfO2, Nb2O5, and Ti2O3 is preferably 1% or less, more preferably 0.5% or less, and even more preferably 0.1% or less, in order to suppress the influence on other properties.

[0054] In addition, SO3, chlorides, and fluorides may be appropriately contained as clarifiers for melting the glass. The total content of components functioning as clarifiers is preferably 2% or less, more preferably 1% or less, and even more preferably 0.5% or less, expressed as mass% on an oxide basis, since excessive addition affects the strengthening properties. While there is no particular lower limit, typically, a total of 0.05% or more, expressed as mass% on an oxide basis, is preferred.

[0055] When SO3 is used as a fining agent, if the content is too low, no effect is observed, so the content is preferably 0.01% or more, more preferably 0.05% or more, and even more preferably 0.1% or more, expressed as mass% on the oxide basis. Also, when SO3 is used as a fining agent, the content of SO3 is preferably 1% or less, more preferably 0.8% or less, and even more preferably 0.6% or less, expressed as mass% on the oxide basis.

[0056] When Cl is used as a fining agent, if it is added too much, it will affect physical properties such as strengthening characteristics, so the Cl content is preferably 1% or less, more preferably 0.8% or less, and even more preferably 0.6% or less, expressed as mass% on the oxide basis. Also, if the Cl content is too low when Cl is used as a fining agent, no effect will be seen, so the Cl content is preferably 0.05% or more, more preferably 0.1% or more, and even more preferably 0.2% or more, expressed as mass% on the oxide basis.

[0057] When SnO2 is used as a fining agent, the content of SnO2 is preferably 1% or less, more preferably 0.5% or less, and even more preferably 0.3% or less, expressed as mass% on the oxide basis. Furthermore, when SnO2 is used as a fining agent, if the content of SnO2 is too low, the effect is not seen, so the content is preferably 0.02% or more, more preferably 0.05% or more, and even more preferably 0.1% or more, expressed as mass% on the oxide basis.

[0058] It is preferable that P2O5 is not contained. If P2O5 is contained, the content is preferably 2.0% or less, more preferably 1.0% or less, and most preferably zero.

[0059] It is preferable that As2O3 is not contained. When Sb2O3 is contained, it is preferable that it is 0.3% or less, more preferably 0.1% or less, and most preferably it is not contained.

[0060] Another preferred embodiment of the composition of the glass plate is, in mole percent on an oxide basis, SiO2 60-76%, Al2O3 0-10%, Na2O 10-18%, K2O 0-5%, MgO 2-12%, It is preferable that CaO is contained in an amount of 0 to 15%. Hereinafter, details of another embodiment (second glass composition) of a more preferable composition for the glass plate will be described. Note that hereinafter, percentages indicate contents expressed as mole percentages on an oxide basis, unless otherwise specified.

[0061] SiO2 is known as a component that forms a network structure in the glass microstructure and is a major component that constitutes glass. The SiO2 content is preferably 61% or more, and even more preferably 62% or more. The SiO2 content is more preferably 74% or less, even more preferably 72% or less, and particularly preferably 70% or less.

[0062] Al2O3 is a component that improves the weather resistance of glass and has the effect of improving ion exchange performance in chemical strengthening. The Al2O3 content is more preferably 0.1% or more, even more preferably 0.2% or more, particularly preferably 0.5% or more, and may be 1.0% or more. The Al2O3 content is more preferably 9% or less.

[0063] Na2O is a component that reduces the high-temperature viscosity and devitrification temperature of glass and improves the meltability and formability of glass. It is also a component that forms compressive stress through ion exchange and has the effect of increasing the compressive stress layer depth DOL. The Na2O content is more preferably 11% or more, and even more preferably 12% or more. The Na2O content is more preferably 16% or less, and even more preferably 15% or less.

[0064] Although K2O is not essential, it may be contained for one or more purposes of improving the meltability of the glass, improving chemical durability, and increasing the ion exchange rate. When K2O is contained, the K2O content is more preferably 4% or less. When K2O is contained, the K2O content is more preferably 0.1% or more, and even more preferably 0.5% or more. The second glass composition does not necessarily contain K2O.

[0065] MgO is a component that stabilizes glass. The MgO content is more preferably 3% or more, and even more preferably 4% or more. The MgO content is more preferably 11% or less.

[0066] CaO is not essential, but it is a component that stabilizes the glass. To improve water resistance and chemical resistance, the CaO content is preferably 5% or more, even more preferably 6% or more, and particularly preferably 7% or more. The CaO content is more preferably 13% or less, and even more preferably 11% or less. The second glass composition does not necessarily contain CaO.

[0067] The second glass composition may contain components other than those mentioned above (other components). Examples of other components include fining agents such as sulfates, Fe2O3, TiO2, ZrO2, SnO2, and Sb2O3. The total content of other components is preferably 1% or less.

[0068] The thickness of the glass plate to be subjected to the etching step is not particularly limited, but is often 0.1 mm or more, preferably 0.5 mm or more, more preferably 1.0 mm or more, and is often 10 mm or less, preferably 4 mm or less, more preferably 3 mm or less.

[0069] In the etching step, the glass plate is subjected to an etching treatment. Examples of the etching treatment method include a method in which the glass plate is brought into contact with an etching solution.

[0070] The etching solution is fluoride ions (F - ) and hexafluorosilicate ion (SiF6 2-Specific examples of the fluorine-containing compound include hydrogen fluoride (HF), ammonium fluoride (NHF), hexafluorosilicic acid (HSiF), and hexafluorosilicic acid ((NH)SiF). In addition to the above compounds, the etching solution preferably contains other acidic compounds, such as at least one compound selected from the group consisting of sulfuric acid (H2SO4), nitric acid (HNO3), hydrogen chloride (HCl), and phosphoric acid (H3PO4). The content of the fluorine-containing compound in the etching solution is preferably 0.01 to 15 mass %, more preferably 0.1 to 10 mass %, and even more preferably 1 to 8 mass %, relative to the total mass of the etching solution. In the etching solution, only one type of the fluorine-containing compound may be used, or two or more types may be used. The content of the other acidic compounds in the etching solution is preferably 0.1 to 30 mass %, more preferably 1 to 25 mass %, and even more preferably 5 to 20 mass %, relative to the total mass of the etching solution. In the etching solution, only one type of the other acidic compounds may be used, or two or more types may be used. The remainder of the etching solution is usually water.

[0071] The method for bringing the glass plate into contact with the etching solution is not particularly limited, but examples thereof include a method of immersing the glass plate in the etching solution, a method of showering the glass plate with the etching solution, and a method of spraying the etching solution onto the glass plate. When the glass plate is immersed in the etching solution, it is also preferable to carry out the etching while causing convection of the etching solution.

[0072] When the etching treatment is carried out by a method of contacting a glass plate with an etching solution, the treatment temperature is preferably 0° C. or higher, more preferably 10° C. or higher, even more preferably 20° C. or higher, and may be 40° C. or higher. The treatment temperature is often less than 100° C., and is preferably 90° C. or lower, more preferably 70° C. or lower.

[0073] When the etching treatment is carried out by contacting the glass plate with the etching solution, the contact time between the glass plate and the etching solution can be appropriately adjusted, but is, for example, preferably 30 seconds or more, more preferably 1 minute or more, and even more preferably 5 minutes or more, and the contact time is preferably 10 hours or less, preferably 1 hour or less, and even more preferably 30 minutes or less.

[0074] In the etching step, etching is followed by cleaning. The cleaning method is not particularly limited, but an example is a method in which the etched glass plate is brought into contact with a cleaning solution. The cleaning liquid is not particularly limited, but is preferably water. Examples of water include industrial water, tap water, distilled water, ion-exchanged water, and ultrapure water, with distilled water, ion-exchanged water, and ultrapure water being preferred.

[0075] Examples of methods for contacting the etched glass plate with the cleaning liquid include a method of immersing the glass plate in the cleaning liquid, a method of showering the cleaning liquid onto the glass plate, and a method of spraying the cleaning liquid onto the glass plate. When the glass plate is immersed in the cleaning solution, it is also preferable to carry out the immersion while causing convection in the cleaning solution.

[0076] The cleaning in the etching step may be carried out repeatedly. In the etching step, etching and washing may be repeated. For example, etching and washing may be repeated two or more times. When etching and washing are repeated, the number of times may be, for example, five or less.

[0077] The glass plate to be subjected to the etching step may have a protective film provided on one surface thereof, or an anti-reflection layer (AR layer) formed on one surface thereof. When a protective film is provided on the glass plate to be subjected to the etching step, it is preferable to use a protective film made of a material that is not altered by the etching solution used in the etching step.

[0078] The etching step may be performed on only one surface of the glass plate, or on both one surface and the other surface of the glass plate.

[0079] [Resin layer formation process] In the method for producing a glass plate with a resin layer of the present invention, the etching step is followed by the formation of a resin layer. This results in a glass plate with a resin layer (see FIG. 1). Here, in the method for producing a glass plate with a resin layer of the present invention, the resin layer is formed without substantially increasing scratches on the one surface. The resin layer forming step may be carried out on at least the surface that has been etched in the etching step, and may be carried out on only one surface or on both surfaces. The material for forming the resin layer is not particularly limited, and known resins can be used. Examples of materials for forming the resin layer include polyolefins (e.g., polyethylene, polypropylene, etc.), polyesters (polyethylene terephthalate, polyethylene naphthalate, etc.), polycarbonates, polyurethanes, and polyimides. The resin layer may also be a pressure-sensitive adhesive layer or an adhesive layer. Examples of materials that can be used to form the pressure-sensitive adhesive layer or adhesive layer include polyacrylic resins, polyolefin resins, polyvinyl alcohol resins, ethylene vinyl acetate resins, silicone resins, epoxy resins, and rubber resins. The resin layer may consist of one layer, or two or more layers.

