Method for producing glass plate with functional layer and device for forming functional layer

Abstract

A method and a device are desired with which it is possible to increase the range of applicable raw materials and increase the number of kinds of functional layers formable on glass plates. This method for producing a glass plate with a functional layer formes a functional layer on a first main surface of a glass plate having the first main surface and a second main surface. The method comprises a preparation step (#21) in which the glass plate is prepared, a conveyance step (#22) in which a mist-state substance for forming a functional layer is conveyed with a carrier gas to a position facing the first main surface, a supply step (#24) in which the mist-state substance is supplied from said position toward the first main surface, and a functional-layer formation step (#25) in which the functional layer is formed on the first main surface.

Description

Manufacturing method of glass plate with functional layer and functional layer forming device

[0001] The present invention relates to a method for producing a glass plate with a functional layer and a functional layer forming apparatus.

[0002] BACKGROUND ART Conventionally, a technique for forming a functional layer such as a transparent conductive film on a main surface of a glass plate by, for example, a CVD method or the like is known.

[0003] JP 2014-80644 A

[0004] However, in conventional methods, the raw materials for the functional layer must be gaseous, and the applicable raw materials are limited, so the types of functional layers that can be formed on a glass plate are limited.

[0005] In view of the above circumstances, there has been a demand for a method and apparatus that can increase the range of applicable raw materials and the types of functional layers that can be formed on a glass plate.

[0006] The method for manufacturing a glass plate with a functional layer of the present invention is a method for manufacturing a glass plate with a functional layer, which comprises a glass plate having a first main surface and a second main surface, and which forms a functional layer on the first main surface of the glass plate, and includes a preparation step for preparing the glass plate, a transport step for transporting a mist-like substance for forming the functional layer to a position opposite the first main surface using a carrier gas, a supply step for supplying the mist-like substance from the opposite position toward the first main surface, and a functional layer formation step for forming a functional layer on the first main surface.

[0007] According to the above configuration, a mist-like substance is transported toward the first principal surface of the glass sheet using a carrier gas, and a functional layer can be formed on the first principal surface of the glass sheet using the mist-like substance. Therefore, there is no need to gasify the substance used to form the functional layer. Liquid substances, such as solution substances or powder substances dispersed in a liquid, can be misted and used to form the functional layer on the first principal surface. Because there is no need to gasify the substance, the range of substances that can be used to form the functional layer is expanded, and the number of types of functional layers that can be formed on the glass sheet can be increased.

[0008] In the above configuration, in the supply step, it is preferable that the mist-like substance is supplied from a supply nozzle provided from the opposing position toward the first main surface, and a protective gas that protects the mist-like substance is supplied along the inner wall surface of the supply nozzle from the opposing position toward the first main surface.

[0009] According to the above configuration, the protective gas flows along the inner wall surface of the supply nozzle toward the first main surface of the glass sheet. As a result, the protective gas guides the mist-like substance toward the first main surface within the supply nozzle. As a result, the mist-like substance can be prevented from adhering to the inner wall surface of the supply nozzle and agglomerating. Furthermore, the protective gas can reduce the influence of the ambient temperature. As a result, the mist-like substance can be supplied to the first main surface while preventing the mist-like substance from being influenced by the ambient temperature.

[0010] In the above configuration, it is preferable that the preparation step is a shaping step of shaping molten raw material of the glass sheet in a float bath when manufacturing a glass sheet by a float method, and that in the supply step, the mist-like substance is supplied toward the first main surface of the glass sheet during the shaping step.

[0011] According to the above configuration, the functional layer can be suitably formed online in the float method, which is often used as a method for manufacturing glass.

[0012] In the above-described configuration, it is preferable that the transporting step includes a temperature adjusting step of adjusting the temperature of the mist-like substance.

[0013] The forming step in the float method is performed at a high temperature, for example, about 600° C. Therefore, by performing a temperature adjustment step to cool the mist-like substance, it is possible to prevent the solvent, such as water, in the mist from evaporating, and to transport the mist-like substance while maintaining it in a mist state.

[0014] In the above configuration, it is preferable that the functional layer forming step includes a functional film forming step of forming, on the first main surface, a functional film using the mist-like substance as at least a part of a raw material or a precursor of a raw material.

[0015] With the above-described configuration, a functional film can be suitably formed using the mist-like substance as a raw material or at least a part of the raw material.

[0016] In the above configuration, it is preferable that the functional film forming step is performed by mist CVD.

[0017] With the above configuration, a functional film can be suitably formed by mist CVD.

[0018] In the above configuration, the functional layer forming step includes a modifying step of modifying a portion of the first main surface of the glass plate with the mist-like substance to form the functional layer.

