Method for manufacturing a glass plate with a resin layer, glass plate with a resin layer, glass plate, solar power generation module, and method for manufacturing a solar power generation module

Abstract

An object of the present invention is to provide a method for manufacturing a glass plate with a resin layer, which can obtain a glass with a resin layer having excellent resistance to falling objects. The method for manufacturing a glass plate with a resin layer according to the present invention performs etching and cleaning on at least one surface of the glass plate, and then forms a resin layer on the above-mentioned one surface without substantially increasing the scratches on the above-mentioned one surface.

Description

Technical Field

[0001] The present invention relates to a method for manufacturing 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 Art

[0002] In recent years, cover glass has been used for the purpose of protecting and enhancing the aesthetics of display devices such as mobile phones, smartphones, and tablet terminals. Cover glass for these applications is required to have excellent strength in order to suppress breakage due to impacts and the like. In addition, the cover glass as described above may be used for protecting a photovoltaic module, various sensors, and the like.

[0003] On the other hand, as one of the techniques for thinning a glass plate, a method by etching is known. 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

Summary of the Invention

Problems to be Solved by the Invention

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

[0006] The present invention has been made in view of the above problems, and an object thereof is to provide a method for manufacturing a glass plate with a resin layer, which can obtain a glass with a resin layer having 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 solar power generation module and a method for manufacturing the same.

Means for Solving the Problems

[0007] As a result of intensive studies on the above problems, the present inventors have found that when a resin layer is formed on the surface of a glass plate after etching without substantially increasing the scratches on one surface, a glass plate with a resin layer having excellent resistance to falling objects can be obtained, and thus the present invention has been achieved. That is, the inventors have found that the above problems can be solved by the following configuration.

[0008] 〔1〕 A method for manufacturing a glass plate with a resin layer, wherein etching and cleaning are performed on at least one surface of a glass plate, and then a resin layer is formed on the above one surface without substantially increasing the scratches on the above one surface. 〔2〕 The method for manufacturing a glass plate with a resin layer according to 〔1〕, wherein the resin layer is formed on the above one surface without touching the resin layer other than the above resin layer. 〔3〕 The method for manufacturing a glass plate with a resin layer according to 〔1〕 or 〔2〕, wherein the glass plate is chemically strengthened glass or physically strengthened glass. 〔4〕 The method for manufacturing a glass plate with a resin layer according to 〔1〕 or 〔2〕, wherein etching is performed only on one surface of the glass plate. 〔5〕 A glass plate with a resin layer having a glass plate and a resin layer, Before and after performing an etching test on the above glass plate, the increase amount of the number density of the recesses on at least one surface of the above glass plate is 10 pieces / cm 2 The following is a glass plate with a resin layer. However, the above etching test is a test in which a glass plate is immersed for 10 minutes in an etching solution containing 5% by mass of hydrogen fluoride, 15% by mass of hydrogen chloride, and 80% by mass of water, with the temperature of the etching solution being 25°C. 〔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 requirement 1 and requirement 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 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 having, on at least one surface of the glass plate, recesses with a diameter of 1 to 100 μm and a depth of 0.01 to 10 μm, with 0.1 or more per cm 2 or more. 〔9〕 The glass plate according to 〔8〕, wherein the increase amount of the number density of the recesses on at least one surface before and after performing the etching test on the glass plate is 10 per cm 2 or less. However, the above etching test is a test in which a glass plate is immersed for 10 minutes in an etching solution containing 5% by mass of hydrogen fluoride, 15% by mass of hydrogen chloride, and 80% by mass of water, with the temperature of the etching solution being 25°C. 〔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 requirement 1 and requirement 2. 〔12〕 The glass plate according to any one of 〔8〕 to 〔11〕, which contains 52 to 75% of SiO2, 0 to 20% of Al2O3, and 1 to 20% of Na2O in terms of mol% based on oxides. 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 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 having the glass plate according to any one of 〔8〕 to 〔12〕 and a photovoltaic substrate, Before and after performing the etching test on the glass plate, the increase amount of the number density of the recesses is 10 pieces / cm 2 A photovoltaic module in which the surface that is the following is disposed on the photovoltaic substrate side. 〔14〕 A photovoltaic module having a glass plate and a photovoltaic substrate, wherein the glass plate is physically strengthened glass, and on the surface of the glass plate on the photovoltaic substrate side, there are recesses having a diameter of 1 to 100 μm and a depth of 0.01 to 10 μm, and the number of the recesses is 0.1 piece / cm 2 or more. 〔15〕 A photovoltaic module having a light receiving surface, a back surface opposite to the light receiving surface, and a photovoltaic substrate, and a light receiving surface side glass plate disposed on the light receiving surface side of the photovoltaic substrate, wherein the light receiving surface side glass plate satisfies any one or more of the following requirement A1, requirement A2, and requirement A3. Requirement A1: The depth of the compressive stress layer on the photovoltaic substrate side of the light receiving surface side glass plate is smaller than the depth of the compressive stress layer on the side opposite to the photovoltaic substrate side of the light receiving surface side glass plate. Requirement A2: The compressive stress on the photovoltaic substrate side of the light receiving surface side glass plate is smaller than the compressive stress on the side opposite to the photovoltaic substrate side of the light receiving surface side glass plate. Requirement A3: The light receiving surface side glass plate is convexly warped on the side opposite to the photovoltaic substrate side. 〔16〕 The photovoltaic module according to 〔15〕, having a stepped portion in which the plate thickness of the light receiving surface side glass plate is reduced at at least a part of the peripheral portion of the light receiving surface side glass plate on the surface opposite to the photovoltaic substrate side of the light receiving surface side glass plate. 〔17〕A method for manufacturing a solar power generation module, comprising performing etching and cleaning on at least one surface of a glass plate and disposing a solar power generation substrate on the one surface side. 〔18〕A method for manufacturing a solar power generation module, comprising disposing a light-receiving surface side glass plate on the light-receiving surface side of a solar power generation substrate having a light-receiving surface and a back surface opposite to the light-receiving surface, and disposing a back surface side glass plate on the back surface side to obtain a solar power generation module, wherein etching and cleaning are performed on at least one of the side of the light-receiving surface side glass plate on the solar power generation substrate side and the side of the back surface side glass plate opposite to the solar power generation substrate side. 〔19〕The method for manufacturing a solar power generation module according to 〔18〕, wherein etching and cleaning are performed on the back surface side glass plate having holes.

Advantages of the Invention

[0009] According to the present invention, it is possible to provide a method for manufacturing a glass plate with a resin layer, which can obtain a glass plate with a resin layer having excellent resistance to falling objects. Further, according to the present invention, it is possible to provide a glass plate with a resin layer. Further, according to the present invention, it is possible to provide a glass plate. Further, according to the present invention, it is possible to provide a solar power generation module and a method for manufacturing a solar power generation module.

Brief Description of the Drawings

[0010]

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Embodiments for Carrying Out the Invention

[0011] The present invention will be described in detail below. However, the present invention is not limited to the following embodiments, and can be arbitrarily modified and implemented without departing from the gist of the present invention. In this specification, the glass composition is shown in terms of molar percentage based on oxides, and mol% may be simply described as %. Further, "~" indicating a numerical range is used in the sense of including the numerical values described before and after it as the lower limit value and the upper limit value.

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

[0013] In this specification, the surface of the glass plate refers to either one of the two major surfaces with the largest area of the glass plate.

[0014] "Substantially not contained" in the glass composition means not contained except for inevitable impurities contained in raw materials, etc., that is, it is not intentionally contained. Specifically, for components other than those described as the glass composition, for example, less than 0.1 mol% is preferable, less than 0.08 mol% is more preferable, and less than 0.05 mol% is even more preferable.

[0015] In this specification, the "stress profile" is a pattern representing the compressive stress value with the depth from the glass surface as a variable. A negative compressive stress value means tensile stress. In this specification, the measurement of the "stress profile" can be performed by a method using a combination of an optical waveguide surface stress meter and a scattered light photoelastic stress meter.

[0016] The optical waveguide surface stress meter can accurately measure the stress of the glass in a short time. Examples of the optical waveguide surface stress meter include the FSM-6000 manufactured by Oriehara Seisakusho Co., Ltd. However, in principle, the optical waveguide surface stress meter can measure stress only when the refractive index decreases from the sample surface toward the inside. In chemically strengthened glass, the layer obtained by replacing sodium ions inside the glass with potassium ions outside has a decreasing refractive index from the sample surface toward the inside, so the stress can be measured with an optical waveguide surface stress meter. However, the stress of the layer obtained by replacing lithium ions inside the glass with sodium ions outside 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. Examples of the scattered light photoelastic stress meter include the SLP2000 manufactured by Oriehara Seisakusho Co., Ltd. However, the scattered light photoelastic stress meter is easily affected by surface scattering and may not be able to accurately measure the stress near the surface. For the above reasons, accurate stress measurement becomes possible by using a combination of two types of measuring devices, namely, a surface stress meter using an optical waveguide and a scattered light photoelastic stress meter.

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

[0019] <Method for manufacturing a glass plate with a resin layer> The method for manufacturing a glass plate with a resin layer according to the present invention is to perform etching and cleaning on at least one surface of the glass plate, and then form the resin layer without substantially increasing the scratches on the above-mentioned one surface. Although the mechanism by which the method for manufacturing a glass plate with a resin layer according to the present invention provides a glass plate with a resin layer having excellent resistance to falling objects is not necessarily clear, the inventors speculate as follows. In the method for manufacturing a glass plate with a resin layer according to the present invention, etching and cleaning are performed. By performing etching, it is considered that the shape of the scratches existing on the glass plate changes, and it becomes difficult for fractures to occur starting from the scratches. Here, in the method for manufacturing a glass plate with a resin layer according to the present invention, the resin layer is formed on the surface where etching and cleaning have been performed without substantially increasing the scratches. Then, it is considered that the shape of the scratches changed by etching is maintained, and furthermore, no new scratches are formed during the formation of the resin layer and subsequent processes, and a state where fractures are difficult to occur is maintained. As a result, according to the method for manufacturing a glass plate with a resin layer of the present invention, a glass plate with a resin layer having excellent resistance to falling objects (see FIG. 1) can be obtained.

[0020] Hereinafter, the step of performing etching and cleaning on at least one surface of the glass plate is also referred to as the "etching step". Also, the step of forming the resin layer on one surface is also referred to as the "resin layer forming step". Also, hereinafter, in this specification, the scratches on the glass plate include scratches observable by the naked eye and scratches not observable by the naked eye (also referred to as "hidden scratches"). Hereinafter, the method for manufacturing a glass plate with a resin layer according to the present invention will be described.

[0021] [Etching process] In the method for manufacturing a glass plate with a resin layer of the present invention, an etching process for performing etching and cleaning is carried out on at least one surface of the glass plate. The glass plate to be subjected to the etching process is not particularly limited, and various glass plates can be used. For example, the type of the glass plate is not particularly limited, and it may be a template glass or a float glass. Further, it may be glass obtained by the fusion method or flat glass obtained by the roll-out method. Further, the above glass plate may be tempered glass. That is, the above glass plate may be chemically tempered glass or physically tempered glass. Examples of the above glass plate include a glass plate obtained by subjecting a template glass to a physical tempering treatment, a glass plate obtained by subjecting a template glass to a chemical tempering treatment, a glass plate obtained by subjecting a float glass to a physical tempering treatment, and a glass plate obtained by subjecting a float glass to a chemical tempering treatment. Hereinafter, examples of the glass plate to be subjected to the etching process will be described in detail.