[0080] In the resin layer forming step, "not substantially increasing scratches" means that the number of visible scratches is not increased and the number of invisible scratches (latent scratches) is not substantially increased. Here, "not substantially increasing latent scratches" means that when an etching test described later is carried out, the increase in the number density of recesses on the surface of the glass plate on which the resin layer is to be formed is 10 / cm. 2 The increase in the number density of the recesses is 5 / cm or less. 2 Less than 1 piece / cm is preferable. 2 It is more preferable that the increase in the number density of the recesses is 0 / cm. 2 It may be more than that. The increase in number density is measured according to the method described below.

[0081] Examples of methods for carrying out the resin layer forming step of the present invention include a method of forming a resin layer on the one surface without touching anything other than the resin layer.Specifically, for example, a method of laminating a resin layer to the surface of the glass plate that has been subjected to etching treatment.Furthermore, the resin layer may be formed by applying a composition containing components that constitute the resin layer. The phrase "forming a resin layer on one surface without touching anything other than the resin layer" means that no step of bringing anything other than the resin layer into contact with the one surface is carried out between the etching step and the resin layer forming step. The step of bringing anything other than the resin layer into contact with the one surface refers to a step of bringing a solid other than the resin layer into contact with the one surface, and examples of such steps include a step of polishing the one surface, a step of bringing the one surface into contact with a transport roller or the like to transport the one surface, and a step of storing the one surface in contact with another object.

[0082] Furthermore, the method for carrying out the resin layer forming step of the present invention is not limited to the method of forming a resin layer on the one surface without touching anything other than the resin layer. For example, a method may be used in which the member in contact with the one surface is made of a soft material such as resin, the glass sheet is conveyed in contact with the member, and then a resin layer is formed. Another method is to increase the smoothness of the surface of the member that comes into contact with the glass sheet, transport the glass sheet in contact with the member, and then form a resin layer thereon. Another method is to transport the glass sheet while contacting only the side surface of the glass sheet, and then form the resin layer.

[0083] The resin layer may be formed on the entire surface of the one surface of the glass plate, or may be formed on only a part of the surface. When the resin layer is formed only on a portion of the one surface of the glass plate (for example, an area excluding a 20 mm peripheral area of ​​the glass plate), the area where the resin layer is not formed (for example, an area within a 20 mm peripheral area of ​​the glass plate) may be contacted by the above-mentioned conveying roller or the like.

[0084] The thickness of the resin layer is, for example, 0.1 μm or more, preferably 1 μm or more, more preferably 10 μm or more, and even more preferably 30 μm or more, and 5000 μm or less, preferably 3000 μm or less, more preferably 300 μm or less, and even more preferably 100 μm or less. When the resin layer is made up of two or more layers, the total thickness of the resin layers preferably falls within the above preferred range.

[0085] The method for producing a resin layer-attached glass plate of the present invention may include steps other than those described above. For example, a drying step may be included between the etching step and the resin layer-forming step. The drying step refers to a step of removing droplets that have adhered to the surface of the glass plate in the etching step. That is, in the method for producing a glass plate with a resin layer of the present invention, the surface of the glass plate may be dried between the etching step and the resin layer-forming step. The method for carrying out the drying step is not particularly limited, and examples thereof include a method of supplying a gas to the surface of the glass plate and a method of heating the glass plate. In this specification, supplying a gas to the surface of the glass sheet in the drying step satisfies the requirement that "one surface is not in contact with anything other than the resin layer."

[0086] Hereinafter, more specific embodiments of the method for producing a resin layer-coated glass plate of the present invention will be described.

[0087] [Aspect 1] One embodiment of the method for producing a resin layer-attached glass plate of the present invention includes forming a precursor film of an antireflection film on one surface of a glass plate, physically strengthening the glass plate on which the precursor film of the antireflection film has been formed, attaching a chemical-resistant protective film to the surface of the glass plate on which the precursor film has been formed, and subjecting the glass plate to the above-mentioned etching step and resin layer-forming step. In the above embodiment, when the glass plate on which the precursor film of the anti-reflection film has been formed is physically strengthened, the precursor film of the anti-reflection film is heated, and the anti-reflection film is formed. In the above embodiment, etching is performed only on the surface and side of the glass plate opposite to the side on which the chemical-resistant protective film is attached. Furthermore, if the area of ​​the protective film is smaller than the area of ​​the surface of the glass plate, etching is also performed on the portion where the protective film is not placed (for example, the peripheral portion described below), and a step portion described below is formed on the surface of the glass plate. In the above embodiment, the chemical-resistant protective film attached to the glass plate may be peeled off. In the above embodiment, the form of the glass plate is not particularly limited, but it is preferably a patterned glass plate. Furthermore, as the chemical-resistant protective film, a known protective film can be used, and for example, a resin layer formed in the resin layer forming step can be appropriately selected.

[0088] [Aspect 2] Furthermore, one embodiment of the method for producing a resin layer-attached glass plate of the present invention includes chemically strengthening a glass plate to obtain a chemically strengthened glass plate, attaching a chemically resistant protective film to one surface of the chemically strengthened glass plate, and subjecting the chemically strengthened glass plate to the etching step and the resin layer forming step described above. In the above embodiment, etching is performed only on the surface of the chemically strengthened glass plate opposite to the surface on which the chemical-resistant protective film is attached and on the side surfaces. Furthermore, a step portion may be formed during etching as described in embodiment 1. In the above embodiment, the chemical-resistant protective film attached to the chemically strengthened glass plate may be peeled off. In the above embodiment, the type of the glass plate is not particularly limited, but it is preferably float glass.

[0089] [Aspect 3] In addition, one embodiment of the method for producing a resin layer-attached glass plate of the present invention includes a method in which a chemical-resistant protective film is attached to one surface of the glass plate, and the glass plate is subjected to the etching step and the resin layer-forming step described above. In the above embodiment, etching is performed only on the surface of the glass plate opposite to the surface on which the chemical-resistant protective film is attached, and on the side surfaces. Furthermore, a step may be formed during etching, as described in embodiment 1. In the above embodiment, the chemical-resistant protective film attached to the glass plate may be peeled off. In the above embodiment, the type of the glass plate is not particularly limited, but it is preferably float glass.

[0090] [Aspect 4] Furthermore, one embodiment of the method for producing a resin layer-attached glass plate of the present invention includes forming a precursor film of an antireflection film on one surface of the glass plate, heating the precursor film to form an antireflection film, attaching a chemical-resistant protective film to the surface of the glass plate on the side on which the antireflection film has been formed, and subjecting the glass plate to the above-mentioned etching step and resin layer-forming step. In the above embodiment, etching is performed only on the surface of the glass plate opposite to the surface on which the chemical-resistant protective film is attached, and on the side surfaces. Also, a step may be formed during etching, as described in embodiment 1. In the above embodiment, the chemical-resistant protective film attached to the glass plate may be peeled off. In the above embodiment, the type of the glass plate is not particularly limited, but it is preferably float glass.

[0091] [Aspect 5] In one embodiment of the method for producing a resin layer-attached glass plate of the present invention, a chemical-resistant film is not attached to the glass plate, and the glass plate is subjected to the etching step and the resin layer-forming step. In the above embodiment, etching is performed on both surfaces of the glass plate and on the side surface of the glass plate. In the above embodiment, the resin layer formed in the resin layer forming step is preferably formed on only one surface of the glass plate. In the above embodiment, the type of the glass plate is not particularly limited, but it is preferably float glass.

[0092] <Glass plate with resin layer> The resin layer-attached glass plate of the present invention has a glass plate and a resin layer, and is characterized in that the increase in the number density of recesses on at least one surface before and after an etching test is 10 / cm 2 The following is the result. The etching test will be described in detail later. The resin layer-coated glass plate of the present invention can be obtained by the above-described method for producing a resin layer-coated glass plate of the present invention. The resin layer-attached glass plate of the present invention does not have an increase in the number density of recesses before and after the etching test, and therefore has few scratches and is thought to have excellent resistance to falling objects.

[0093] FIG. 1 is a cross-sectional view showing an example of a resin layer-attached glass plate of the present invention. The resin layer-attached glass plate 30 shown in Fig. 1 has a glass plate 10 and a resin layer 20. Fig. 1 shows an example in which the resin layer 20 is provided only on one surface of the glass plate 10. In the resin layer-attached glass plate 30 shown in Fig. 1, the increase in the number density of recesses on one surface of the glass plate 10 (the surface on which the resin layer 20 is provided) is 10 / cm 2 The following is the result.

[0094] The resin layer-attached glass plate of the present invention will be described in detail below.

[0095] [Resin layer] The resin layer-attached glass plate of the present invention has a resin layer. Examples of the resin layer included in the resin layer-coated glass plate of the present invention and preferred embodiments thereof are the same as those described in the method for producing a resin layer-coated glass plate of the present invention, and therefore further description thereof will be omitted. The resin layer-attached glass plate of the present invention may have a resin layer provided on only one surface, or may have a resin layer provided on both surfaces of the glass plate.

[0096] [Glass plate] The resin layer-attached glass plate of the present invention has a glass plate. Examples of the glass plate and preferred embodiments of the resin layer-coated glass plate of the invention are the same as those described in the method for producing a resin layer-coated glass plate of the invention, and therefore further description will be omitted. For example, the glass plate included in the resin layer-coated glass plate of the present invention may be tempered glass (for example, chemically tempered glass or physically tempered glass).