[0019] With the above-described configuration, the functional layer can be suitably formed by modifying the portion of the first main surface of the glass plate with the mist-like substance.

[0020] The functional layer forming apparatus of the present invention is a functional layer forming apparatus used in the above-mentioned method for manufacturing a glass plate with a functional layer, and is equipped with a transport flow path that transports a mist-like substance for forming the functional layer to a position opposite the first main surface using a carrier gas, and a supply nozzle that is connected to the transport flow path and supplies the mist-like substance from the opposite position toward the first main surface.

[0021] With the above configuration, it is possible to obtain a functional layer forming apparatus that can suitably carry out the method for producing a glass plate with a functional layer.

[0022] In the above-described configuration, it is preferable that the supply nozzle has a supply opening that spans the entire width direction perpendicular to the direction of relative movement between the glass sheet and the supply nozzle.

[0023] According to this configuration, since the supply nozzle has a supply opening that spans the entire width of the glass sheet, which is perpendicular to the direction of relative movement between the glass sheet and the supply nozzle, the mist-like substance can be supplied uniformly across the entire width of the glass sheet, thereby forming a homogeneous functional layer across the entire first main surface of the glass sheet.

[0024] In the above-mentioned configuration, it is preferable to further include a protective gas supply means for supplying a protective gas for protecting the mist-like substance along the inner wall surface of the supply nozzle.

[0025] According to the above configuration, the protective gas flows along the inner wall surface of the supply nozzle toward the first main surface of the glass sheet. As a result, the protective gas guides the mist-like substance toward the first main surface within the supply nozzle. As a result, the mist-like substance can be prevented from adhering to the inner wall surface of the supply nozzle and agglomerating. Furthermore, the protective gas can reduce the influence of the ambient temperature. As a result, the mist-like substance can be supplied to the first main surface while preventing the mist-like substance from being influenced by the ambient temperature.

[0026] In the above configuration, it is preferable to provide a heat medium jacket that covers the transport flow path.

[0027] By providing a heat medium jacket as in the above configuration, the temperature of the transport flow path can be adjusted. As a result, at high temperatures, by cooling the transport flow path, evaporation of the solvent such as water in the mist can be prevented, and the mist-like substance can be transported while maintaining its mist state. Furthermore, at low temperatures, by heating the transport flow path, aggregation of the mist-like substance can be prevented, and the mist-like substance can be transported while maintaining its mist state. Note that when the supply step is performed at low temperatures, by heating the mist-like substance in the temperature adjustment step, aggregation of the mist-like substance can be prevented.

[0028] It is a diagram showing one embodiment of a manufacturing line for a glass plate with a functional layer. It is a cross-sectional view showing one embodiment of a functional layer forming apparatus. It is a perspective view showing a main part of one embodiment of a functional layer forming apparatus. It is a flow showing a manufacturing method of a glass plate with a functional layer.

[0029] Hereinafter, embodiments of a method for manufacturing a functional layer-equipped glass plate 10 and a functional layer-forming apparatus according to the present invention will be described with reference to the drawings. However, the present invention is not limited to the following embodiments, and various modifications are possible within the scope of the present invention.

[0030] 1 , a glass sheet production line 100 includes, from upstream to downstream, a melting furnace 1, a float bath 2, an annealing furnace 3, a cutting device 4, and the like, arranged in this order. In addition, for example, a functional layer forming device 20 is provided in the float bath 2.

[0031] The molten raw material supplied from the melting furnace 1 to the float bath 2 is formed in the float bath 2. That is, in the float bath 2, the molten raw material is formed on the molten tin in the float bath 2. In the float bath 2, a functional layer 12 is formed on a first main surface (upper surface) of a pre-cutting glass sheet (glass ribbon 11′) being formed. The functional layer-forming device 20 then forms the pre-cutting glass sheet 10 by annealing it in the annealing furnace 3 and then cutting it to a predetermined length in the cutting device 4. In the following description, the pre-cutting glass sheet (glass ribbon 11′) including the glass sheet being formed in the float bath 2 and the glass sheet being annealed in the annealing furnace 3 and the cut glass sheet 11 will also be collectively referred to as the “glass sheet 11.”

[0032] 2 and 3, the functional layer forming apparatus 20 has a mist transport path 21 (corresponding to a transport flow path) and a supply nozzle 22. It also has a protective gas supply pipe 23. The mist transport path 21 and the protective gas supply pipe 23 are covered with a water-cooled jacket 24 (an example of a heat medium jacket). The heat medium in the heat medium jacket is not limited to water, and may be something other than water, such as oil.