[0022] Examples of the above chemically tempered glass include glass obtained by subjecting a glass plate to a chemical tempering treatment. Examples of the method of chemical tempering treatment include the ion exchange method. In the ion exchange method, the glass is immersed in a treatment liquid (for example, a molten salt containing at least one of potassium nitrate and sodium nitrate), and ions with a small ionic radius contained in the glass (for example, Li ions and Na ions) are exchanged for ions with a larger ionic radius (for example, Na ions and K ions) to generate a compressive stress on the glass surface. The compressive stress is generated uniformly over the entire surface of the glass, and a compressive stress layer with a uniform depth is formed over 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 liquid, 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, more preferably 500 MPa or more. On the other hand, the surface compressive stress is, for example, 1,200 MPa or less, preferably 900 MPa or less, 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, 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, more preferably 40 μm or less.

[0024] The chemically strengthened glass is not limited as long as it is ion-exchanged. For example, it is obtained by chemically strengthening aluminosilicate glass, soda glass, soda-lime glass, lithium silicate glass, etc.

[0025] Examples of the above-mentioned physically strengthened glass include glass obtained by thermally strengthening glass having a glass transition temperature of 500 °C or higher and an average expansion coefficient α 50~350 of 70×10 -7 / °C. Examples of the glass having the above characteristics include soda-lime glass. Thermal strengthening treatment refers to a treatment in which a uniformly heated glass plate is rapidly cooled from a temperature near the softening point to generate compressive stress on the glass surface due to the temperature difference between the glass surface and the glass interior. As thermal strengthening, air-cooling strengthening in which plate-shaped glass is manufactured by the float method or the like, the cut glass plate is heated to a temperature near the softening point or the yield point, and then a cooling medium is sprayed on the surface for rapid cooling is typical. Compressive stress is generated uniformly over the entire surface of the glass, and a compressive stress layer of uniform depth is formed over the entire surface of the glass. Thermal strengthening treatment is more suitable for strengthening thick glass plates than chemical strengthening treatment.

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

[0027] The above-mentioned template glass refers to glass formed by pressing a roll mold against the glass by the roll-out method. The pattern on the surface of the template glass is not particularly limited and may have a known pattern. As described above, physical strengthening treatment or chemical strengthening treatment may be performed on the template glass. In addition, in the case of physically strengthened glass and chemically strengthened glass, increasing the compressive stress can make the surface less likely to be scratched. Also, increasing the depth of the compressive stress layer can make the glass less likely to be scratched even deeper.

[0028] The composition of the glass plate is not particularly limited. For example, a glass plate having a composition containing 52 to 75% of SiO2, 0 to 20% of Al2O3, and 1 to 20% of Na2O in terms of mol% based on oxides is preferred. Hereinafter, a more preferred composition of the glass plate will be described.

[0029] One of the more preferred compositional embodiments of the glass plate is, in terms of mol% based on oxides, SiO2 is 52 to 75%, Al2O3 is 0 to 20%, Li2O is 0 to 18%, Na2O is 1 to 20%, K2O is 0 to 5%, MgO is 0 to 20%, CaO is 0 to 20%, SrO is 0 to 20%, BaO is 0 to 20%, ZnO is 0 to 10% TiO2 is 0 to 1% ZrO2 is 0 to 8%, Y2O3 is 0 to 5% contained. Hereinafter, one of the more preferred compositional embodiments of the glass (the first glass composition) will be described.

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

[0031] Al2O3 is a component that can increase the surface compressive stress by chemical strengthening. When containing Al2O3, the content of Al2O3 is preferably 1% or more, more preferably 2% or more, still more preferably 4% or more, and particularly preferably 6% or more. On the other hand, in terms of not raising the devitrification temperature of the glass too much, the content of Al2O3 is preferably 20% or less, more preferably 18% or less, still more preferably 17% or less, further preferably 16% or less in order, and most preferably 15% or less.

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

[0033] K2O, like Na2O, is a component that lowers the melting temperature of glass and forms surface compressive stress by ion exchange. When containing K2O, its content is preferably 0% or more, more preferably 0.1% or more, still more preferably 0.3% or more, even more preferably 0.4% or more, and particularly preferably 0.5% or more. If there is too much K2O, the chemical strengthening characteristics will deteriorate or the chemical durability will deteriorate, so it is preferably 5% or less, more preferably 4.8% or less, still 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, more preferably 2% or more, from the viewpoint of improving the meltability of the glass raw material and forming a surface compressive stress by ion exchange.

[0035] Li2O is a component that forms a surface compressive stress by ion exchange. When Li2O is contained, its content is preferably 1% or more, more preferably 2% or more, still more preferably 4% or more, and particularly preferably 5% or more. On the other hand, for the purpose of stabilizing the glass, the content of Li2O is preferably 18% or less, more preferably 17% or less, still 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, because the chemical strengthening characteristics and the chemical durability can be enhanced. K2O / R2O is more preferably 0.15 or less, and still more preferably 0.10 or less. In addition, R2O is preferably 10% or more, more preferably 12% or more, and still more preferably 15% or more. Also, R2O is preferably 20% or less, more preferably 18% or less.

[0037] MgO is a component that stabilizes the glass and also enhances the mechanical strength and chemical resistance. Therefore, when the Al2O3 content is relatively low, etc., it is preferably contained. When MgO is contained, the content of MgO is preferably 1% or more, more preferably 2% or more, still 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 and devitrification or phase separation is likely to occur. The content of MgO is preferably 20% or less, more preferably 19% or less, still 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 the glass and a component that improves the crushability of the glass when it is made into chemically strengthened glass, and it may be contained. When CaO is contained, the content is preferably 0.5% or more, more preferably 1% or more, still more preferably 2% or more, particularly preferably 3% or more, and most preferably 5% or more. On the other hand, when the content of CaO exceeds 20%, the ion exchange performance is significantly reduced, so 20% or less is preferable. The content of CaO is more preferably 14% or less, and still more preferably, step by step, 10% or less, 8% or less, 6% or less, 3% or less, 1% or less.

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

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

[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, more preferably 0.5% or more. On the other hand, when the content of ZnO exceeds 10%, the weather resistance of the glass significantly decreases. Therefore, the content of ZnO is preferably 10% or less, more preferably, step by step, 8% or less, 6% or less, 3% or less, 1% or less.

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

[0044] For the purpose of enhancing chemical durability, ZrO2 / R2O is preferably 0.02 or more, more preferably 0.04 or more, still 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, still more preferably 0.16 or less, and particularly preferably 0.14 or less.

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

[0046] When Y2O3 is used as chemically strengthened glass, it is a component that has the effect of making it difficult for fragments to scatter when the glass breaks and can be contained. The content of Y2O3 is preferably 0.3% or more, more preferably 0.5% or more, still 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 content of Y2O3 is preferably 5% or less, and more preferably 4% or less.

[0047] The first glass composition may contain components (other components) other than those described above. Examples of other components include SnO2, B2O3, La2O3, Nb2O5, Ta2O5, and CeO2.

[0048] SnO2 is not essential, but when contained, it is preferably 0.5% or more, more preferably 1% or more, still 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, still more preferably 3% or less, and particularly preferably 2.5% or less.

[0049] B2O3 is a component that improves the chipping resistance of the glass and also improves the meltability and may be contained. When B2O3 is contained, the content is preferably 0.5% or more, more preferably 1% or more, and still more preferably 2% or more in order to improve the meltability. On the other hand, if the content of B2O3 is too high, veins may occur during melting or phase separation may easily occur, and the quality of the chemically strengthened glass tends to deteriorate, so it is preferably 10% or less. The content of B2O3 is more preferably 8% or less, still more preferably 6% or less, and particularly preferably 4% or less.

[0050] La2O3, Nb2O5, and Ta2O5 are all components that, when used as chemically strengthened glass, make it difficult for fragments to scatter when the glass breaks, 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, still more preferably 1.5% or more, and particularly preferably 2% or more. Also, in order to make the glass less likely to devitrify during melting, La2O3 + Nb2O5 + Ta2O5 is preferably 4% or less, more preferably 3% or less, still more preferably 2% or less, and particularly preferably 1% or less.

[0051] Also, CeO2 may be included. CeO2 may suppress coloring by oxidizing the glass. When CeO2 is included, the content is preferably 0.03% or more, more preferably 0.05% or more, and still more preferably 0.07% or more. The content of CeO2 is preferably 1.5% or less, more preferably 1.0% or less, in order to enhance transparency.

[0052] When using the chemically strengthened glass after coloring, coloring components may be added within a range that does not inhibit the achievement of the desired chemical strengthening properties. Examples of coloring components include Co3O4, MnO2, Fe2O3, NiO, CuO, Cr2O3, V2O5, Bi2O3, SeO2, Er2O3, and Nd2O3.

[0053] The total content of the coloring components is preferably in the range of 1% or less. When it is desired to increase the visible light transmittance of the glass, it is preferably substantially free of these components.

[0054] In order to enhance the weather resistance against ultraviolet light irradiation, HfO2, Nb2O5, and Ti2O3 may be added. When added for the purpose of enhancing the weather resistance against ultraviolet light irradiation, the total content of HfO2, Nb2O5, and Ti2O3 is preferably 1% or less, still more preferably 0.5% or less, and even more preferably 0.1% or less, in order to suppress the influence on other properties.

[0055] In addition, as a fining agent or the like during the melting of glass, SO3, SnO2, chlorides, and fluorides may be appropriately contained. The total content of the components functioning as a fining agent is preferably 2% or less, more preferably 1% or less, and even more preferably 0.5% or less in terms of mass% based on oxides, because adding too much will affect the strengthening properties. The lower limit is not particularly limited, but typically, in terms of mass% based on oxides, a total of 0.05% or more is preferable.

[0056] When using SO3 as a fining agent, the content of SO3 is preferably 0.01% or more, more preferably 0.05% or more, and even more preferably 0.1% or more in terms of mass% based on oxides, because if it is too little, no effect can be observed. Also, when using SO3 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 in terms of mass% based on oxides.

[0057] When using chlorides as a fining agent, the content of chlorides is preferably 1% or less, more preferably 0.8% or less, and even more preferably 0.6% or less in terms of mass% based on oxides, because adding too much will affect physical properties such as strengthening properties. Also, when using chlorides as a fining agent, the content of chlorides is preferably 0.05% or more, more preferably 0.1% or more, and even more preferably 0.2% or more in terms of mass% based on oxides, because if it is too little, no effect can be observed.

[0058] When using SnO2 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 in terms of mass% based on oxides. Also, when using SnO2 as a fining agent, the content of SnO2 is preferably 0.02% or more, more preferably 0.05% or more, and even more preferably 0.1% or more in terms of mass% based on oxides, because if it is too little, no effect can be observed.

[0059] It is preferably free of P2O5. When containing P2O5, it is preferably 2.0% or less, more preferably 1.0% or less, and most preferably not contained.

[0060] It is preferably free of As2O3 and Sb2O3. When containing Sb2O3, it is preferably 0.3% or less, more preferably 0.1% or less, and most preferably not contained.

[0061] As another aspect of the more preferred composition of the glass sheet, in terms of mol% based on oxides, SiO2 is 60 - 76%, Al2O3 is 0 - 10%, Na2O is 10 - 18%, K2O is 0 - 5%, MgO is 2 - 12%, CaO is preferably contained in an amount of 0 - 15%. Hereinafter, other aspects (the second glass composition) of the more preferred composition of the glass sheet will be described. Hereinafter, the percentage represents the content in terms of mol percentage based on oxides, unless otherwise specified.

[0062] SiO2 is known as a component that forms a network structure in the fine structure of the glass and is a main component constituting the glass. The content of SiO2 is more preferably 61% or more, even more preferably 62% or more. Also, the content of SiO2 is more preferably 74% or less, even more preferably 72% or less, and particularly preferably 70% or less.