[0097] When the glass plate of the resin layer-attached glass plate is tempered glass (for example, chemically tempered glass or physically tempered glass), it is preferable that at least one of the following requirements 1 and 2 be satisfied. Requirement 1: The depth of the compressive stress layer on one surface of the glass plate is smaller than the depth of the compressive stress layer on the other surface of the glass plate. Requirement 2: The compressive stress on the one surface of the glass plate is smaller than the compressive stress on the other surface of the glass plate. An example of a method for obtaining a glass plate that satisfies at least one of the requirements 1 and 2 is a method in which, when obtaining the tempered glass, the tempering conditions are adjusted for the one surface side and the other surface side. Another example is a method in which, after obtaining the tempered glass, a chemical-resistant film is attached to the other surface of the tempered glass, and a layer of a predetermined thickness is removed from the one surface side by etching or the like. When at least one of the requirements 1 and 2 is satisfied, the surface strength of the other surface side in the requirements 1 and 2 is likely to be improved. When the surface strength of the other surface side is high, cracks are less likely to occur, and therefore, for example, it is preferable to use the other surface side by arranging it on the photovoltaic substrate side of a photovoltaic module described later.

[0098] [Etching test] In the resin layer-attached glass plate of the present invention, the increase in the number density of recesses on at least one surface before and after the etching test is 10 / cm 2 The following is the result. The etching test involves immersing a glass plate in an etching solution containing 5% by mass of hydrogen fluoride, 15% by mass of hydrogen chloride, and 80% by mass of water at a temperature of 25°C for 10 minutes.

[0099] More specifically, the etching test is carried out in the following manner. First, the resin layer of the resin layer-attached glass plate is peeled off. When peeling off the resin layer, the resin layer is peeled off so as not to touch the number density measurement region, which will be described later, on the surface on which the resin layer is formed. When the resin layer-attached glass plate has resin layers formed on both sides of the glass plate, the resin layers on both sides are peeled off. After the resin layer is peeled off, the glass plate is immersed in the etching solution under the conditions described above.

[0100] The number density of recesses on one surface of the glass plate is measured before and after the etching test. The measurement of the number density of recesses is carried out at least on the surface of the resin layer-coated glass plate from which the resin layer has been peeled off. The number density of recesses on one surface of the glass plate is measured using an optical microscope, such as a laser microscope equipped with a white light interferometer (VK-X3000) manufactured by Keyence Corporation. Specifically, a 1.5 mm square area is observed, and recesses with a diameter of 1 to 100 μm and a depth of 0.01 to 10 μm are counted as recesses. When observing the 1.5 mm square area, the 1.5 mm square area may be divided and observed. For example, a 250 μm square area may be observed while changing the position, and 1.5 mm square areas may be observed. The number of recesses thus obtained is then divided by the measured area to obtain the number density of recesses on one side of the glass plate. The above observations are carried out over a total measurement area of ​​1 cm 2 Repeat this process while changing your field of view until you achieve this. When the increase in the number density of the recesses was observed using the optical microscope, the increase in the number density of the recesses was 10 / cm 2 Preferably less than 5 pieces / cm 2 The increase in the number density of the recesses is preferably 0 pieces / cm or less. 2 may be. However, the above recesses do not include recesses with an aspect ratio of 10 or more. The aspect ratio refers to the ratio of the maximum diameter to the minimum diameter. Furthermore, the above recesses do not include visible shapes of the patterned glass. The surface of the recess is often configured with a smooth curve, and the outline of the recess is often substantially circular or elliptical in plan view, or a shape formed by connecting these. The shape of the recess will be described in detail in the examples section below.

[0101] Furthermore, when recesses having a diameter of 5 to 100 μm and a depth of 0.01 to 10 μm are counted as the recesses and the increase in the number density of the recesses is observed, the increase in the number density of the recesses is preferably in the same range as when recesses having a diameter of 1 to 100 μm and a depth of 0.01 to 10 μm are counted as the recesses. Furthermore, when recesses having a diameter of 10 to 100 μm and a depth of 0.01 to 10 μm are counted as the recesses and the increase in the number density of the recesses is observed, the increase in the number density of the recesses is preferably in the same range as when recesses having a diameter of 1 to 100 μm and a depth of 0.01 to 10 μm are counted as the recesses. When recesses having a diameter of 15 to 100 μm and a depth of 0.01 to 10 μm are counted as the recesses and the increase in the number density of the recesses is observed, the increase in the number density of the recesses is preferably in the same range as when recesses having a diameter of 1 to 100 μm and a depth of 0.01 to 10 μm are counted as the recesses.

[0102] In the resin layer-attached glass plate of the present invention, the increase in the number density of recesses on at least one surface before and after the etching test is 10 / cm 2 In the resin layer-provided glass plate of the present invention, the increase in the number density of recesses on one surface and the increase in the number density of recesses on the other surface before and after the etching test were both 10 / cm 2 It may be the following: The increase in number density is 5 particles / cm 2 Less than 1 piece / cm is preferable. 2 The increase in the number density is preferably 0 particles / cm or less. 2 may be.

[0103] The number density of recesses can also be measured by the following method. First, light from a white LED is irradiated from the edge of the glass plate (the surface perpendicular to the one surface). That is, the white LED light is irradiated using an edge light method. The irradiation of the white LED light is adjusted to 150,000 to 190,000 lx at the center of the one surface of the glass plate. With the white LED light irradiating the glass plate under the above conditions, an image is taken with a digital camera from one side of the glass plate. The magnification of the digital camera used for imaging is such that one pixel corresponds to a 10 μm square. Next, the captured image is processed by setting the brightness of the pixel with the highest brightness to 255 and the brightness of the pixel with the lowest brightness to 0, resulting in a processed image. Next, an area is selected in the processed image so that the inspection range is 27 mm square. Within the selected area, areas where pixels with a brightness of 40 or higher are grouped together in groups of 3 or more pixels vertically and 3 or more pixels horizontally are counted as recesses. The recesses are counted within the selected area, and the number of recesses counted is divided by the area of ​​the selected area to obtain the number density of recesses on one surface of the glass plate.

[0104] The processed image obtained by the above procedure is subjected to binarization processing in which a brightness threshold is set to 127, pixels below this threshold are set to 0 (black), and pixels above this threshold are set to 1 (white), thereby obtaining a binarized image. The ratio of the number of white pixels to the number of black pixels (hereinafter also referred to as the "white pixel ratio") may be calculated for the obtained binarized image. The white pixel ratio is preferably 0.20% or less, more preferably 0.10% or less, and even more preferably 0.05% or less, and may be 0.00%.

[0105] The resin layer-coated glass plate of the present invention may have another glass plate. The other glass plate is, for example, disposed on the resin layer side of the resin layer-coated glass plate of the present invention.

[0106] <Applications of glass sheets with resin layer> The glass plate with a resin layer obtained by the method for producing a glass plate with a resin layer of the present invention and the glass plate with a resin layer of the present invention can be applied to various applications. In particular, the glass plate with a resin layer of the present invention is useful as various cover glasses because it has excellent resistance to falling objects. The glass plate with a resin layer of the present invention is particularly preferably used as a component of a photovoltaic module. The glass plate with a resin layer of the present invention has excellent resistance to falling objects, and therefore is preferable because the photovoltaic module is less likely to be damaged even when hit by falling objects such as hail. The photovoltaic module is not particularly limited as long as it contains the glass plate with a resin layer of the present invention, and any known configuration can be adopted. For example, the photovoltaic module can be configured to have, in this order, a light-receiving faceplate that is the glass plate with a resin layer of the present invention and a photovoltaic substrate. Any known configuration can be adopted as the configuration of the photovoltaic module other than the above. When the resin layer-coated glass plate of the present invention is used in a photovoltaic module, the resin layer side of the resin layer-coated glass plate (the increase in the number density of recesses is 10 / cm 2 It is preferable that the surface side (hereinafter referred to as the "surface side") is disposed on the photovoltaic substrate side of the photovoltaic module. In the photovoltaic module, an antireflection film may be formed on the side of the resin layer-provided glass plate of the present invention opposite to the photovoltaic substrate side. Furthermore, in the photovoltaic module, an antiglare film may be formed on the side of the resin layer-provided glass plate of the present invention opposite to the photovoltaic substrate side. In addition, the photovoltaic module may further have another glass plate (rear-side glass plate) on the side of the photovoltaic substrate opposite to the resin layer-coated glass plate side. The rear-side glass plate may be the resin layer-coated glass plate of the present invention, the glass plate of the present invention described below, or a conventionally known glass plate. Furthermore, the rear-side glass plate may be a glass plate obtained by removing the resin layer from the resin layer-coated glass plate. As will be described later, the photovoltaic module may be obtained by using a glass plate obtained by peeling off the resin layer from a glass plate with a resin layer.

[0107] Furthermore, the resin layer-coated glass plate of the present invention may be used for other purposes, such as window glass, greenhouse glass, and laminated glass.

[0108] <Glass plate> The glass plate of the present invention has recesses having a diameter of 1 to 100 μm and a depth of 0.01 to 10 μm formed on at least one surface of the glass plate at a density of 0.1 / cm. 2 In the glass plate of the present invention, the number of recesses is 1 / cm 2It is preferable that the number of particles is 50 or more per cm. 2 More preferably, it has 100 particles / cm or more. 2 It is more preferable that the number is 200 or more per cm. 2 In the glass plate of the present invention, the upper limit of the number of recesses is not particularly limited, but it is particularly preferred that the number of recesses is 1000 / cm. 2 The following cases are common: The number density of the recesses can be measured by the same method as the method for measuring the number density of the recesses of the resin layer-coated glass plate of the present invention using an optical microscope (a laser microscope equipped with a white light interferometer). That is, the definition of the recesses is also the same as that of the resin layer-coated glass plate of the present invention. The number density of recesses having a diameter of 5 to 100 μm and a depth of 0.01 to 10 μm is preferably in the same range as recesses having a diameter of 1 to 100 μm and a depth of 0.01 to 10 μm. The number density of recesses having a diameter of 10 to 100 μm and a depth of 0.01 to 10 μm is preferably in the same range as recesses having a diameter of 1 to 100 μm and a depth of 0.01 to 10 μm. The number density of recesses having a diameter of 15 to 100 μm and a depth of 0.01 to 10 μm is preferably in the same range as recesses having a diameter of 1 to 100 μm and a depth of 0.01 to 10 μm.

[0109] In addition, the glass plate of the present invention has a glass plate having a glass surface in which the increase in the number density of recesses on at least one surface before and after the etching test is 10 / cm. 2 It is also preferable that: The etching test involves immersing a glass plate in an etching solution containing 5% by mass of hydrogen fluoride, 15% by mass of hydrogen chloride, and 80% by mass of water at a temperature of 25°C for 10 minutes. The glass plate of the present invention is similar to the glass plate with a resin layer of the present invention (see FIG. 1) except that it does not have a resin layer, and therefore further explanation will be omitted. For example, the glass plate of the present invention may be chemically strengthened glass or physically strengthened glass, and it is also preferable that it satisfies at least one of the above-mentioned requirements 1 and 2. The glass plate of the present invention can be obtained, for example, by removing the resin layer from the resin layer-attached glass plate of the present invention. The removal of the resin layer is preferably carried out without substantially increasing scratches on the surface on which the resin layer is disposed. The glass plate of the present invention may also be obtained by subjecting the glass plate to an etching treatment. The etching method is the same as that of the glass plate with a resin layer of the present invention, and therefore will not be described further. The etching treatment forms the above-described recesses on at least one surface of the glass plate. That is, when a glass plate having the above-described recesses on at least one surface is obtained by performing the etching treatment, the glass plate is considered to be the glass plate of the present invention, even if further steps such as forming and removing a resin layer are not performed. The glass plate of the present invention has excellent resistance to falling objects, similar to the resin layer-provided glass plate of the present invention.

[0110] <Applications of glass plates> The glass plate of the present invention can be applied to various applications. In particular, the glass plate of the present invention is useful as various cover glasses because it has excellent resistance to falling objects. The glass plate of the present invention is particularly preferably used as a component of a photovoltaic module. The glass plate of the present invention has excellent resistance to falling objects, and is therefore preferable because the photovoltaic module is less likely to be damaged even when struck by falling objects such as hail. The photovoltaic module is not particularly limited except that it contains the glass plate of the present invention, and any known configuration can be used. For example, the photovoltaic module can be configured to have a light-receiving faceplate made of the glass of the present invention and a photovoltaic substrate in this order. Any other known configuration can be used for the photovoltaic module. When the glass plate of the present invention is used in a photovoltaic module, the increase in the number density of the recesses on the glass plate before and after the etching test is 10 / cm 2 It is preferable that the surface side having the following property is disposed on the photovoltaic substrate side of the photovoltaic module. In the photovoltaic module, an antireflection film may be formed on the side of the glass plate of the present invention opposite to the photovoltaic substrate side. Furthermore, in the photovoltaic module, an antiglare film may be formed on the side of the glass plate of the present invention opposite to the photovoltaic substrate side.

[0111] The glass plate of the present invention may also be used for other purposes, such as window glass, greenhouse glass, and laminated glass.

[0112] <Solar power generation module> One embodiment of the photovoltaic module of the present invention is a photovoltaic module having a glass plate and a photovoltaic substrate, wherein the glass plate is physically tempered glass, and recesses each having a diameter of 1 to 100 μm and a depth of 0.01 to 10 μm are formed at a rate of 0.1 / cm on the surface of the glass plate facing the photovoltaic substrate. 2 We have the above. The number density of recesses on the surface of the glass plate facing the photovoltaic substrate is measured by the same method as the method for measuring the number density of recesses using an optical microscope (laser microscope equipped with a white light interferometer) on the resin layer-coated glass plate of the present invention. The preferred embodiments of the glass plate in the photovoltaic module are the same as the preferred embodiments of the glass plate of the present invention described above. The aspects of the solar photovoltaic module of the present invention and the aspects of other components of the solar photovoltaic module of the present invention are the same as those of the solar photovoltaic module described in the section on uses of the glass plate with a resin layer, and therefore, description thereof will be omitted. For example, the photovoltaic module may further include another glass plate (rear-side glass plate) on the side opposite to the glass plate side of the photovoltaic substrate. The rear-side glass plate may be a conventionally known glass plate, or may be the same glass plate as the glass plate of one embodiment of the photovoltaic module of the present invention having the predetermined recess. Furthermore, the rear-side glass plate may be the resin-layer-attached glass plate of the present invention described above, or may be the glass plate of the present invention described above.

[0113] FIG. 2 is a cross-sectional view showing an example of a photovoltaic power generation module of the present invention. The photovoltaic module 50 shown in Fig. 2 has a light-receiving surface glass plate 12 and a photovoltaic substrate 40. The photovoltaic substrate 40 has a light-receiving surface 40a and a back surface 40b (the surface opposite the light-receiving surface 40a). In Fig. 2, the light-receiving surface glass plate 12 is disposed on the light-receiving surface 40a side of the photovoltaic substrate 40. The light-receiving side glass plate 12 has the recesses of the above-described type formed at a density of 0.1 / cm on the surface facing the photovoltaic power generation substrate 40. 2 We have the above.

[0114] FIG. 3 is a cross-sectional view showing another example of the photovoltaic power generation module of the present invention. 3 has, in this order, a light-receiving surface glass plate 12, a photovoltaic substrate 40, and a back surface glass plate 14. As described above, the photovoltaic substrate 40 has a light-receiving surface 40a and a back surface 40b, and the light-receiving surface glass plate 12 is disposed on the light-receiving surface 40a side of the photovoltaic substrate 40. The back surface glass plate 12 is disposed on the back surface 40b side of the photovoltaic substrate 40. Similarly to the above, the light-receiving side glass plate 12 has the recesses of the above-described type formed at a density of 0.1 / cm on the surface facing the photovoltaic power generation substrate 40. 2 We have the above. The rear glass plate 14 may have holes as described below.

[0115] In addition, in the embodiment shown in FIG. 3, the photovoltaic substrate 40 and the light-receiving side glass plate 12 are arranged adjacent to each other, but other configurations may be present between the photovoltaic substrate 40 and the light-receiving side glass plate 12. The other configuration is not particularly limited, but may be the above-mentioned resin layer (more preferably a pressure-sensitive adhesive layer or an adhesive layer). Fig. 4 shows a cross-sectional view of a modified example of another example of the photovoltaic power generation module. 4 has, in this order, a light-receiving surface glass plate 12, a resin layer 16, a photovoltaic substrate 40, another resin layer 16, and a back surface glass plate 14. As described above, the photovoltaic substrate 40 has a light-receiving surface 40a and a back surface 40b, and the light-receiving surface glass plate 12 is disposed on the light-receiving surface 40a side of the photovoltaic substrate 40. The back surface glass plate 14 is disposed on the back surface 40b side of the photovoltaic substrate 40. In the case of a configuration having the above-mentioned resin layer, the above-mentioned resin-layer-attached glass plate of the present invention may be applied, or a resin layer may be separately formed on the glass plate of the present invention. Examples of the resin layer are as described above, and may be a pressure-sensitive adhesive layer or an adhesive layer. Furthermore, the resin layers 16 shown in Fig. 4 may be the same resin layer or different resin layers. Furthermore, two or more resin layers 16 may be disposed between the photovoltaic substrate 40 and the light-receiving side glass plate 12. Also, two or more resin layers 16 may be disposed between the photovoltaic substrate 40 and the back side glass plate 14.

[0116] Furthermore, for example, the solar photovoltaic module of the present invention is a solar photovoltaic module having a solar photovoltaic substrate having a light-receiving surface and a back surface opposite the light-receiving surface, and a glass plate arranged on the light-receiving surface side of the solar photovoltaic substrate, in which the glass plate satisfies one or more of the following requirements A1, A2, and A3: Requirement A1: The compressive stress layer depth on the photovoltaic substrate side of the glass plate is smaller than the compressive stress layer depth on the opposite side of the glass plate from the photovoltaic substrate side. Requirement A2: The compressive stress on the photovoltaic substrate side of the glass plate is smaller than the compressive stress on the opposite side of the glass plate from the photovoltaic substrate side. Requirement A3: The glass plate is warped convexly on the side opposite to the solar power generation substrate. The requirement A1 is an embodiment in which the glass plate of the present invention that satisfies the requirement 1 described above is arranged such that the side with the smaller compressive stress layer depth faces the photovoltaic substrate. Furthermore, the above-mentioned requirement A2 is an embodiment in which the glass plate of the present invention that satisfies the above-mentioned requirement 2 is arranged such that the side with the smaller compressive stress faces the photovoltaic power generation substrate.