[0063] Al2O3 is a component that improves the weather resistance of the glass and has an effect of improving the ion exchange performance in chemical strengthening. The content of Al2O3 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. Also, the content of Al2O3 is more preferably 9% or less.

[0064] Na2O is a component that lowers the high-temperature viscosity and devitrification temperature of the glass, and improves the melting and formability of the glass. It is also a component that forms compressive stress by ion exchange and has the effect of increasing the depth of the compressive stress layer DOL. The content of Na2O is more preferably 11% or more, and even more preferably 12% or more. Also, the content of Na2O is more preferably 16% or less, and even more preferably 15% or less.

[0065] K2O is not essential, but it may be contained for any one or more of the purposes of improving the melting property of the glass, improving the chemical durability, and increasing the ion exchange rate. When K2O is contained, the content of K2O is more preferably 4% or less. When K2O is contained, the content of K2O is more preferably 0.1% or more, and even more preferably 0.5% or more. Note that the second glass composition may not contain K2O.

[0066] MgO is a component that stabilizes the glass. The content of MgO is more preferably 3% or more, and even more preferably 4% or more. Also, the content of MgO is more preferably 11% or less.

[0067] CaO is not essential, but it is a component that stabilizes the glass. In order to improve the water resistance and chemical resistance, the content of CaO is more preferably 5% or more, even more preferably 6% or more, and particularly preferably 7% or more. Also, the content of CaO is more preferably 13% or less, and even more preferably 11% or less. Note that the second glass composition may not contain CaO.

[0068] The second glass composition may contain components (other components) other than those described above. Examples of other components include clarifying agents such as sulfates, Fe2O3, TiO2, ZrO2, SnO2, and Sb2O3. The total content of other components is preferably 1% or less.

[0069] The thickness of the glass plate to be subjected to the etching process is not particularly limited, but it is often 0.1 mm or more, preferably 0.5 mm or more, and more preferably 1.0 mm or more. Also, the thickness of the glass plate is often 10 mm or less, preferably 4 mm or less, and more preferably 3 mm or less.

[0070] In the etching process, an etching treatment is performed on the glass plate. Examples of the method of the etching treatment include a method of bringing the glass plate into contact with an etching solution.

[0071] As the etching solution, an aqueous solution containing a fluorine-containing compound capable of releasing fluoride ions (F - ) and hexafluorosilicate ions (SiF6 2- ) can be mentioned. Specific examples of the fluorine-containing compound include hydrogen fluoride (HF), ammonium fluoride (NH4F), hexafluorosilicic acid (H2SiF6), and ammonium hexafluorosilicate ((NH4)2SiF6). It is also preferable that the etching solution contains other acidic compounds in addition to the above compounds. Examples of other acidic compounds include 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% by mass, more preferably 0.1 to 10% by mass, and even more preferably 1 to 8% by mass with respect to the total mass of the etching solution. In the etching solution, only one kind of the fluorine-containing compound may be used, or two or more kinds may be used. Also, the content of the other acidic compound in the etching solution is preferably 0.1 to 30% by mass, more preferably 1 to 25% by mass, and even more preferably 5 to 20% by mass with respect to the total mass of the etching solution. In the etching solution, only one kind of the other acidic compound may be used, or two or more kinds may be used. Note that the balance of the etching solution is usually water.

[0072] The method of bringing the glass plate into contact with the etching solution is not particularly limited. For example, there are a method of immersing the glass plate in the etching solution, a method of showering the etching solution onto the glass plate, and a method of spraying the etching solution onto the glass plate. When immersing the glass plate in the etching solution, it is also preferable to carry out the process while causing the etching solution to convect.

[0073] When the etching treatment is carried out by a method of bringing the glass plate into contact with the etching solution, the treatment temperature is preferably 0°C or higher, more preferably 10°C or higher, still more preferably 20°C or higher, and may be 40°C or higher. Further, the treatment temperature is often less than 100°C, preferably 90°C or lower, and more preferably 70°C or lower.

[0074] When the etching treatment is carried out by a method of bringing the glass plate into contact with the etching solution, the contact time between the glass plate and the etching solution can be adjusted as appropriate. For example, it is preferably 30 seconds or longer, more preferably 1 minute or longer, and still more preferably 5 minutes or longer. Further, the contact time is preferably 10 hours or shorter, preferably 1 hour or shorter, and still more preferably 30 minutes or shorter.

[0075] In the etching step, washing is carried out after the etching. The washing method is not particularly limited. For example, there is a method of bringing the etched glass plate into contact with the washing solution. The washing solution is not particularly limited, but water is preferable. Examples of water include industrial water, tap water, distilled water, ion-exchanged water, and ultrapure water, and distilled water, ion-exchanged water, or ultrapure water is preferable.

[0076] Examples of the method of bringing the etched glass plate into contact with the washing solution include a method of immersing the glass plate in the washing solution, a method of showering the washing solution onto the glass plate, and a method of spraying the washing solution onto the glass plate. When immersing the glass plate in the washing solution, it is also preferable to carry out the process while causing the washing solution to convect.

[0077] The cleaning in the etching process may be carried out repeatedly. Also, in the etching process, etching and cleaning may be carried out repeatedly. For example, etching and cleaning may be repeated two or more times. When etching and cleaning are repeated, the number of repetitions may be, for example, five or less.

[0078] The glass plate used in the etching process may have a protective film provided on one surface. Also, the glass plate used in the etching process may have an antireflection layer (AR layer) formed on one surface. When a protective film is provided on the glass plate used in the etching process, for example, it is preferable to use a protective film made of a material that is not altered by the etching solution used in the above etching process.

[0079] The above etching process may be performed on only one surface of the glass plate, or may be performed on one surface and the other surface of the glass plate.

[0080] [Resin layer formation process] In the method for manufacturing a glass plate with a resin layer of the present invention, after performing the above etching process, resin layer formation is carried out. Thereby, a glass plate with a resin layer (see FIG. 1) is obtained. Here, in the method for manufacturing a glass plate with a resin layer of the present invention, the resin layer is formed without substantially increasing the scratches on the above one surface. The resin layer formation process may be performed at least on the surface where etching was performed in the above etching process, and may be performed on only one side or both sides. The material constituting the resin layer to be formed is not particularly limited, and known resins can be used. Examples of the material constituting the resin layer include polyolefins (e.g., polyethylene, polypropylene, etc.), polyesters (polyethylene terephthalate, polyethylene naphthalate, etc.), polycarbonate, polyurethane, and polyimide. Also, the resin layer may be an adhesive layer or an adhesive layer. Examples of materials constituting the adhesive layer or the bonding agent 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.

[0081] In the resin layer forming step, "substantially not increasing the scratches" means that visible scratches do not increase and invisible scratches (hidden scratches) do not substantially increase. Here, "not substantially increasing the hidden scratches" means that when the etching test described later is performed, the increase amount of the number density of the recesses on the surface of the glass plate on the side where the resin layer is formed is 10 pieces / cm 2 or less. The increase amount of the number density of the above-mentioned recesses is preferably 5 pieces / cm 2 or less, and more preferably 1 piece / cm 2 or less. Note that the increase amount of the number density of the above-mentioned recesses may be 0 pieces / cm 2 or more. The method for measuring the increase amount of the number density follows the method described later.

[0082] Examples of the method for performing the resin layer forming step of the present invention include a method of forming a resin layer without touching the surface other than the resin layer on the above-mentioned one surface. Specifically, for example, a method of bonding the surface of the glass plate on the side where the etching treatment is performed and the resin layer can be mentioned. Further, the resin layer may be formed by applying a composition containing components constituting the resin layer. Note that "forming the resin layer without touching the surface other than the resin layer on the above-mentioned one surface" means that no step of bringing an object other than the resin layer into contact with the above-mentioned one surface is performed between the etching step and the resin layer forming step. The step of bringing an object other than the resin layer into contact with the above-mentioned one surface refers to a step of bringing a solid other than the resin layer into contact with the above-mentioned one surface. Examples of the above-mentioned step include a step of polishing the above-mentioned one surface, a step of performing conveyance by bringing the above-mentioned one surface into contact with a conveyance roller or the like, and a step of storing by bringing another object into contact with the above-mentioned one surface.

[0083] In addition, as a method for carrying out the resin layer forming step of the present invention, it is not limited to a method of forming a resin layer without touching anything other than the resin layer on the one surface. For example, a method in which a member in contact with the one surface is made of a soft material such as resin, a glass plate is conveyed in contact with the member, and then a resin layer is formed can also be mentioned. In addition, a method in which the smoothness of the surface of the member in contact with the glass plate on the one surface is increased, the glass plate is conveyed in contact with the member, and then a resin layer is formed can also be mentioned. In addition, a method in which the glass plate is conveyed while contacting only the side surface of the glass plate and then a resin layer is formed can also be mentioned.

[0084] The resin layer may be formed over the entire surface of the one surface of the glass plate, or may be formed only on a part thereof. When the resin layer is formed only on a part of the one surface of the glass plate (for example, a region excluding a peripheral portion of 20 mm of the glass plate), the above-described conveying roller or the like may come into contact with the region where the resin layer is not formed (for example, a region of 20 mm of the peripheral portion of the glass plate).

[0085] 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. The thickness of the resin layer is, for example, 5,000 μm or less, preferably 3,000 μm or less, more preferably 300 μm or less, and even more preferably 100 μm or less. When the resin layer is composed of two or more layers, it is preferable that the total thickness of the resin layer is within the above preferable range.

[0086] The manufacturing method of the glass plate with a resin layer of the present invention may have steps other than the above. For example, a drying step may be provided between the etching step and the resin layer forming step. The drying step refers to a step of removing droplets adhering to the surface of the glass plate in the etching step. That is, in the manufacturing method of the 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 of performing the drying process 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 the present specification, supplying a gas to the surface of the glass plate in the above drying process satisfies the requirement of "without touching other than the resin layer on one surface".

[0087] Hereinafter, more specific embodiments of the method for manufacturing a glass plate with a resin layer of the present invention will be described.

[0088] [Aspect 1] As one aspect of the method for manufacturing a glass plate with a resin layer of the present invention, an antireflection film precursor film is formed on one surface of the glass plate, physical strengthening is performed on the glass plate on which the antireflection film precursor film is formed, a protective film having chemical resistance is attached to the surface on the side where the precursor film of the glass plate is formed, and the glass plate is subjected to the etching process and the resin layer forming process described above. In the above aspect, when physical strengthening is performed on the glass plate on which the antireflection film precursor film is formed, the antireflection film precursor film is heated and the antireflection film is formed. In the above aspect, etching is performed only on the surface and side surfaces on the side opposite to the side where the protective film having chemical resistance is attached to the glass plate. Further, when the area of the protective film is smaller than the surface area of the glass plate, etching is also performed in the portion where the protective film is not disposed (for example, the peripheral portion described later), and a stepped portion described later is formed on the surface of the glass plate. In the above aspect, the protective film having chemical resistance attached to the glass plate may be peeled off. In the above aspect, the form of the glass plate is not particularly limited, but it is preferably template glass. As the protective film having chemical resistance, a known protective film can be used, and for example, the resin layer formed in the resin layer forming process can be appropriately selected.

[0089] [Aspect 2] As one aspect of the method for manufacturing a glass plate with a resin layer of the present invention, chemical strengthening is performed on the glass plate to obtain a chemically strengthened glass plate, a protective film having chemical resistance is attached to one surface of the chemically strengthened glass plate, and the chemically strengthened glass plate is subjected to the etching step and the resin layer forming step described above. In the above aspect, etching is performed only on the surface and side surfaces opposite to the side where the protective film having chemical resistance is attached to the chemically strengthened glass plate. Further, a stepped portion may be formed as described in Aspect 1 during etching. In the above aspect, the protective film having chemical resistance attached to the chemically strengthened glass plate may be peeled off. In the above aspect, the form of the glass plate is not particularly limited, but it is preferably float glass.