[0117] Furthermore, with regard to the above-mentioned requirement A3, when a glass sheet warps, the stress acting on the surface of the glass sheet differs between the two surfaces, and the compressive stress acting on the convex surface is often greater. For example, a glass sheet of the present invention that satisfies at least one of the above-mentioned requirements 1 and 2 warps convexly on the side on which the compressive stress acting on the surface of the glass sheet is greater. That is, when requirement A3 is satisfied, the compressive stress acting on the surface of the glass sheet is often greater on the side opposite to the photovoltaic substrate side than on the photovoltaic substrate side. A schematic diagram of a case where the above requirement A3 is satisfied is shown in Figure 5. Figure 5 is a cross-sectional schematic diagram of a photovoltaic power generation module where the above requirement A3 is satisfied. Note that the scale in Figure 5 is exaggerated for the sake of explanation. 5 has, in this order, a light-receiving surface glass plate 12a, a photovoltaic substrate 40, and a back surface glass plate 14. The photovoltaic substrate 40 has a light-receiving surface 40a and a back surface 40b, and the light-receiving surface glass plate 12a is disposed on the light-receiving surface 40a side of the photovoltaic substrate 40. The back surface glass plate 14 is disposed on the back surface 40b side of the photovoltaic substrate 40. Here, the light-receiving surface glass plate 12a satisfies the above-mentioned requirement A3. That is, the light-receiving surface glass plate 12a is warped convexly on the side opposite to the photovoltaic substrate 40. In the photovoltaic module 50c shown in Fig. 5, the entire module is warped due to the warpage of the light-receiving surface glass plate 12a. 5, the light-receiving surface glass plate 12a is warped convexly on the side opposite to the photovoltaic power generation substrate 40, so when the light-receiving surface glass plate 12a is placed with the convex side facing the ground (the side in the direction of gravity), the edge of the light-receiving surface glass plate 12a is spaced apart from the placement surface. Having the edge of the light-receiving surface glass plate 12a spaced apart from the placement surface improves workability. In the embodiment shown in FIG. 5, the rear surface side glass plate 14 may further satisfy the above requirement A3.

[0118] Examples of glass plates that satisfy the above-mentioned requirements A1, A2, and A3 include the above-mentioned glass plate of the present invention and the resin layer-coated glass plate of the present invention. In one aspect of the photovoltaic module of the present invention, the glass plate may satisfy two or more of requirements A1, A2 and A3, or may satisfy all three of them.

[0119] In one aspect of the photovoltaic module of the present invention, the glass plate preferably has a stepped portion on the surface opposite to the photovoltaic substrate, where the thickness of the glass plate is thinner at at least a part of the periphery of the glass plate. The stepped portion is preferably thinner than the central portion of the glass plate. The step portion will be described with reference to the drawings. FIG. 6 is a top view of a glass plate 10b used in one embodiment of the photovoltaic module of the present invention, which has a stepped portion at the periphery of the glass plate where the plate thickness of the glass plate is thinner. The glass plate 10b has a main surface S1 inside the peripheral edge of the glass plate 10b, and has a step S2 at the peripheral edge. FIG. 7 is a cross-sectional view of the glass plate 10b shown in FIG. 6 taken along the line AA. In FIG. 7, the thickness of the glass plate 10b at the step portion S2 is thinner than that of the portion forming the main surface S1.

[0120] 6 and 7 show an embodiment in which the step S2 is provided along the entire peripheral edge of the glass plate 10b, but the step S2 may be formed only in a part of the peripheral edge of the glass plate 10b.

[0121] A glass plate having such a step portion can be produced, for example, by the above-mentioned methods for producing a resin layer-coated glass plate of the present invention, such as the first to fourth embodiments. More specifically, in the first to fourth embodiments, a chemical-resistant protective film is attached to one surface of the glass plate, and the etching step is carried out. The protective film used in this step may be made smaller than the outer shape of the glass plate. That is, the glass plate may be subjected to the etching step in a state where the protective film is attached to the main surface of the glass plate, without the protective film being attached to the peripheral edge of the glass plate. When the glass plate is subjected to an etching process in this state, etching proceeds in the area where the protective film is not present (periphery) in the same manner as on the surface where the protective film is not attached, forming a step. After etching, the protective film is peeled off to obtain a glass plate having a step as shown in Figures 6 and 7. A glass plate having a step portion may be obtained by a method other than the above, but when a glass plate having a step portion is obtained by the above method, it is preferable that the surface without the step portion (the lower side of the paper in Figure 7) is placed on the photovoltaic substrate side. A glass plate having a step portion often satisfies one or more of the above requirements A1, A2 and A3.

[0122] When a glass plate having a step portion as shown in Figures 6 and 7 is applied to the photovoltaic module of the present invention as the light-receiving surface glass plate, it is preferable to position the surface having the step portion on the side opposite to the photovoltaic substrate side. Furthermore, when a glass plate having a step portion is used as the back surface glass plate in the photovoltaic module of the present invention, it is preferable to arrange the surface having the step portion on the photovoltaic substrate side.

[0123] A specific embodiment in which a glass plate having a stepped portion is applied to the photovoltaic power generation module of the present invention will be described with reference to the drawings. Fig. 8 is a cross-sectional schematic diagram of an embodiment in which a glass plate having a step portion is used as the light-receiving surface glass plate of a photovoltaic module. In the embodiment shown in Fig. 8, a photovoltaic substrate 40 has a light-receiving surface 40a and a back surface 40b, and the light-receiving surface glass plate 12b is disposed on the light-receiving surface 40a side of the photovoltaic substrate 40. As described above, the light-receiving surface glass plate 12b has a step portion. Fig. 9 is a cross-sectional schematic diagram of a modified example of an embodiment in which a glass plate having a step portion is used as the light-receiving surface-side glass plate of a photovoltaic module. Fig. 9 differs from Fig. 8 in that a back surface-side glass plate 14 is arranged on the back surface 40b side of the photovoltaic substrate 40. Since other points are the same as those in the embodiment shown in Fig. 8, description thereof will be omitted. Note that in Fig. 9, the back surface-side glass plate 14 may be a glass plate having the above-mentioned step portion. When a glass plate having a step portion is used as the back surface-side glass plate 14, it is preferable to arrange the surface having the above-mentioned step portion on the photovoltaic substrate side.

[0124] A specific embodiment in which a glass plate having a stepped portion is applied as the back surface side glass plate to the photovoltaic module of the present invention will be described with reference to the drawings. Fig. 10 is a cross-sectional schematic diagram of an embodiment in which a glass plate having a step portion is used as the back surface glass plate of a photovoltaic module. In the embodiment shown in Fig. 10, a photovoltaic substrate 40 has a light-receiving surface 40a and a back surface 40b, and a back surface glass plate 14a is disposed on the back surface 40b side of the photovoltaic substrate 40. As described above, the back surface glass plate 14a has a step portion, and is disposed so that the surface having the step portion faces the photovoltaic substrate 40. In addition, a light-receiving surface glass plate 12 is disposed on the light-receiving surface 40a side of the photovoltaic substrate 40.

[0125] In the embodiments shown in Figures 8 to 10, the above-mentioned resin layer may be present between the light-receiving side glass plate and the photovoltaic substrate, or between the back side glass plate and the photovoltaic substrate (see Figure 4). A preferred embodiment of the resin layer is the same as that shown in FIG. 4, and therefore a description thereof will be omitted.

[0126] <Solar power generation module manufacturing method> In the method for manufacturing a photovoltaic module of the present invention, etching and cleaning are performed on at least one surface of a glass plate, and a photovoltaic substrate is disposed on the one surface side. According to the method for manufacturing a photovoltaic power generation module of the present invention, the glass plate has excellent resistance to falling objects, and therefore a photovoltaic power generation module that is less likely to be damaged even when struck by falling objects such as hail can be obtained. The aspects of the solar photovoltaic module of the present invention and the aspects of other components of the solar photovoltaic module of the present invention are the same as those of the solar photovoltaic module described in the section on uses of the glass plate with a resin layer, and therefore, description thereof will be omitted. For example, the photovoltaic module may further include another glass plate on the side opposite to the glass plate side of the photovoltaic substrate. The other glass plate may be a conventionally known glass plate, or may be the same glass plate as the glass plate of one embodiment of the photovoltaic module of the present invention having the predetermined recess. Furthermore, the other glass plate may be the resin layer-provided glass plate of the present invention described above, or may be the glass plate of the present invention described above.

[0127] Furthermore, one aspect of the method for manufacturing a photovoltaic module of the present invention may be an aspect that uses a photovoltaic substrate having a light-receiving surface and a back surface opposite to the light-receiving surface. More specifically, the method may be a method for manufacturing a photovoltaic module that obtains a photovoltaic module by arranging a light-receiving surface-side glass plate on the light-receiving surface side of a photovoltaic substrate having a light-receiving surface and a back surface opposite to the light-receiving surface, and arranging a back surface-side glass plate on the back surface side. Here, in one aspect of the manufacturing method of the photovoltaic module of the present invention, etching and cleaning are performed on at least one of the photovoltaic substrate side of the light-receiving surface glass plate and the side of the back surface glass plate opposite to the photovoltaic substrate side. The light-receiving side glass plate and the back side glass plate may be the resin layer-attached glass plate of the present invention described above, or may be the glass plate of the present invention described above.

[0128] Furthermore, in one aspect of the method for manufacturing a photovoltaic module of the present invention, it is also preferable to etch and clean the back surface glass plate having a hole. That is, in one aspect of the method for manufacturing a photovoltaic module of the present invention, the back surface glass may have a hole in a part thereof. It is also preferable that the hole is a hole for drawing wiring of the photovoltaic substrate to the outside of the photovoltaic module. The hole refers to a space that penetrates the glass plate in the plate thickness direction. A specific example of a back surface glass obtained by etching and cleaning a back surface glass having holes will be described with reference to the drawings. Fig. 11 is a top view of a back surface glass having holes. The back surface glass 14b shown in Fig. 11 has circular holes H1, H2, and H3. The back surface glass 14b also has a main surface S1 and a step S2. The back surface glass 14b can be obtained, for example, by forming the circular holes H1, H2, and H3 in a glass plate, attaching a protective film having the above-mentioned chemical resistance and smaller than the outer shape of the glass plate to one surface, and then subjecting the glass to the above-mentioned etching process.

[0129] 11 shows an embodiment in which three holes are formed, the arrangement of the holes on the back surface side glass plate is not particularly limited, and there may be only one hole, or two or more holes. Furthermore, the shape of the holes is not limited to a circle, and may be, for example, a rectangle, an oval, or an ellipse. The size of the hole in the in-plane direction of the rear surface side glass plate is not particularly limited, but for example, when the hole is circular, the diameter of the circle is 5 mm or more, may be 10 mm or more, or may be 20 mm or more. The upper limit of the diameter of the circle is not particularly limited, but is, for example, 100 mm or less. Furthermore, in FIG. 11, an embodiment having the step portion S2 has been described, but the rear surface side glass having the hole does not necessarily have to have the step portion S2. When the rear glass has the above-mentioned holes, it is preferable to perform etching after forming the holes, since this allows etching to reach the side surfaces of the holes.

[0130] Here, it is also preferable to arrange the photovoltaic substrate on one side after etching and cleaning without substantially increasing scratches on the one side. With respect to the glass plate, "without substantially increasing scratches on one surface" has the same meaning as in the resin layer forming step of the method for producing a resin layer-coated glass plate of the present invention. That is, "without substantially increasing scratches on one side" means that there is no increase in visible scratches and when the etching test is carried out, the increase in the number density of recesses on the surface of the one side of the glass plate is 10 / cm. 2 The increase in the number density of the recesses is 5 / cm or less. 2 Less than 1 piece / cm is preferable. 2 It is more preferable that the increase in the number density of the recesses is 0 / cm. 2 It may be more than that.

[0131] The etching and cleaning carried out in the method for producing a photovoltaic power generation module of the present invention can be carried out by the same method as the etching step in the method for producing a resin layer-coated glass plate of the present invention described above.

[0132] The method for producing a photovoltaic module of the present invention may include the method for producing a resin layer-attached glass plate described above. More specifically, the method for producing a photovoltaic module of the present invention may include any of the above-mentioned [Mode 1] to [Mode 5] of the method for producing a glass plate with a resin layer. The method for producing a photovoltaic module of the present invention may further include a step of peeling off the resin layer from the glass plate with a resin layer obtained by the method for producing a glass plate with a resin layer. The step of peeling off the resin layer is preferably carried out before carrying out the assembly step described below.

[0133] In the method for manufacturing the photovoltaic module of the present invention, a glass plate may be subjected to the etching step described in the method for manufacturing a glass plate with a resin layer, and then the glass plate that has been subjected to the etching step may be subjected to the assembly step described below without forming a resin layer.

[0134] The method for manufacturing a photovoltaic module of the present invention may include an assembly step. The assembly step refers to a step of assembling a photovoltaic module, and more specifically includes a step of bonding a glass plate to a photovoltaic substrate. At this time, the glass plate is placed so that the one surface (the surface on which etching and cleaning have been performed) faces the photovoltaic power generation substrate. A more specific example of the assembly process is a method in which an adhesive film is placed on a photovoltaic power generation substrate, a glass plate is attached to the adhesive film, and the resulting assembly is then autoclaved. A more specific example of the assembly process is a method in which an adhesive film is placed on a glass plate, a photovoltaic power generation substrate is attached to the adhesive film, and the resulting mixture is then autoclaved.

[0135] In the assembling step, a glass plate may be bonded to only one side of the photovoltaic substrate, or to both sides of the photovoltaic substrate. That is, the assembling step may be performed by placing a first adhesive film on a first glass plate, placing the photovoltaic substrate on the side of the first adhesive film opposite the first glass plate, placing a second adhesive film on the side of the photovoltaic substrate opposite the first glass plate, and placing a second glass plate on the side of the second adhesive film opposite the photovoltaic substrate. At least one of the first and second glass plates is an etched and cleaned glass plate. When the first and second glass plates are the glass plates of the present invention, it is also preferable that the etched surface of the first glass plate is disposed on the photovoltaic substrate side, and the etched surface of the second glass plate is disposed on the opposite side from the photovoltaic substrate side. The other of the first and second glass plates may be an unetched glass plate. In the above embodiment, after the first glass plate, the first adhesive film, the photovoltaic substrate, the second adhesive film, and the second glass plate are obtained, autoclave treatment may be carried out.

[0136] The adhesive film (including the first adhesive film and the second adhesive film) used in the assembling step can be a known adhesive film, and for example, the adhesive layer or adhesive layer described in the method for producing a glass plate with a resin layer of the present invention can be used. As the adhesive film, for example, an ethylene vinyl acetate resin is preferable.

[0137] The assembly process may further include other steps. For example, after the autoclave treatment, a step of attaching a peripheral frame may be included, and a step of connecting wiring may also be included. Furthermore, the process may include at least one of a quality inspection step and a packaging step. [Example]

[0138] The present invention will be described in more detail below with reference to examples. The materials, amounts used, ratios, treatment details, treatment procedures, etc. shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the following examples. Note that the latter examples 1, 3 to 5, 7, 8, 10, 11, 13 to 16, 18 and 20 are working examples, and examples 2, 6, 9, 12, 17 and 19 are comparative examples.

[0139] <Example 1> [Preparation of glass plate with resin layer] Glass raw materials were prepared so as to have the following composition expressed in mole percentages based on oxides, and the mixture was heated to obtain molten glass. The molten glass was formed into a plate-shaped glass ribbon by the float process, and the glass ribbon was slowly cooled in an annealing furnace to obtain a glass plate having a thickness of 0.7 mm. Glass material A: SiO264.5%, Al2O38.0%, Na2O 12.5%, K2O 4.0%, MgO 10.5%, ZrO20.5%

[0140] The obtained glass plate was immersed in an etching solution having the following composition to carry out an etching treatment. Specifically, the immersion time was adjusted so that the etching depth per side of the glass plate was 75 μm. The etching solution contained 5 mass % hydrogen fluoride, 15 mass % hydrogen chloride, and 80 mass % water.

[0141] After the etching treatment, both surfaces of the glass plate were washed with ion-exchanged water by showering the ion-exchanged water onto the surface of the glass plate. After washing, the glass plate was dried. After the etching, the diameter and depth of the recesses present on the surface of the glass plate were measured using the method described above. Fig. 14 shows a schematic diagram of a microscope image of the recesses after etching. Fig. 14 shows the outlines of the recesses formed after etching. In the schematic diagram of the microscope image shown in Fig. 14, recesses C1, C2, C3, and C4 are shown. The contour of the recess C1 is approximately circular and has a diameter d1, while the contour of the recess C2 is approximately elliptical and has a diameter d2 in the major axis direction (maximum diameter). Furthermore, the recesses C3 and C4 have a structure in which their contours are connected to each other. In FIG. 14, the contours of the recesses C3 and C4 are interpolated and shown by dotted lines. When the contours of the recesses C3 and C4 are interpolated, it can be seen that they are both circular. The diameter of the recess C3 is d3. Similarly, the diameter of the recess C4 is d4. In addition, when the contours of the recesses are interconnected and can be separated from each other by interpolating the contour shapes as described above, the recesses are counted as being separately present. Here, the number of recesses observed in the schematic diagram of the microscope observation image shown in Fig. 14 is 4. That is, the above d1 to d4 are each 1 to 100 µm. Table 1 shows typical shapes of recesses after etching. The shape of the contour line of the recesses after etching was approximately circular or approximately elliptical in plan view. On the other hand, before etching, the number of recesses having a diameter of 1 to 100 μm, a depth of 0.01 to 10 μm, an aspect ratio of 10 or less, and formed by smooth curves was 0.1 / cm. 2 It was less than.

[0142] [Table 1]

[0143] Next, a resin layer was formed on one surface of the washed glass plate. From the washing of the glass plate to the formation of the resin layer, the surface on which the resin layer was to be formed was not allowed to come into contact with anything other than the resin layer. Sanitect (registered trademark) PAC-3-70 (film thickness 70 μm) manufactured by San-A Kaken Co., Ltd. was used as the resin layer, and the resin layer was attached to one surface of the cleaned glass plate. Through the above procedure, a glass plate with a resin layer was obtained.

[0144] [Rubbing test] Without peeling off the resin layer from the obtained glass plate with a resin layer, a rubbing test simulating roller conveyance was carried out on the resin layer side. Specifically, a #180 SiC sandpaper was pressed against the resin layer side with a load of 500 g, and the rubbing test was carried out by stroking five times. The stroke width of the rubbing test was 20 mm, and the speed was 80 times / min. By the above procedure, a glass plate with a resin layer of Example 1 was obtained. The glass plate was then subjected to an etching test under the conditions described above. After the etching test, the number density of recesses on the surface on which the resin layer had been formed was measured by the method described above. In addition, the resin layer of a glass plate with a resin layer obtained by the same procedure was peeled off from the glass plate, and the number density of recesses on the surface on which the resin layer had been formed was measured by the method described above. From the measurement results of the number density of the recesses, the increase in the number density of the recesses on the surface on which the resin layer was formed was calculated by the above-mentioned method before and after the etching test, and was found to be 0 / cm 2 It was. The resin layer-attached glass plate of Example 1, which had few scratches, was less likely to break from scratches and had excellent resistance to falling objects.