[0090] [Aspect 3] As one aspect of the method for manufacturing a glass plate with a resin layer of the present invention, a protective film having chemical resistance 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 aspect, etching is performed only on the surface and side surfaces opposite to the side where the protective film having chemical resistance is attached to the glass plate. Further, a stepped portion may be formed as described in Aspect 1 during etching. In the above aspect, the protective film having chemical resistance attached to the glass plate may be peeled off. In the above aspect, the form of the glass plate is not particularly limited, but it is preferably float glass.

[0091] [Aspect 4] As one aspect of the method for manufacturing a glass plate with a resin layer of the present invention, a precursor film of an antireflection film is formed on one surface of the glass plate, the precursor film is heated to form an antireflection film, a protective film having chemical resistance is attached to the surface of the glass plate on the side where the antireflection film is formed, and the glass plate is subjected to the etching step and the resin layer forming step described above. Also, in the above aspect, etching is performed only on the surface and side surfaces opposite to the side where the protective film having chemical resistance of the glass plate is attached. Also, as described in Embodiment 1, a stepped portion may be formed during etching. In the above aspect, the protective film having chemical resistance attached to the glass plate may be peeled off. In the above aspect, the form of the glass plate is not particularly limited, but it is preferably float glass.

[0092] [Embodiment 5] Also, as one aspect of the method for manufacturing a glass plate with a resin layer of the present invention, there is an aspect in which a film having chemical resistance is not attached to the glass plate, and the glass plate is subjected to the above-described etching step and resin layer forming step. In the above aspect, etching is performed on both surfaces of the glass plate and the side surfaces of the glass plate. In the above aspect, it is preferable that the resin layer formed in the resin layer forming step is formed only on one side of the glass plate. In the above aspect, the form of the glass plate is not particularly limited, but it is preferably float glass.

[0093] <Glass plate with resin layer> The glass plate with a resin layer of the present invention has a glass plate and a resin layer, and the increase amount of the number density of the recesses on at least one surface of the glass plate is 10 pieces / cm 2 or less before and after performing an etching test on the glass plate. Details of the etching test will be described in detail later. The glass plate with a resin layer of the present invention is obtained by the method for manufacturing a glass plate with a resin layer of the present invention described above. Since the number density of the recesses does not increase before and after performing the etching test on the glass plate with a resin layer of the present invention, it is considered that the number of scratches is small and it has excellent resistance to falling objects.

[0094] FIG. 1 is a schematic cross-sectional view showing an example of the glass plate with a resin layer of the present invention. The glass plate 30 with a resin layer 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 glass plate 30 with a resin layer shown in Fig. 1, the increase amount of the number density of the recesses on one surface (the surface on which the resin layer 20 is provided) of the glass plate 10 is 10 pieces / cm 2 is as follows.

[0095] Hereinafter, the glass plate with a resin layer of the present invention will be described in detail.

[0096] [Resin layer] The glass plate with a resin layer of the present invention has a resin layer. Examples of the aspect of the resin layer included in the glass plate with a resin layer of the present invention, and preferred aspects are the same as those described in the manufacturing method of the glass plate with a resin layer of the present invention, and thus the description will be omitted. Note that the glass plate with a resin layer of the present invention may be provided on only one surface, or resin layers may be provided on both surfaces of the glass plate.

[0097] [Glass plate] The glass plate with a resin layer of the present invention has a glass plate. Examples of the aspect of the glass plate included in the glass plate with a resin layer of the invention, and preferred aspects are the same as those described in the manufacturing method of the glass plate with a resin layer of the present invention, and thus the description will be omitted. For example, the glass plate included in the glass plate with a resin layer of the present invention may be tempered glass (for example, chemically tempered glass or physically tempered glass).

[0098] When the glass plate included in the glass plate with a resin layer is tempered glass (for example, chemically tempered glass or physically tempered glass), it is preferable to satisfy at least one of the following requirement 1 and requirement 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. As a method for obtaining a glass plate satisfying at least one of the above-mentioned requirement 1 and requirement 2, for example, when obtaining the above-mentioned tempered glass, a method of adjusting the tempering conditions on the one surface side and the other surface side can be mentioned. Additionally, after obtaining the above-mentioned tempered glass, a method of attaching a film having chemical resistance to the other surface of the tempered glass and removing a layer having a predetermined thickness from the one surface side by etching or the like can also be mentioned. When at least one of the above-mentioned requirement 1 and requirement 2 is satisfied, the surface strength on the other surface side in requirement 1 and requirement 2 is likely to be improved. When the surface strength on the other surface side is high, cracks are less likely to occur. Therefore, for example, it is preferable to arrange and use the other surface side on the side of the solar power generation substrate of the solar power generation module described later.

[0099] [Etching test] In the glass plate with a resin layer of the present invention, the increase amount of the number density of the recesses on at least one surface before and after performing the above-mentioned etching test is 10 pieces / cm 2 or less. However, the above-mentioned etching test is a test in which a glass plate is immersed in an etching solution containing 5% by mass of hydrogen fluoride, 15% by mass of hydrogen chloride, and 80% by mass of water for 10 minutes with the temperature of the etching solution being 25°C.

[0100] The etching test is more specifically carried out according to the following procedure. First, the resin layer of the glass plate with a resin layer is peeled off. When peeling off the resin layer, it is carried out so as not to touch the number density measurement region described later among the surfaces on which the resin layer is formed. When resin layers are formed on both surfaces of the glass plate in the glass plate with a resin layer, the resin layers on both surfaces are peeled off. After peeling off the resin layer, the glass plate is immersed in the above-mentioned etching solution. The conditions are as described above.

[0101] Also, before and after the etching test, the number density of the recesses on one surface of the glass plate is measured. The measurement of the number density of the recesses is carried out at least for the surface from which the resin layer of the glass plate with a resin layer has been peeled off. The measurement of the number density of the recesses on one surface of the glass plate is carried out by an optical microscope. As the above optical microscope, a laser microscope (VK-X3000) equipped with a white interferometer manufactured by Keyence Corporation can be used. Specifically, an area of 1.5 mm square 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 area of 1.5 mm square, the area of 1.5 mm square may be divided for observation. For example, the area of 250 μm square may be observed while changing the position, and the area of 1.5 mm square may be observed. Next, the number of the obtained recesses is divided by the measurement area to obtain the number density of the recesses on one surface of the glass plate. The above observation is repeated while changing the field of view until the total measurement area becomes 1 cm 2 2. When observing the increase amount of the number density of the recesses by the above optical microscope, the increase amount of the number density of the recesses is preferably 10 pieces / cm 2 or less, more preferably 5 pieces / cm 2 or less. Further, the increase amount of the number density of the recesses may be 0 pieces / cm 2 . 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. Further, the above recesses do not include visible shapes of the template glass. The surface forming the above recesses is often composed of a smooth curve. Further, the contour line of the above recesses often has a substantially circular or substantially elliptical shape, or a shape formed by connecting them, in plan view. Details of the shape of the above recesses will be described in the part of the following examples.

[0102] In addition, when recesses with a diameter of 5 to 100 μm and a depth of 0.01 to 10 μm are counted as the above recesses and the increase amount of the number density of the recesses is observed, the increase amount of the number density of the recesses is preferably in the same range as when recesses with a diameter of 1 to 100 μm and a depth of 0.01 to 10 μm are counted as recesses. Also, when the recesses with a diameter of 10 to 100 μm and a depth of 0.01 to 10 μm are counted as the above-mentioned recesses and the increase amount of the number density of the recesses is observed, the increase amount of the number density of the recesses is preferably in the same range as when the recesses with a diameter of 1 to 100 μm and a depth of 0.01 to 10 μm are counted as the recesses. When the recesses with a diameter of 15 to 100 μm and a depth of 0.01 to 10 μm are counted as the above-mentioned recesses and the increase amount of the number density of the recesses is observed, the increase amount of the number density of the recesses is preferably in the same range as when the recesses with a diameter of 1 to 100 μm and a depth of 0.01 to 10 μm are counted as the recesses.

[0103] In the glass plate with a resin layer of the present invention, before and after performing the etching test, the increase amount of the number density of the recesses on at least one surface is 10 pieces / cm 2 or less. In the glass plate with a resin layer of the present invention, before and after performing the etching test, the increase amount of the number density of the recesses on one surface and the increase amount of the number density of the recesses on the other surface may both be 10 pieces / cm 2 or less. The increase amount of the above-mentioned number density is preferably 5 pieces / cm 2 or less, more preferably 1 piece / cm 2 or less. The increase amount of the above-mentioned number density may be 0 pieces / cm 2 either.

[0104] Also, the measurement of the number density of the recesses can also be carried out by the following method. First, irradiate the light of a white LED from the direction of the end of the glass plate (the surface orthogonal to the above-mentioned one surface). That is, irradiate the white LED light by the edge lighting method. The irradiation of the above-mentioned white LED light is adjusted to be 150,000 to 190,000 lx at the central portion of the above-mentioned one surface of the glass plate. While irradiating the glass plate with the light of the white LED under the above-mentioned conditions, image-capture is performed with a digital camera from the above-mentioned one surface side of the glass plate. The magnification of the digital camera used for image-capture is such that 1 pixel (1 pixel) corresponds to a 10 μm square. Next, for the captured image, a process is performed in which the brightness of the pixel showing the highest brightness is set to 255 and the brightness of the pixel showing the lowest brightness is set to 0, to obtain a processed image. Next, in the processed image, select a region such that the inspection range is 27 mm square. In the selected region, count as a recess any region where pixels with a brightness of 40 or more are aggregated in a vertical direction of 3 pixels or more and in a horizontal direction of 3 pixels or more. Perform the counting of the recesses within the selected region, and divide the number of counted recesses by the area of the selected region to obtain the number density of the recesses on one surface of the glass plate.

[0105] For the processed image obtained by the above procedure, perform binarization processing with a brightness threshold of 127, setting pixels below the threshold to 0 (black) and pixels above the threshold to 1 (white) to obtain a binarized image. For the obtained binarized image, it is also possible to calculate the ratio of the number of white pixels to the number of black pixels (hereinafter also referred to as the "white pixel ratio"). The above white pixel ratio is preferably 0.20% or less, more preferably 0.10% or less, and even more preferably 0.05% or less. Also, the white pixel ratio may be 0.00%.

[0106] Note that the glass plate with a resin layer of the present invention may have another glass plate. The other glass plate is, for example, disposed on the resin layer side of the glass plate with a resin layer of the present invention.

[0107] <Use of the glass plate with a resin layer> The glass plate with a resin layer obtained by the manufacturing method of the 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 uses. Among them, the glass plate with a resin layer of the present invention has excellent resistance to falling objects, and thus is useful as various cover glasses. The glass plate with a resin layer of the present invention is particularly preferably used as a member of a photovoltaic module. Since the glass plate with a resin layer of the present invention has excellent resistance to falling objects, for example, even if a falling object such as hail collides, the photovoltaic module is less likely to be damaged, which is preferable. The above-mentioned solar power generation module is not particularly limited as long as it includes the glass plate with a resin layer of the present invention, and a known configuration can be adopted. For example, as the configuration of the above-mentioned solar power generation module, a configuration having a light receiving panel, which is the glass plate with a resin layer of the present invention, and a solar power generation substrate in this order can be mentioned. As the configuration of the solar power generation module other than the above, a known configuration can be adopted. In addition, when the glass plate with a resin layer of the present invention is adopted for the solar power generation module, the resin layer side of the glass plate with a resin layer (the surface side where the increase amount of the number density of the concave portions is 10 pieces / cm before and after performing the etching test on the glass plate) is preferably disposed on the solar power generation substrate side of the above-mentioned solar power generation module. 2 Further, in the above-mentioned solar power generation module, an antireflection film may be formed on the side opposite to the solar power generation substrate side of the glass plate with a resin layer of the present invention. Furthermore, in the above-mentioned solar power generation module, an antiglare film may be formed on the side opposite to the solar power generation substrate side of the glass plate with a resin layer of the present invention. In addition, the solar power generation module may further have another glass plate (rear surface side glass plate) on the side opposite to the glass plate with a resin layer side of the solar power generation substrate. The above-mentioned rear surface side glass plate may be the glass plate with a resin layer of the present invention, may be the glass plate of the present invention described later, or may be a conventionally known glass plate. Also, the above-mentioned rear surface side glass plate may be a glass plate obtained by removing the resin layer from the glass plate with a resin layer. Also, as described later, the above-mentioned solar power generation module may be obtained by using a glass plate obtained by peeling the resin layer from the glass plate with a resin layer.

[0108] Further, the glass plate with a resin layer of the present invention may be applied to other uses, for example, it may be applied to window glass, greenhouse glass, laminated glass, and the like.

[0109] <Glass plate> The glass plate of the present invention has concave portions with a diameter of 1 to 100 μm and a depth of 0.01 to 10 μm on at least one surface of the glass plate, and the number of the concave portions is 0.1 piece / cm 2has the above. In the glass plate of the present invention, the above concave portions are 1 piece / cm 2 or more, preferably 50 pieces / cm 2 or more, more preferably 100 pieces / cm 2 or more, still more preferably 200 pieces / cm 2 or more, particularly preferably. In the glass plate of the present invention, the upper limit of the above concave portions is not particularly limited, but is often 1,000 pieces / cm 2 or less. The measurement of the number density of the above concave portions can be measured by the same measurement method as the measurement method of the number density of the concave portions by an optical microscope (laser microscope equipped with a white interferometer) of the glass plate with a resin layer of the present invention. That is, the definition of the concave portions is also the same as that of the glass plate with a resin layer of the present invention. In addition, the number density of the concave portions having a diameter of 5 to 100 μm and a depth of 0.01 to 10 μm is preferably in the same range as that of the concave portions having a diameter of 1 to 100 μm and a depth of 0.01 to 10 μm. In addition, the number density of the concave portions having a diameter of 10 to 100 μm and a depth of 0.01 to 10 μm is preferably in the same range as that of the concave portions having a diameter of 1 to 100 μm and a depth of 0.01 to 10 μm. In addition, the number density of the concave portions having a diameter of 15 to 100 μm and a depth of 0.01 to 10 μm is preferably in the same range as that of the concave portions having a diameter of 1 to 100 μm and a depth of 0.01 to 10 μm.

[0110] In addition, in the glass plate of the present invention, the increase amount of the number density of the concave portions on at least one surface before and after performing an etching test on the glass plate is 10 pieces / cm 2 or less, which is also preferable. However, the etching test is a test in which the glass plate is immersed 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. Since the glass plate of the present invention is the same as the aspect of the glass plate with a resin layer of the present invention (see FIG. 1) except that it does not have a resin layer, the description is omitted. For example, the glass plate of the present invention may be chemically strengthened glass or physically strengthened glass, and it is also preferable to satisfy at least one of the above-mentioned requirement 1 and requirement 2. Note that the glass plate of the present invention can be obtained, for example, by removing the resin layer from the glass plate with a resin layer of the present invention. It is preferable that the removal of the resin layer is performed without substantially increasing the scratches on the surface on which the resin layer is disposed. Further, the glass plate of the present invention may be obtained by performing an etching process on the glass plate. Since the method of etching is the same as that of the glass plate with a resin layer of the present invention, the description thereof is omitted. By the etching process, the above-described concave portions are formed on at least one surface of the glass plate. That is, when a glass plate having the above-described concave portions on at least one surface is obtained by performing the etching process, even if the formation and removal of the resin layer are not further performed, the glass plate is considered to be the glass plate of the present invention. The glass plate of the present invention has excellent resistance to falling objects, similar to the glass plate with a resin layer of the present invention.

[0111] <Use of the glass plate> The glass plate of the present invention can be applied to various uses. Among them, since the glass plate of the present invention has excellent resistance to falling objects, it is useful as various cover glasses. The glass plate of the present invention is particularly preferably used as a member of a photovoltaic module. Since the glass plate of the present invention has excellent resistance to falling objects, for example, even if a falling object such as hail collides, the photovoltaic module is less likely to be damaged, which is preferable. The above photovoltaic module is not particularly limited except that it includes the glass plate of the present invention, and a known configuration can be adopted. For example, as the configuration of the above photovoltaic module, a configuration having a light receiving surface plate that is the glass of the present invention and a photovoltaic substrate in this order can be mentioned. As the configuration of the photovoltaic module other than the above, a known configuration can be adopted. Note that when the glass plate of the present invention is adopted in a photovoltaic module, the increase amount of the number density of the concave portions of the glass plate before and after the above etching test is 10 pieces / cm 2 It is preferable to dispose the following surface side on the photovoltaic substrate side of the above photovoltaic module. In addition, in the above 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. Further, in the above 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.

[0112] Further, the glass plate of the present invention may be applied to other uses, for example, it may be applied to window glass, greenhouse glass, laminated glass, etc.

[0113] <Photovoltaic module> One aspect 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 strengthened glass, and on the surface of the glass plate on the photovoltaic substrate side, there are recesses having a diameter of 1 to 100 μm and a depth of 0.01 to 10 μm, with 0.1 pieces / cm 2 or more. The number density of the recesses on the surface of the glass plate on the photovoltaic substrate side is measured by the same measurement method as the measurement method of the number density of the recesses by the optical microscope (laser microscope equipped with a white interferometer) of the glass plate with a resin layer of the present invention. Note that the preferred aspect of the glass plate in the photovoltaic module is the same as the preferred aspect of the glass plate of the present invention. Regarding the aspect of the photovoltaic module of the present invention and the aspect of other members included in the photovoltaic module of the present invention, since they are the same as the aspect of the photovoltaic module described in the part of the use of the glass plate with a resin layer of the present invention, the description is omitted. For example, the photovoltaic module may further have another glass plate (rear surface side glass plate) on the side opposite to the glass plate side of the photovoltaic substrate. The above rear surface side glass plate may be a conventionally known glass plate, or may be the same glass plate as the glass plate included in one aspect of the photovoltaic module of the present invention having the above predetermined recesses. Further, the above rear surface side glass plate may be the glass plate with a resin layer of the present invention described above, or may be the glass plate of the present invention described above.

[0114] Figure 2 is a schematic cross-sectional view showing an example of the photovoltaic module of the present invention. The photovoltaic module 50 shown in Figure 2 has a light-receiving surface side 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 to the light-receiving surface 40a). In Figure 2, the light-receiving surface side glass plate 12 is disposed on the light-receiving surface 40a side of the photovoltaic substrate 40. Note that the light-receiving surface side glass plate 12 has recesses in the above-described manner at a rate of 0.1 or more per cm 2 on the surface on the side of the photovoltaic substrate 40.

[0115] Figure 3 is a schematic cross-sectional view showing another example of the photovoltaic module of the present invention. The photovoltaic module 50a shown in Figure 3 has a light-receiving surface side glass plate 12, a photovoltaic substrate 40, and a back surface side glass plate 14 in this order. The photovoltaic substrate 40 has a light-receiving surface 40a and a back surface 40b as described above, and the light-receiving surface side glass plate 12 is disposed on the light-receiving surface 40a side of the photovoltaic substrate 40. Also, the back surface side glass plate 12 is disposed on the back surface 40b side of the photovoltaic substrate 40. The light-receiving surface side glass plate 12 has recesses in the above-described manner at a rate of 0.1 or more per cm 2 on the surface on the side of the photovoltaic substrate 40. The back surface side glass plate 14 may have holes described later.

[0116] In the embodiment shown in Figure 3, the photovoltaic substrate 40 and the light-receiving surface side glass plate 12 are disposed adjacent to each other, but other configurations may be provided between the photovoltaic substrate 40 and the light-receiving surface side glass plate 12. The above-described other configurations are not particularly limited, but examples include the above-described resin layer (more preferably, an adhesive layer or a bonding agent layer). Figure 4 shows a schematic cross-sectional view of a modified example of another example of the photovoltaic module. The photovoltaic module 50b shown in FIG. 4 has a light-receiving surface side glass plate 12, a resin layer 16, a photovoltaic substrate 40, a resin layer 16, and a back surface side glass plate 14 in this order. Note that, as described above, the photovoltaic substrate 40 has a light-receiving surface 40a and a back surface 40b, and the light-receiving surface side glass plate 12 is disposed on the light-receiving surface 40a side of the photovoltaic substrate 40. Further, the back surface side glass plate 14 is disposed on the back surface 40b side of the photovoltaic substrate 40. In the case of the configuration having the resin layer, the glass plate with a resin layer of the present invention described above 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 it may be an adhesive layer or an adhesive agent layer. Also, 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 surface side glass plate 12. Also, two or more resin layers 16 may be disposed between the photovoltaic substrate 40 and the back surface side glass plate 14.

[0117] Also, for example, the photovoltaic module of the present invention is a photovoltaic module having a photovoltaic substrate having a light-receiving surface and a back surface opposite to the light-receiving surface, and a glass plate disposed on the light-receiving surface side of the photovoltaic substrate, and an aspect in which the glass plate satisfies any one or more of the following requirement A1, the following requirement A2, and the following requirement A3 can be mentioned. Requirement A1: The depth of the compressive stress layer on the photovoltaic substrate side of the glass plate is smaller than the depth of the compressive stress layer on the side of the glass plate opposite to 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 side of the glass plate opposite to the photovoltaic substrate side. Requirement A3: The glass plate warps convexly on the side opposite to the photovoltaic substrate side. The above requirement A1 is an aspect in which the glass plate of the present invention satisfying the above requirement 1 is disposed with the side having a smaller depth of the compressive stress layer on the photovoltaic substrate side. Further, the above requirement A2 is an aspect in which the glass plate of the present invention satisfying the above-described requirement 2 has the side with a small compressive stress disposed on the photovoltaic substrate side.

[0118] Regarding the above requirement A3, when the glass plate is warped, the stress acting on the surface of the glass plate is different on both sides, and in many cases, the compressive stress acting on the convex surface side is large. For example, the glass plate of the present invention satisfying at least one of the above-described requirements 1 and 2 warps convexly on the side where the compressive stress acting on the surface of the glass plate is large. That is, when requirement A3 is satisfied, in many cases, the compressive stress acting on the surface of the glass plate is larger on the side opposite to the photovoltaic substrate side than on the photovoltaic substrate side. A schematic diagram in the case of satisfying the above requirement A3 is shown in FIG. 5. FIG. 5 is a cross-sectional schematic diagram of a photovoltaic module in the case of satisfying the above requirement A3. Note that the scale is exaggerated in FIG. 5 for the purpose of explanation. The photovoltaic module 50c shown in FIG. 5 includes a light-receiving surface side glass plate 12a, a photovoltaic substrate 40, and a back surface side glass plate 14 in this order. The photovoltaic substrate 40 has a light-receiving surface 40a and a back surface 40b, and the light-receiving surface side glass plate 12a is disposed on the light-receiving surface 40a side of the photovoltaic substrate 40. Further, the back surface side glass plate 14 is disposed on the back surface 40b side of the photovoltaic substrate 40. Here, the light-receiving surface side glass plate 12a satisfies the above requirement A3. That is, the light-receiving surface side glass plate 12a warps convexly on the side opposite to the photovoltaic substrate 40 side. In the photovoltaic module 50c shown in FIG. 5, the whole is warped due to the warp of the light-receiving surface side glass plate 12a. In the aspect shown in FIG. 5, since the light-receiving surface side glass plate 12a warps convexly on the side opposite to the photovoltaic substrate 40 side, when the convex surface of the light-receiving surface side glass plate 12a is placed with the ground side (the direction of the action of gravity) facing down, the end portion of the light-receiving surface side glass plate 12a is in a state of being separated from the placement surface. When the end portion of the light-receiving surface side glass plate 12a is separated from the placement surface, workability can be improved. Note that in the aspect shown in FIG. 5, the back surface side glass plate 14 may further satisfy the above requirement A3.