[0145] <Example 2> First, molten glass made from glass material B was formed by a roll-out method to obtain a patterned glass plate having a thickness of 3.2 mm. One side of the obtained patterned glass plate was an embossed surface with fine irregularities, and the other side was matte. Next, a slightly adhesive film (the same resin layer as in Example 1 above) was attached to the embossed surface. The patterned glass plate was used as the glass plate of Example 2. The composition of the glass material B (expressed in mole percentage based on oxides) is as follows: Glass material B: SiO271.76%, Al2O30.64%, Na2O 12.31%, K2O 0.06%, MgO 6.13%, CaO 8.89%, SO30.16%, Sb2O30.04% The glass plate thus obtained was cut into pieces measuring 100 mm x 100 mm and placed in a thermal tempering bath for physical tempering. When the embossed surface of the physically tempered glass plate was observed with a laser microscope, scratches were found in the embossed convex portions, but these were 1 to 100 μm in diameter and 0.01 to 10 μm in depth, and did not correspond to smoothly curved concave portions. Specifically, the scratches in the embossed convex portions were greater than 100 μm in diameter. The glass plate of Example 2 obtained by the above procedure was evaluated for strength against a falling object by the following method. The method for evaluating strength against a falling object will be described with reference to the drawings.

[0146] FIG. 12 is a schematic diagram of a ball drop strength tester 60 used to evaluate the strength against a falling object (ball drop strength). 12 is capable of measuring the ball drop strength of a sample 74 by dropping a steel ball 62 from a predetermined height toward the sample 74 and causing it to collide with the sample 74. The sample 74 is made of resin and is placed on a frame-shaped jig 72, and the jig 72 and the sample 74 are placed on a pedestal 70. Furthermore, before the steel ball 62 is dropped, it is held by a stopper 66, and by unlocking the stopper 66, the steel ball 62 is allowed to fall freely. The steel ball 62 is connected to a winding thread 64, which is connected to the main body (not shown) of the ball drop strength tester 60, and by winding the winding thread 64, the steel ball 62 is returned to a predetermined position. The stopper 66 is connected to the main body (not shown) of the ball drop strength tester 60 so that the drop height (vertical direction on the paper surface of FIG. 12) can be changed. The glass plate of Example 2 above was placed in a ball drop strength tester 60 as sample 74, and a steel ball 62 was dropped onto sample 74 while changing the drop height, causing the steel ball 62 to collide with sample 74. The above operation was repeated until a crack appeared in sample 74 (see FIG. 13 ), and the collision energy (unit: J) at the time when the crack appeared was taken as the ball drop strength of sample 74. The above-mentioned drop ball strength measurement was performed on 10 samples, and the maximum, average, minimum, and B10 values ​​of the drop ball strength were determined. The maximum, average, minimum, and B10 values ​​of the drop ball strength of the glass plate of Example 2 are shown in the table below. The B10 value is the drop ball strength at which 10% cracks occur, as determined from the Weibull distribution. The steel ball 62 had a diameter of 60 mm and a mass of 877 g. The glass plate of Example 2 was placed on the jig 72 with the embossed surface facing the ground (the side opposite to the side where the steel ball 62 hits).

[0147] <Example 3> The glass plate of Example 2 was subjected to an etching treatment to form a resin layer similar to that of Example 2, thereby obtaining a glass plate of Example 3. Specifically, the immersion time for the etching treatment was adjusted so that the etching depth was 50 μm per side of the glass plate. The etching solution contained 5% by mass of hydrogen fluoride, 15% by mass of hydrogen chloride, and 80% by mass of water. After the etching process, when the embossed surface was observed, the scratches observed in the embossed convex portions were circular or elliptical concave portions, each with a major axis of 10 to 50 μm and a depth of approximately 0.1 to 0.3 μm. After the etching process, a resin layer similar to that in Example 2 was attached. The glass plate of Example 3 thus obtained was subjected to evaluation of the falling ball strength in the same manner as in Example 2. The results are shown in the table below. Furthermore, when a resin layer is formed on at least one surface of the glass plate of Example 3 by the procedure described above, the glass plate with a resin layer of the present invention can be obtained.

[0148] <Example 4> The glass plate of Example 4 was obtained without attaching a slightly adhesive resin layer to the glass of Example 3. It was confirmed that when the glass plate of Example 4 was handled during transportation or the like, scratches were generated on the convex portions of the embossed surface. The resulting glass plate of Example 4 was evaluated for ball drop strength in the same manner as in Example 2. The results are shown in the table below.

[0149] <Example 5> In the same manner as in Example 2, a patterned glass was obtained in which one side was an embossed surface with fine irregularities and the other side was a matte surface (matte finish). The resulting patterned glass was cut to a size of 1717 mm x 1128 mm and chamfered. An anti-reflection coating layer (AR coating layer) mainly composed of SiO2 was then formed on the matte finish. Thereafter, a protective film for preventing etching was attached to the surface of the glass plate on the AR coating layer side, and the protective film had a shape that was 5 mm smaller than the edge of the patterned glass. The glass plate with the protective film attached was subjected to an etching treatment in the same manner as in Example 3. After etching, the protective film was peeled off, and a resin layer was formed on the embossed surface in the same manner as in Example 2, thereby obtaining a glass plate of Example 5. The glass plate of Example 5 had a step portion on the peripheral edge of the matte surface side. The resulting glass plate of Example 5 was evaluated for ball drop strength in the same manner as in Example 2. The results are shown in the table below.

[0150] <Example 6 to Example 8> First, molten glass made of glass material C was formed by the float method to obtain a float glass having a thickness of 2.0 mm. The obtained float glass had a smooth surface. The composition of the glass material B (expressed in mole percentage based on oxides) is as follows: Glass material C: SiO268.84%, Al2O32.99%, Na2O 14.1%, K2O 0.2%, MgO 6.32%, CaO 7.56% The glass plate thus obtained was cut into a size of 100 mm x 100 mm, and placed in a thermal tempering bath to be physically tempered. The above resin layer was formed on the float glass immediately after physical strengthening to prepare a glass plate of Example 6. When the surface of the glass plate of Example 6 was observed, it was confirmed that linear scratches (scratches that did not correspond to the above-mentioned recesses) had occurred. Furthermore, the float glass immediately after physical strengthening was subjected to an etching treatment to obtain a glass plate of Example 7. Specifically, the immersion time for the etching treatment was adjusted so that the etching depth was 10 μm per side of the glass plate. The etching solution contained 5% by mass of hydrogen fluoride, 15% by mass of hydrogen chloride, and 80% by mass of water. Observation of the surface after etching revealed that the width of the linear scratches had increased compared to before etching, resulting in a smooth cross-sectional shape. Circular or elliptical depressions were also observed. The major axis of the depressions was 5 to 60 μm, and the depth was approximately 0.1 to 10 μm. Next, a resin layer was formed on the obtained glass plate of Example 7 in the same manner as in Example 3 to obtain a glass plate of Example 8. It was confirmed that when the obtained glass plate of Example 7 was handled during transportation or the like, the above-mentioned linear scratches were generated. The resulting glass plates of Examples 6 to 8 were evaluated for their falling ball strength in the same manner as in Example 2. The results are shown in the table below.

[0151] For convenience, the glass plates of Examples 2 to 8 will be referred to as glass plate B2 to glass plate B8, respectively.

[0152] <Example 9 to Example 20> Photovoltaic power generation modules were fabricated using the glass plates and other members described above, and their strength against falling objects was evaluated. Below, a representative method for fabricating the photovoltaic power generation module in Example 9 and a method for evaluating the strength against falling objects will be described, and only the differences from Example 9 will be explained for other examples.

[0153] The photovoltaic module of Example 9 had, in this order, a light-receiving surface-side glass, a photovoltaic substrate, and a rear surface-side member. The photovoltaic module of Example 9 was obtained by the following procedure. First, the glass plate B2 was placed on a workbench with the matte side facing down, and the resin layer on the embossed side was removed. Next, an adhesive layer made of ethylene vinyl acetate resin was formed on the embossed side of the glass plate B2. A crystalline silicon photovoltaic substrate was placed on the adhesive layer, and an adhesive layer was further formed on the side of the photovoltaic substrate opposite the glass plate B2 side. Furthermore, a film based on polyethylene terephthalate (PET) resin (backsheet manufactured by Keiwa Co., Ltd., Appli-Sola (registered trademark)) was placed on the side of the adhesive layer opposite the photovoltaic substrate side, followed by autoclaving and attaching a frame to obtain the photovoltaic module of Example 9. The obtained photovoltaic module of Example 9 had, in this order, a glass plate B2, an adhesive layer, a photovoltaic substrate, an adhesive layer, and a PET film. The surface of glass plate B2 opposite to the photovoltaic substrate side was matte.

[0154] An ice ball with a diameter of 65 mm was collided with the glass plate B2 side of the obtained solar power generation module of Example 9 at a speed of 36.7 m / s (89 J) to check whether the glass plate cracked. The results are shown in the table below.

[0155] The photovoltaic module of Example 10 was obtained in the same manner as in Example 9, except that glass plate B3 was used as the light-receiving side glass, and was evaluated in the same manner.

[0156] The photovoltaic power generation module of Example 11 was obtained in the same manner as in Example 10, except that glass plate B9 was used as the rear surface side member, and was evaluated in the same manner. The glass plate B9 was a patterned glass obtained in the same manner as the glass plate B2, except that the thickness was adjusted to 2.0 mm. The photovoltaic module of Example 11 was obtained by placing the matte side of the glass plate B9 opposite the photovoltaic substrate side.

[0157] The photovoltaic module of Example 12 was obtained in the same manner as in Example 11, except that the glass plate B9 was used as the light-receiving side glass. The surface of the glass plate B9 opposite to the photovoltaic substrate side was matte finished. An ice ball with a diameter of 55 mm was collided with the glass plate B9 on the light-receiving side of the obtained photovoltaic module of Example 11 at a speed of 33.9 m / s (46 J) to check whether the glass plate cracked. The results are shown in the table below.

[0158] The photovoltaic module of Example 13 was obtained in the same manner as in Example 12, except that glass plate B10 was used as the light-receiving side glass, and was evaluated in the same manner as in Example 12. The glass plate B10 was obtained by subjecting the glass plate B9 to an etching treatment under the same conditions as those for the glass plate B3.

[0159] The solar power generation module of Example 14 was obtained in the same manner as in Example 13, except that the back side glass plate was glass plate B9H, which had three holes with a diameter of 15 mm in the center of the glass plate B9, and was evaluated in the same manner as in Example 13.

[0160] The solar power generation module of Example 15 was obtained in the same manner as in Example 14, except that glass plate B10H, which was obtained by etching glass plate B9H under the same conditions as glass plate B10, was used as the back side glass plate, and was evaluated in the same manner as in Example 14. When obtaining the glass plate B10H, the cross-sectional portions of the holes were also etched. The glass plate B10H was placed so that the matte finish side was opposite the photovoltaic power generation substrate side.

[0161] The photovoltaic power generation module of Example 16 was obtained in the same manner as in Example 15, except that glass plate B11H was used as the back surface glass plate, and evaluations were carried out in the same manner as in Example 15. The glass plate B11H was obtained by attaching a protective film to the embossed surface of the glass plate B9H in the same manner as the glass plate B5, and then etching the glass plate B11H under the same conditions as the glass plate B10H. That is, the glass plate B11H had holes and a step on the embossed surface. When obtaining the glass plate B11H, the cross-sections of the holes were also etched. The glass plate B11H was positioned so that the matte surface was opposite the photovoltaic substrate.

[0162] The photovoltaic module of Example 17 was obtained in the same manner as in Example 9, except that the glass plate B6 was used as the light-receiving side glass, and was evaluated in the same manner as in Example 9.

[0163] The photovoltaic module of Example 18 was obtained in the same manner as in Example 9, except that the glass plate B8 was used as the light-receiving side glass, and was evaluated in the same manner as in Example 9.

[0164] The photovoltaic module of Example 19 was obtained in the same manner as in Example 13, except that glass plate B12 was used as the light-receiving side glass plate and glass plate B13 was used as the back side glass plate, and was evaluated in the same manner as in Example 13. The glass plate B12 was obtained by adjusting the thickness to 2.0 mm in the same manner as in obtaining the glass plate B6. The glass plate B13 was obtained by etching the glass plate B12 under the same conditions as those for the glass plate B8, to form a resin layer.

[0165] The photovoltaic module of Example 20 was obtained in the same manner as in Example 19, except that the glass plate B13 was used as the light-receiving side glass plate and the glass plate B13H was used as the back side glass plate, and was evaluated in the same manner as in Example 19. The glass plate B13H was prepared by using the glass plate B12 having holes in the procedure for obtaining the glass plate B 13. When obtaining the glass plate B13H, the cross-sectional portions of the holes were also etched.

[0166] The glass used in Example 16 satisfied the above requirements A1 to A3.

[0167] <Result> Table 2 shows the conditions for obtaining each of the glass plates, the number density of the recesses measured by the above-mentioned method, and the falling ball strength. The configuration of each of the above solar power generation modules and the evaluation results of the ball drop strength are listed in Table 3. For the light-receiving side glass and back side glass, if they did not break, they are listed as "A", and if they did break, they are listed as "B".

[0168] [Table 2]

[0169] [Table 3]

[0170] From the results shown in Table 2, it was found that recesses having a diameter of 1 to 100 μm and a depth of 0.01 to 10 μm were formed at a rate of 0.1 / cm on at least one surface of the glass plate. 2 It was confirmed that the glass plate having the above properties has high strength against falling objects. From the results shown in Table 3, it is also found that the number of recesses having a diameter of 1 to 100 μm and a depth of 0.01 to 10 μm is 0.1 / cm 2 It was confirmed that when the glass plate having the above properties is applied to a solar power generation module, the module has increased strength against falling objects. Furthermore, in the above Example 20, a photovoltaic power generation module was obtained using the resin layer as an adhesive layer without peeling it off, and when the same evaluation as in Example 20 was carried out, the same results as in Example 20 were obtained. [Explanation of symbols]

[0171] 10 Glass Plate 12, 12a, 12b Light receiving surface side glass plate 14, 14a, 14b Rear glass plate 16,20 Resin layer 30 Glass plate with resin layer 40 Photovoltaic Power Generation Board 40a Photosensitive surface 40b back 50, 50a, 50b, 50c, 50d, 50e, 50f solar power generation modules 60 Drop ball strength tester 62 steel ball 64 Winding thread 66 Stopper 70 pedestal 72 Jig 74 samples

Claims

1. A method for producing a glass plate with a resin layer, comprising: etching and cleaning at least one surface of a glass plate; and then forming a resin layer on the one surface without substantially increasing scratches on the one surface.

2. The method for producing a resin layer-attached glass plate according to claim 1 , wherein the resin layer is formed on the one surface without touching anything other than the resin layer.

3. The method for producing a resin layer-attached glass plate according to claim 1 or 2, wherein the glass plate is a chemically tempered glass or a physically tempered glass.

4. The method for producing a resin layer-attached glass plate according to claim 1 or 2, wherein etching is carried out on only one surface of the glass plate.

5. A resin layer-attached glass plate having a glass plate and a resin layer, The increase in the number density of recesses on at least one surface of the glass plate before and after the etching test is 10 / cm ２ The following is a glass plate with a resin layer. The etching test involves immersing a glass plate in an etching solution containing 5 mass % hydrogen fluoride, 15 mass % hydrogen chloride, and 80 mass % water at a temperature of 25° C. for 10 minutes.

6. The resin layer-provided glass plate according to claim 5 , wherein the glass plate is a chemically strengthened glass or a physically strengthened glass.

7. The resin layer-provided glass plate according to claim 6 , which satisfies at least one of the following requirements 1 and 2: Requirement 1: The depth of the compressive stress layer on one surface side of the glass plate is smaller than the depth of the compressive stress layer on the other surface side of the glass plate. Requirement 2: The compressive stress on the one surface side of the glass plate is smaller than the compressive stress on the other surface side of the glass plate.

8. A glass plate, at least one surface of which is provided with recesses each having a diameter of 1 to 100 μm and a depth of 0.01 to 10 μm at a rate of 0.1 / cm ２ A glass plate having the above.

9. The glass plate is subjected to an etching test, and the increase in the number density of recesses on at least one surface of the glass plate is 10 / cm ２ 9. The glass sheet according to claim 8, wherein: The etching test involves immersing a glass plate in an etching solution containing 5 mass % hydrogen fluoride, 15 mass % hydrogen chloride, and 80 mass % water at a temperature of 25° C. for 10 minutes.

10. The glass plate according to claim 8, which is chemically strengthened glass or physically strengthened glass.

11. The glass plate according to claim 10, which satisfies at least one of the following requirements 1 and 2: Requirement 1: The depth of the compressive stress layer on one surface side of the glass plate is smaller than the depth of the compressive stress layer on the other surface side of the glass plate. Requirement 2: The compressive stress on the one surface side of the glass plate is smaller than the compressive stress on the other surface side of the glass plate.

12. In mole percent based on oxides, SiO ２ 52 to 75% Al ２ O ３ を0~20%、 Na ２ The glass plate according to claim 8, containing 1 to 20% O.

13. A photovoltaic module comprising the glass plate according to any one of claims 8 to 12 and a photovoltaic substrate, The increase in the number density of recesses before and after the etching test on the glass plate was 10 / cm ２ A photovoltaic module, wherein a surface that is:

14. A photovoltaic module having a glass plate and a photovoltaic substrate, wherein the glass plate is physically strengthened glass, and recesses each having a diameter of 1 to 100 μm and a depth of 0.01 to 10 μm are formed at 0.1 count / cm on a surface of the glass plate facing the photovoltaic substrate. ２ A solar power generation module having the above.

15. A photovoltaic module including a photovoltaic substrate having a light-receiving surface and a back surface opposite to the light-receiving surface, and a light-receiving surface-side glass plate disposed on the light-receiving surface side of the photovoltaic substrate, A photovoltaic power generation module, wherein the light-receiving surface side glass plate satisfies one or more of the following requirements A1, A2, and A3: Requirement A1: The compressive stress layer depth on the photovoltaic substrate side of the light-receiving surface glass plate is smaller than the compressive stress layer depth on the side of the light-receiving surface glass plate opposite to the photovoltaic substrate side. Requirement A2: The compressive stress on the photovoltaic substrate side of the light-receiving surface glass plate is smaller than the compressive stress on the side of the light-receiving surface glass plate opposite to the photovoltaic substrate side. Requirement A3: The light-receiving surface side glass plate is warped convexly on the side opposite to the photovoltaic power generation substrate side.

16. 16. The photovoltaic module according to claim 15, wherein the light-receiving surface glass plate has a stepped portion where the thickness of the light-receiving surface glass plate is thinner in at least a part of a peripheral edge of the light-receiving surface glass plate on a surface of the light-receiving surface glass plate opposite to the photovoltaic substrate side.

17. A method for manufacturing a photovoltaic module, comprising: etching and cleaning at least one surface of a glass plate; and arranging a photovoltaic substrate on the one surface.

18. A method for manufacturing a photovoltaic module, comprising: arranging a light-receiving surface-side glass plate on a light-receiving surface side of a photovoltaic substrate having a light-receiving surface and a back surface opposite to the light-receiving surface; and arranging a back surface-side glass plate on the back surface side to obtain a photovoltaic module, a photovoltaic module manufacturing method, comprising etching and cleaning at least one of the photovoltaic substrate side of the light-receiving side glass plate and the side of the back side glass plate opposite to the photovoltaic substrate side;

19. The method for manufacturing a photovoltaic module according to claim 18 , further comprising the step of etching and cleaning the rear surface glass plate having the hole.

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