[0119] Examples of the glass plate that satisfies the above requirements A1, A2, and A3 include the glass plate of the present invention described above and the glass plate with a resin layer of the present invention. In one aspect of the solar power generation module of the present invention, the glass plate may satisfy two or more of the requirements A1, A2, and A3, or may satisfy all three of them.

[0120] In addition, in one aspect of the solar power generation module of the present invention, on the surface of the glass plate opposite to the side of the solar power generation substrate, it is also preferable that at least a part of the peripheral edge of the glass plate has a stepped portion where the thickness of the glass plate is reduced. The stepped portion preferably has a thickness smaller than that of the central portion of the glass plate. The above stepped portion will be described with reference to the drawings. FIG. 6 is a top view of a glass plate 10b used in one aspect of the solar power generation module of the present invention, which has a stepped portion where the thickness of the glass plate is reduced at the peripheral edge of the glass plate. The glass plate 10b has a main surface S1 inside the peripheral edge of the glass plate 10b and has a stepped portion S2 at the peripheral edge. FIG. 7 is a cross-sectional view taken along line A-A of the glass plate 10b shown in FIG. 6. In FIG. 7, the stepped portion S2 has a thickness smaller than that of the portion forming the main surface S1 of the glass plate 10b.

[0121] In FIGS. 6 and 7, an embodiment in which the stepped portion S2 is provided at the entire peripheral edge of the glass plate 10b is shown, but the stepped portion S2 may be formed at a part of the peripheral edge of the glass plate 10b.

[0122] The glass plate having the stepped portion as described above can be manufactured, for example, by the aspects 1 to 4 of the method for manufacturing a glass plate with a resin layer of the present invention described above. More specifically, in the above aspects 1 to 4, a protective film having chemical resistance is attached to one surface of the glass plate, and an etching process is carried out. At this time, the protective film used may be made smaller than the outer shape of the glass plate. That is, the protective film is not attached to the peripheral portion of the glass plate, and the glass plate may be subjected to the etching process in a state where the protective film is attached to the main surface of the glass plate. When subjected to the etching process in the above state, etching proceeds in the region (peripheral portion) where the protective film does not exist, similarly to the surface on the side where the protective film is not attached, and a stepped portion is formed. After etching, when the protective film is peeled off, a glass plate having the stepped portion in the aspect shown in FIGS. 6 and 7 can be obtained. The glass plate having the stepped portion may be obtained by a method other than the above, but when a glass plate having the stepped portion is obtained by the above method, it is preferable that the surface on the side without the stepped portion (the lower side of the paper surface in FIG. 7) is arranged on the side of the solar power generation substrate. The glass plate having the stepped portion often satisfies any one or more of the above requirements A1, A2, and A3.

[0123] When applying the glass plate having the stepped portion as shown in FIGS. 6 and 7 as the light-receiving surface side glass plate to the solar power generation module of the present invention, it is preferable to arrange the surface having the stepped portion on the side opposite to the solar power generation substrate side. Also, when applying the glass plate having the stepped portion as the back surface side glass plate to the solar power generation module of the present invention, it is preferable to arrange the surface having the stepped portion on the solar power generation substrate side.

[0124] A specific aspect of applying the glass plate having the stepped portion to the solar power generation module of the present invention will be described with reference to the drawings. FIG. 8 is a schematic cross-sectional view of an embodiment in which a glass plate having a stepped portion is used as the light-receiving surface side glass plate of a photovoltaic module. In the embodiment shown in FIG. 8, the photovoltaic substrate 40 has a light-receiving surface 40a and a back surface 40b, and the light-receiving surface side glass plate 12b is disposed on the light-receiving surface 40a side of the photovoltaic substrate 40. As described above, the light-receiving surface side glass plate 12b has a stepped portion. FIG. 9 is a schematic cross-sectional view of a modified example of an embodiment in which a glass plate having a stepped portion is used as the light-receiving surface side glass plate of a photovoltaic module. In FIG. 9, the difference from FIG. 8 is that a back surface side glass plate 14 is disposed 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, the description thereof is omitted. In FIG. 9, the back surface side glass plate 14 may be the glass plate having the stepped portion. When a glass plate having a stepped portion is applied as the back surface side glass plate 14, it is preferable to dispose the surface having the stepped portion on the photovoltaic substrate side.

[0125] A specific embodiment in which a glass plate having a stepped portion is applied to the photovoltaic module of the present invention as the back surface side glass plate will be described with reference to the drawings. FIG. 10 is a schematic cross-sectional view of an embodiment in which a glass plate having a stepped portion is used as the back surface side glass plate of a photovoltaic module. In the embodiment shown in FIG. 10, the photovoltaic substrate 40 has a light-receiving surface 40a and a back surface 40b, and the back surface side glass plate 14a is disposed on the back surface 40b side of the photovoltaic substrate 40. As described above, the back surface side glass plate 14a has a stepped portion, and the surface having the stepped portion is disposed so as to face the photovoltaic substrate 40 side. Further, a light-receiving surface side glass plate 12 is disposed on the light-receiving surface 40a side of the photovoltaic substrate 40.

[0126] In the embodiments shown in FIGS. 8 to 10, at least one of the space between the light-receiving surface side glass plate and the photovoltaic substrate and the space between the back surface side glass plate and the photovoltaic substrate may have the above-described resin layer (see FIG. 4). Since the preferred embodiment of the resin layer is the same as the embodiment of FIG. 4, the description thereof is omitted.

[0127] <Method for manufacturing a photovoltaic module> 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 one surface side. According to the method for manufacturing a photovoltaic module of the present invention, since the glass plate has excellent resistance to falling objects, for example, even if a falling object such as hail collides, a photovoltaic module that is difficult to break can be obtained. Regarding the aspect of the photovoltaic module of the present invention and the aspects of other members included in the photovoltaic module of the present invention, since they are the same as the aspects of the photovoltaic module described in the part of the use of the glass plate with a resin layer, the description thereof is omitted. For example, the photovoltaic module may further have 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 included in one aspect of the photovoltaic module of the present invention having the predetermined recess. Further, the other glass plate may be the glass plate with a resin layer of the present invention described above, or may be the glass plate of the present invention described above.

[0128] Also, one aspect of the method for manufacturing a photovoltaic module of the present invention may be an aspect in which a photovoltaic substrate having a light receiving surface and a back surface opposite to the light receiving surface is used. More specifically, a light receiving surface side glass plate is disposed on the light receiving surface side of the photovoltaic substrate having a light receiving surface and a back surface opposite to the light receiving surface, and a back surface side glass plate is disposed on the back surface side to obtain a photovoltaic module, which may be a method for manufacturing a photovoltaic module. Here, in one aspect of the method for manufacturing a photovoltaic module of the present invention, etching and cleaning are performed on at least one of the side of the light receiving surface side glass plate on the photovoltaic substrate side and the side opposite to the photovoltaic substrate side of the back surface side glass plate. The light receiving surface side glass plate and the back surface side glass plate may be the glass plate with a resin layer of the present invention described above, or may be the glass plate of the present invention described above.

[0129] Furthermore, in one aspect of the method for manufacturing the solar power generation module of the present invention, it is also preferable to perform etching and cleaning on the backside glass plate having the holes. That is, in one aspect of the method for manufacturing the solar power generation module of the present invention, the backside glass may have holes in a part thereof. The holes are preferably holes for leading out the wiring of the solar power generation substrate to the outside of the solar power generation module. Note that the holes refer to spaces penetrating in the plate thickness direction of the glass plate. A specific example of the backside glass obtained by performing etching and cleaning on the backside glass having the holes will be described with reference to the drawings. FIG. 11 is a top view of the backside glass having the holes. The backside glass 14b shown in FIG. 11 has circular holes H1, H2, and H3. The backside glass 14b also has a main surface S1 and a stepped portion S2. The backside glass 14b is obtained, for example, by forming circular holes H1, H2, and H3 in a glass plate, then attaching a protective film having the above-described chemical resistance and smaller than the outer shape of the glass plate to one surface, and subjecting it to the above-described etching process.

[0130] In FIG. 11, an aspect in which three holes are formed is shown. However, the arrangement of the holes in the backside glass plate is not particularly limited, and only one hole may be arranged, or two or more holes may be arranged. Further, the shape of the holes is not limited to circular, and may be, for example, rectangular, oval, or elliptical. The size of the holes in the in-plane direction of the backside glass plate is not particularly limited. For example, when the shape of the holes is circular, the diameter of the circle may be 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. Also, in FIG. 11, an aspect having the stepped portion S2 has been described. However, the backside glass having the holes may not have the stepped portion S2. Note that when the backside glass has the above-described holes, it is preferable to perform etching after forming the holes so that the side surface portion of the holes can be etched.

[0131] Here, after performing etching and cleaning, it is also preferable to dispose the photovoltaic substrate on one surface side without substantially increasing the scratches on one surface. Regarding the above glass plate, "without substantially increasing the scratches on one surface" has the same meaning as in the resin layer forming step of the method for manufacturing a glass plate with a resin layer of the present invention. That is, "without substantially increasing the scratches on one surface" means that visible scratches do not increase, and when the etching test is performed, the increase amount of the number density of the concave portions on the surface of the one surface of the glass plate is 10 pieces / cm 2 or less, and the increase amount of the number density of the concave portions is preferably 5 pieces / cm 2 or less, more preferably 1 piece / cm 2 or less. Note that the increase amount of the number density of the concave portions may be 0 pieces / cm 2 or more.

[0132] Regarding the etching and cleaning performed in the method for manufacturing a photovoltaic module of the present invention, it can be performed in the same manner as the etching step in the method for manufacturing a glass plate with a resin layer of the present invention described above.

[0133] The method for manufacturing a photovoltaic module of the present invention may include the method for manufacturing a glass plate with a resin layer described above. More specifically, the method for manufacturing a photovoltaic module of the present invention may include the manufacturing methods of [Aspect 1] to [Aspect 5] of the method for manufacturing a glass plate with a resin layer described above. Further, in the method for manufacturing a photovoltaic module of the present invention, it may have a step of peeling the resin layer from the glass plate with a resin layer obtained by the method for manufacturing a glass plate with a resin layer. The step of peeling the resin layer is preferably performed before performing the assembly step described later.

[0134] As a method for manufacturing the solar power generation module of the present invention, an etching process described in the method for manufacturing a glass plate with a resin layer may be performed on the glass plate, and the resin layer may not be formed on the glass plate on which the etching process has been performed, and an assembly process described later may be performed.

[0135] The manufacturing method of the solar power generation module of the present invention may have an assembly process. The assembly process refers to a process of assembling the solar power generation module. More specifically, it includes a process of bonding a glass plate to a solar power generation substrate. At this time, the above-mentioned one surface of the glass plate (the surface on the side where etching and cleaning are performed) is arranged to face the solar power generation substrate side. As a more specific method of the assembly process, for example, a method of arranging an adhesive film on the solar power generation substrate, bonding a glass plate to the adhesive film, and performing autoclave treatment can be mentioned. Also, as a more specific method of the assembly process, for example, a method of arranging an adhesive film on the glass plate, bonding the solar power generation substrate to the adhesive film, and performing autoclave treatment can be mentioned.

[0136] Also, in the assembly process, the glass plate may be bonded only to one surface of the solar power generation substrate, or the glass plate may be bonded to both surfaces of the solar power generation substrate. That is, the assembly process includes arranging a first adhesive film on a first glass plate, arranging a solar power generation substrate on the side opposite to the first glass plate of the first adhesive film, arranging a second adhesive film on the side opposite to the first glass plate of the solar power generation substrate, and arranging a second glass plate on the side opposite to the solar power generation substrate side of the second adhesive film. Note that at least one of the first glass plate and the second glass plate is a glass plate that has been etched and cleaned. When the first glass plate and the second glass plate are the glass plates of the present invention, for the first glass plate, the etched surface is preferably arranged on the side of the solar power generation substrate, and for the second glass plate, the etched surface is preferably arranged on the side opposite to the solar power generation substrate side. Also, the other of the first glass plate and the second glass plate may be a glass plate that has not been etched. In the above aspect, after obtaining the laminate of the first glass plate, the first adhesive film, the solar power generation substrate, the second adhesive film, and the second glass plate, an autoclave treatment may be performed.

[0137] As the adhesive film (including the first adhesive film and the second adhesive film) used in the above assembly process, a known adhesive film can be used. For example, the adhesive layer or the adhesive agent layer described in the above-described method for manufacturing a glass plate with a resin layer of the present invention can be used. As the above adhesive film, for example, ethylene vinyl acetate resin is preferable.

[0138] The assembly process may further include other processes. For example, after performing the above autoclave treatment, it may have a process of attaching a peripheral frame. Also, it may have a process of connecting wiring. Furthermore, it may have at least one of a quality inspection process and a packaging process.

Example

[0139] The present invention will be described in more detail below based on examples. The materials, amounts used, ratios, treatment contents, treatment procedures, etc. shown in the following examples can be appropriately changed as long as they do not depart from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the examples shown below.

[0140] Note that Examples 1, 3 to 5, 7, 8, 10, 11, 13 to 16, 18, and 20 in the latter part are examples, and Examples 2, 6, 9, 12, 17, and 19 are comparative examples.

[0141] <Example 1> [Preparation of Glass Plate with Resin Layer] Glass raw materials were prepared to have the following composition expressed in terms of molar percentage based on oxides, heated to obtain molten glass, formed into a plate-shaped glass ribbon using the float method, and the glass ribbon was gradually cooled in a lehr to obtain a glass plate with a thickness of 0.7 mm. Glass Material A: SiO2 64.5%, Al2O3 8.0%, Na2O 12.5%, K2O 4.0%, MgO 10.5%, ZrO2 0.5%

[0142] The obtained glass plate was immersed in an etching solution having the following composition to perform an etching treatment. Specifically, for the etching treatment, the immersion time was adjusted so that the etching amount was 75 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.

[0143] After the above etching treatment, both sides of the glass plate were washed with ion-exchanged water. The washing was performed by supplying ion-exchanged water to the surface of the glass plate by shower. Further, the washed glass plate was dried. Here, after the above etching, the diameter and depth of the recesses present on the surface of the glass plate were measured by the method described above. Fig. 14 shows a schematic diagram of a microscopic observation image of the recesses after etching. In Fig. 14, the contour lines of the recesses generated after etching are shown. In the schematic diagram of the microscopic observation image shown in Fig. 14, recess C1, recess C2, recess C3, and recess C4 are shown. The contour line of recess C1 is substantially circular, and its diameter is d1. Also, the contour line of recess C2 is substantially elliptical, and its diameter is given in the major axis direction (maximum diameter) and is d2. Further, the concave portions C3 and C4 have a structure in which their contour lines are connected to each other. In FIG. 14, the lines interpolating the contour lines of the concave portions C3 and C4 are shown as dotted lines respectively. It can be seen that the concave portions C3 and C4 are circular respectively when the contour lines are interpolated. The diameter of the concave portion C3 is d3. Similarly, the diameter of the concave portion C4 is d4. When the contour lines of the concave portions are connected to each other and can be separated from each other by interpolating the shape of the contour lines as described above, the concave portions are counted as existing separately. Here, in the schematic diagram of the microscopic observation image shown in FIG. 14, the number of concave portions observed is 4. That is, the above d1 to d4 are each 1 to 100 μm. Table 1 describes the typical shapes of the concave portions after etching. Note that the shape of the contour line of the concave portion after etching was substantially circular or substantially elliptical in plan view. On the other hand, before etching, the number of concave portions having a diameter of 1 to 100 μm, a depth of 0.01 to 10 μm, an aspect ratio of 10 or less, and being composed of a smooth curve was less than 0.1 piece / cm. 2

[0144]

Table 1

[0145] Next, a resin layer was formed on one surface of the glass plate after cleaning. Note that from the cleaning of the glass plate to the formation of the resin layer, the surface on the side where the resin layer was formed was carried out without touching anything other than the resin layer. As the above resin layer, SANITECT (registered trademark) PAC-3-70 (film thickness 70 μm) manufactured by Sun Ace Chemical Co., Ltd. was used, and the above resin layer was bonded to one surface of the glass plate after cleaning. Through the above procedure, the glass plate with a resin layer of Example 1-1 was obtained. Also, a glass plate of Example 1-2 was obtained by the same procedure except that the resin layer was not bonded.

[0146] [Rubbing test] ​Without peeling the resin layer of the glass plate with the resin layer of Example 1-1 obtained, a rubbing test simulating roller conveyance was performed on the resin layer side. Specifically, on the resin layer side, a #180 SiC sandpaper with a load of 500 g was pressed against it and stroked 5 times to conduct the rubbing test. The stroke width of the rubbing test was set to 20 mm and the speed was set to 80 strokes / min. After the test, the resin layer of Example 1-1 was peeled off to obtain a glass plate. Similarly, a rubbing test was also performed on the glass plate of Example 1-2. When visually comparing the surface of the glass plate of Example 1-1 where the resin layer was formed after the rubbing test with the glass plate of Example 1-2, more scratches were generated in Example 1-2. After that, the glass plate was subjected to an etching test under the above-described conditions. After the etching test, the number density of the concave portions on the surface where the resin layer was formed was measured by the method described above. Also, the resin layer of the glass plate with the resin layer obtained by the same procedure was peeled off from the glass plate, and the number density of the concave portions on the surface where the resin layer was formed was measured by the method described above. From the measurement results of the number density of the above concave portions, when the increase amount of the number density of the concave portions on the surface where the resin layer was formed before and after the etching test was calculated by the method described above, it was 0 pieces / cm 2 It was. The glass plate with the resin layer of Example 1-1 with few scratches is less likely to have breakage starting from scratches and has excellent resistance to falling objects.

[0147] <Example 2> First, molten glass made of glass material B was formed by the roll-out method to obtain a template glass with a plate thickness of 3.2 mm. One side of the obtained template glass had an embossed surface with fine irregularities, and the other side had a matte finish. Next, a slightly adhesive film (the same resin layer as in Example 1 above) was attached to the embossed surface. The template glass was used as the glass plate of Example 2. Note that the composition of glass material B (expressed as a molar percentage based on oxides) is as follows. Glass material B: SiO2 71.76%, Al2O3 0.64%, Na2O 12.31%, K2O 0.06%, MgO 6.13%, CaO 8.89%, SO3 0.16%, Sb2O3 0.04% The obtained glass plate was cut into a size of 100 mm × 100 mm and introduced into a thermal toughening tank for physical toughening. Regarding the embossed surface side of the glass plate after physical toughening, when observed with a laser microscope, although there were scratches in the convex portions of the embossed shape, they did not correspond to the concave portions composed of smooth curves with a diameter of 1 to 100 μm and a depth of 0.01 to 10 μm. Specifically, the scratches in the convex portions of the embossed shape had a diameter exceeding 100 μm. For the glass plate of Example 2 obtained by the above procedure, the strength against falling objects was evaluated by the following method. The method for evaluating the strength against falling objects will be described with reference to the drawings.

[0148] FIG. 12 is a schematic diagram of a ball-drop strength tester 60 used for evaluating the strength (ball-drop strength) against falling objects. The ball-drop strength tester 60 shown in FIG. 12 can drop a steel ball 62 from a predetermined height toward a sample 74 to cause a collision with the sample 74 and measure the ball-drop strength of the sample 74. The sample 74 is made of resin and is placed on a jig 72 having a frame-like shape, and the jig 72 and the sample 74 are placed on a pedestal 70. Also, the steel ball 62 is held by a stopper 66 before being dropped, and the steel ball 62 is allowed to fall freely by releasing the lock of the stopper 66. The steel ball 62 is connected to a winding thread 64, and the winding thread 64 is connected to the main body (not shown) of the ball-drop strength tester 60. By winding the winding thread 64, the position of 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 (in the vertical direction of the paper surface in FIG. 12) can be changed. The glass plate of Example 2 was installed in the ball-drop strength tester 60 as the sample 74, and the steel ball 62 was dropped onto the sample 74 while changing the drop height to cause the steel ball 62 to collide with the sample 74. The above operation was repeatedly performed until a crack (see FIG. 13) occurred in the sample 74, and the collision energy (unit: J) at the time when the crack occurred was taken as the ball-drop strength of the sample 74. The measurement of the above-mentioned ball-drop strength was performed on 10 samples, and the maximum value, average value, minimum value, and B10 value of the ball-drop strength were determined. The maximum value, average value, minimum value, and B10 value of the glass plate of Example 2 are shown in the table in the following section. The B10 value is the ball-drop strength at which 10% cracking occurs, 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 such that the embossed surface faced the ground side (the side opposite to the side where the steel ball 62 collided).

[0149] <Example 3> An etching process was performed on the glass plate of Example 2, and a resin layer similar to that of Example 2 was formed to obtain the glass plate of Example 3. Specifically, for the etching process, the immersion time was adjusted so that the etching amount was 50 μm per side of the glass plate. The etching solution contained 5 mass% hydrogen fluoride, 15 mass% hydrogen chloride, and 80 mass% water. After the etching process, when observing the embossed surface side, the scratches found on the convex portions of the embossed shape were circular or elliptical concave portions, all having a major axis of 10 - 50 μm and a depth of about 0.1 - 0.3 μm. After the etching process, a resin layer similar to that of Example 2 was attached. The obtained glass plate of Example 3 was evaluated for ball-drop strength in the same manner as in Example 2. The results are shown in the table in the following section. When a resin layer is formed on at least one surface of the glass plate of Example 3 by the above-described procedure, a glass plate with a resin layer of the present invention is obtained.

[0150] <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 by conveyance or the like, scratches occurred on the convex portions of the embossed surface. The obtained 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 in the following section.

[0151] <Example 5> In the same manner as in Example 2, a template glass was obtained in which one surface was an embossed surface having fine irregularities and the other surface was a satin-finished surface (satin-finished surface). The obtained template glass was cut into a size of 1,717 mm × 1,128 mm and chamfered. Thereafter, an antireflection coating layer (AR coating layer) mainly composed of SiO2 was formed on the satin-finished surface. Thereafter, a protective film for preventing etching was attached to the surface of the glass plate on the AR coating layer side. The protective film had a shape that was 5 mm smaller than the edge portion of the template glass. An etching process was performed on the glass plate with the protective film attached in the same manner as in Example 3. After etching, the protective film was peeled off, and a resin layer similar to that in Example 2 was formed on the embossed surface side to obtain the glass plate of Example 5. The glass plate of Example 5 had a stepped portion at the peripheral edge on the satin-finished surface side. The obtained glass plate of Example 5 was evaluated for the ball drop strength in the same manner as in Example 2. The results are shown in the table in the following section.

[0152] <Examples 6 to 8> First, molten glass made of glass material C was formed by the float method to obtain a float glass with a plate thickness of 2.0 mm. The obtained float glass had a smooth surface. The composition of glass material B (expressed as mol percentage based on oxides) is as follows. Glass material C: SiO2 68.84%, Al2O3 2.99%, Na2O 14.1%, K2O 0.2%, MgO 6.32%, CaO 7.56% The obtained glass plate was cut into a size of 100 mm × 100 mm and introduced into a thermal toughening tank for physical strengthening. The resin layer was formed on the float glass immediately after physical strengthening to obtain the glass plate of Example 6. When the surface of the glass plate of Example 6 was observed, it was confirmed that linear scratches (scratches not corresponding to the above-mentioned concave portions) were generated. In addition, an etching process was performed on the float glass immediately after physical strengthening to obtain the glass plate of Example 7. Specifically, in the etching process, the immersion time was adjusted so that the etching amount was 10 μm per one surface 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 treatment, when the surface was observed, the width of the linear scratches was enlarged compared to that before etching, and the cross-sectional shape was smooth. In addition, circular or elliptical concave portions were also observed. The major axis of the above concave portion was 5 to 60 μm, and the depth was about 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 by conveyance or the like, the above linear scratches occurred. The obtained glass plates of Examples 6 to 8 were evaluated for the ball drop strength in the same manner as in Example 2. The results are shown in the table in the following section.

[0153] For the sake of convenience, the glass plates of Examples 2 to 8 are hereinafter referred to as glass plates B2 to B8 in order.

[0154] <Examples 9 to 20> Using the above-described glass plates and other members, a solar power generation module was fabricated, and the strength against falling objects was evaluated. Hereinafter, the method for fabricating the solar power generation module in Example 9 and the method for evaluating the strength against falling objects are typically described, and only the differences from Example 9 will be explained for other examples.

[0155] The solar power generation module of Example 9 had a light-receiving surface side glass, a solar power generation substrate, and a back surface side member in this order. The solar power generation module of Example 9 was obtained by the following procedure. First, the glass plate B2 was placed on a workbench with its matte surface side facing down, and the resin layer disposed on the embossed surface side was removed. Next, an adhesive layer made of ethylene vinyl acetate resin was formed on the embossed surface side of the glass plate B2. A crystalline silicon solar power generation substrate was overlaid on the adhesive layer, and another adhesive layer was formed on the side opposite to the glass plate B2 side of the solar power generation substrate. Further, a film (backsheet manufactured by Ewa Co., Ltd., Appli-Sola (registered trademark)) based on polyethylene terephthalate (PET) resin was overlaid on the side opposite to the solar power generation substrate side of the further formed adhesive layer, autoclave treatment was performed, a frame was attached, and the solar power generation module of Example 9 was obtained. The obtained solar power generation module of Example 9 had a glass plate B2, an adhesive layer, a solar power generation substrate, an adhesive layer, and a PET film in this order. Note that the surface of the glass plate B2 on the side opposite to the solar power generation substrate side was a matte surface.

[0156] A 65-mm-diameter ice ball was made to collide 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 cracks occurred in the glass plate. The results are shown in the table in the following section.

[0157] The solar power generation module of Example 10 was obtained in the same manner as Example 9 except that the glass plate B3 was used as the light-receiving surface side glass, and the same evaluation was performed.

[0158] The solar power generation module of Example 11 was obtained in the same manner as Example 10 except that the glass plate B9 was used as the back surface side member, and the same evaluation was performed. The glass plate B9 is a template glass obtained in the same manner as the glass plate B2 except that the thickness was adjusted to 2.0 mm when obtaining the glass plate B2. Note that the solar power generation module of Example 11 was obtained by arranging the matte surface side of the glass plate B9 to be on the side opposite to the solar power generation substrate side.

[0159] The solar power generation module of Example 12 was obtained in the same manner as Example 11 except that the glass plate B9 was used as the light-receiving surface side glass. Note that the surface of the glass plate B9 on the side opposite to the solar power generation substrate side was made to be the matte surface side. A 55-mm-diameter ice ball was made to collide with the glass plate B9 side on the light-receiving surface side of the obtained solar power generation module of Example 11 at a speed of 33.9 m / s (46 J), and it was confirmed whether cracks occurred in the glass plate. The results are shown in the table in the following section.

[0160] The solar power generation module of Example 13 was obtained in the same manner as Example 12 except that the glass plate B10 was used as the glass on the light-receiving surface side, and the same evaluation as Example 12 was performed. The glass plate B10 was obtained by performing an etching process under the same conditions as the glass plate B3 when obtaining the glass plate B9.

[0161] The solar power generation module of Example 14 was obtained in the same manner as Example 13 except that the glass plate B9H having three 15-mm-diameter holes at the center of the glass plate B9 was used as the back-side glass plate, and the same evaluation as Example 13 was performed.

[0162] The solar power generation module of Example 15 was obtained in the same manner as Example 14 except that the glass plate B10H obtained by performing an etching process on the glass plate B9H under the same conditions as the glass plate B10 was used as the back-side glass plate, and the same evaluation as Example 14 was performed. In addition, when obtaining the glass plate B10H, etching was also performed on the cross-sectional portion of the hole. The glass plate B10H was arranged such that the frosted surface side was on the side opposite to the solar power generation substrate side.

[0163] The solar power generation module of Example 16 was obtained in the same manner as Example 15 except that the glass plate B11H was used as the back-side glass plate, and the same evaluation as Example 15 was performed. The glass plate B11H was obtained by pasting a protective film on the embossed surface side of the glass plate B9H in the same manner as the glass plate B5 and performing an etching process under the same conditions as B10H. That is, the glass plate B11H had holes and a stepped portion on the embossed surface side. In addition, when obtaining the glass plate B11H, etching was also performed on the cross-sectional portion of the hole. The glass plate B11H was arranged such that the frosted surface side was on the side opposite to the solar power generation substrate side.

[0164] 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 surface side glass, and the same evaluation as in Example 9 was performed.

[0165] 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 surface side glass, and the same evaluation as in Example 9 was performed.

[0166] The photovoltaic module of Example 19 was obtained in the same manner as in Example 13, except that the glass plate B12 was used as the light-receiving surface side glass and the glass plate B13 was used as the back surface side glass plate, and the same evaluation as in Example 13 was performed. The above glass plate B12 was obtained by adjusting the thickness to 2.0 mm in the procedure for obtaining the glass plate B6. The above glass plate B13 was obtained by performing an etching treatment on the above glass plate B12 under the same conditions as the above glass plate B8 to form a resin layer.

[0167] The photovoltaic module of Example 20 was obtained in the same manner as in Example 19, except that the above glass plate B13 was used as the light-receiving surface side glass and the glass plate B13H was used as the back surface side glass plate, and the same evaluation as in Example 19 was performed. The above glass plate B13H was obtained by using a glass plate B12 having holes in the procedure for obtaining the glass plate B13. In addition, when obtaining the glass plate B13H, etching was also performed on the cross-sectional portion of the holes.

[0168] In addition, the glass used in Example 16 satisfied the above requirements A1 to A3.

[0169] <Result> Table 2 describes the conditions for obtaining the above respective glass plates, the number density of the recesses measured by the above-described method, and the ball-drop strength. In addition, Table 3 describes the configurations of the above respective photovoltaic modules and the evaluation results of the ball-drop strength. For the light-receiving surface side glass and the back surface side glass, the case where no crack occurred is described as "A", and the case where a crack occurred is described as "B".

[0170]

Table 2

[0171]

Table 3

[0172] From the results shown in Table 2, it was confirmed that a glass plate having at least one surface with recesses having a diameter of 1 to 100 μm and a depth of 0.01 to 10 μm at a density of 0.1 pieces / cm 2 or more has high strength against falling objects. From the results shown in Table 3, it was also confirmed that when a glass plate having recesses having a diameter of 1 to 100 μm and a depth of 0.01 to 10 μm at a density of 0.1 pieces / cm 2 or more is applied to a photovoltaic module, the strength against falling objects increases. Also, in Example 20, a photovoltaic module was obtained by using it as an adhesive layer without peeling the resin layer, and when the same evaluation as in Example 20 was performed, the same results as in Example 20 were obtained.

[0173] The entire contents of the specification, claims, drawings, and abstract of Japanese Patent Application No. 2024-079514 filed on May 15, 2024 are hereby incorporated by reference and made a part of the disclosure of the specification of the present invention.

Explanation of Reference Numerals

[0174] 10 Glass plate 12, 12a, 12b Light-receiving surface side glass plate 14, 14a, 14b Back surface side glass plate 16, 20 Resin layer 30 Glass plate with resin layer 40 Photovoltaic substrate 40a Light-receiving surface 40b Back surface 50, 50a, 50b, 50c, 50d, 50e, 50f Photovoltaic module 60 Falling ball strength tester 62 Steel balls 64 Take-up thread 66 Stopper 70 Pedestal 72 Fixture 74 Sample

Claims

1. A method for manufacturing a photovoltaic module having a glass plate and a photovoltaic substrate, comprising: Etching and cleaning are performed on at least one surface of the glass plate, and then a resin layer is formed on the one surface without substantially increasing scratches on the one surface; The glass plate has 0.1 recesses / cm 2 or more, each recess having a diameter of 1 to 100 μm and a depth of 0.01 to 10 μm, on a surface of the glass plate facing the photovoltaic substrate.

2. The method for manufacturing a photovoltaic power generation module according to claim 1 , further comprising forming the resin layer on the one surface without touching anything other than the resin layer.

3. The method for producing a photovoltaic power generation module according to claim 1 , wherein the glass plate is a chemically strengthened glass or a physically strengthened glass.

4. The method for producing a photovoltaic power generation module according to claim 1 , wherein etching is performed on only one surface of the glass plate.

5. A method for manufacturing a solar power generation module as described in claim 1 or 2, comprising etching and cleaning at least one surface of the glass plate, and placing the solar power generation substrate on the one surface side.

6. The photovoltaic substrate has a light receiving surface and a back surface opposite the light receiving surface, The glass plate is a light-receiving surface side glass plate arranged on the light-receiving surface side of the photovoltaic substrate, The method for producing a photovoltaic power generation module according to claim 1 or 2, wherein 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 glass plate is warped in a convex manner on the side opposite to the photovoltaic power generation substrate.

7. 7. The method for manufacturing a photovoltaic module according to claim 6, wherein a step portion where a plate thickness of the light-receiving surface side glass plate is thinner is provided in at least a part of a peripheral portion of the light-receiving surface side glass plate on a surface of the light-receiving surface side glass plate opposite to the photovoltaic substrate side.

8. The photovoltaic substrate has a light receiving surface and a back surface opposite the light receiving surface, the glass plates include a light-receiving surface glass plate disposed on the light-receiving surface side of the photovoltaic substrate, and a back surface glass plate disposed on the back surface side of the photovoltaic substrate, 3 . The method for manufacturing a photovoltaic module according to claim 1 , further comprising the steps of: etching and cleaning at least one of the side of the light-receiving glass plate facing the photovoltaic substrate and the side of the back glass plate facing away from the photovoltaic substrate.

9. The method for manufacturing a photovoltaic power generation module according to claim 8 , further comprising the steps of: etching and cleaning the rear surface glass plate having the hole.

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