[0033] The mist transport path 21 extends in the width direction of the glass plate 11 (the direction perpendicular to the transport direction of the glass plate, i.e., the direction of relative movement between the glass plate and the supply nozzle 22). The mist transport path 21 is connected to a mist generator (not shown). A mist-like substance for forming the functional layer 12, generated by the mist generator, is transported through the mist transport path 21 by a carrier gas. The mist-like substance is transported to a position opposite the upper surface of the glass plate 11 being formed in the float bath 2 (a position above the glass plate).

[0034] The supply nozzle 22 is provided below the mist transport path 21 and extends along the longitudinal direction of the mist transport path 21. The supply nozzle 22 has one supply opening 22a that extends in the width direction of the glass plate 11 (the direction perpendicular to the transport direction of the glass plate 11). In this embodiment, the supply opening 22a has a rectangular shape with the long side extending in the width direction of the glass plate 11. The supply opening 22a extends in the width direction of the glass plate 11.

[0035] The supply opening 22 a does not necessarily have to have a length that spans the width direction of the glass sheet 11. The number of supply openings 22 a does not necessarily have to be one, and multiple openings may be provided. Any configuration is sufficient as long as the mist-like material can be supplied evenly across the width direction of the glass sheet 11.

[0036] A communication section is provided between the mist transport path 21 and the supply nozzle 22, connecting the mist transport path 21 and the supply nozzle 22. A communication passage 21a is formed in the communication section, connecting the mist transport path 21 and the supply nozzle 22. A plurality of communication passages 21a are provided along the longitudinal direction of the supply nozzle 22 (the width direction of the glass sheet). In other words, the communication passages 21a are provided at equal intervals so as to be evenly spaced across the entire longitudinal area of ​​the supply nozzle 22. By thus evenly arranging the communication passages 21a across the entire longitudinal area of ​​the supply nozzle 22, the mist-like substance can be supplied evenly regardless of the longitudinal direction of the supply opening 22a of the supply nozzle 22.

[0037] Further, a protective gas supply pipe 23 is provided along the longitudinal direction of the mist transport path 21 and the supply nozzle 22. In this embodiment, one protective gas supply pipe 23 is provided on each of the upstream side and downstream side of the supply nozzle 22 in the transport direction of the glass sheet.

[0038] The supply nozzle 22 and the protective gas supply pipe 23 are connected by a protective gas communication passage 23a. A plurality of protective gas communication passages 23a are provided along the longitudinal direction of the supply nozzle 22 (the width direction of the glass sheet 11). Here, the protective gas supply pipes 23 and the protective gas communication passages 23a correspond to a protective gas supply means. The protective gas communication passages 23a are provided at equal intervals so as to be evenly distributed throughout the entire longitudinal direction of the supply nozzle 22. For example, the protective gas communication passages 23a are provided at the same position in the longitudinal direction as the communication passages 21a. Note that the protective gas communication passages 23a and the communication passages 21a do not necessarily have to be provided at the same position in the longitudinal direction, but may also be provided at different positions in the longitudinal direction. For example, the protective gas communication passages 23a are provided at the upstream and downstream portions of the supply nozzle 22 in the transport direction of the glass sheet 11. The protective gas communication passage 23 a may be provided only in one of the upstream portion and the downstream portion in the conveying direction of the glass sheet 11 .

[0039] An exhaust path 30 is also provided. In this embodiment, the exhaust path 30 is provided at two locations, one on the upstream side and one on the downstream side in the conveyance direction of the glass sheet 11, across the supply nozzle 22. An exhaust fan, for example, is provided in the exhaust path 30, and reaction residues of the carrier gas and mist-like substance, etc. are exhausted to the outside via the exhaust path 30.

[0040] The weight (specific gravity) of each particle of mist-like substance is greater than that of gas. For this reason, for example, when the mist-like substance is transported to the mist transport path 21 by a carrier gas, it is difficult to distribute the mist-like substance uniformly throughout the entire longitudinal direction of the mist transport path 21, resulting in a concentration distribution. In other words, if the flow rate or flow velocity of the carrier gas is increased in an attempt to distribute the mist deep into the path, the mist concentration on the upstream side will decrease.

[0041] Therefore, for example, if a single slit-shaped connecting passage extending along the longitudinal direction of the supply nozzle 22 is provided in the tubular member constituting the mist transport path 21 (corresponding to the transport flow path), the concentration of the mist-like substance cannot be made uniform along the longitudinal direction of the supply nozzle 22, and the thickness of the functional layer formed may become uneven.

[0042] 3, by providing a plurality of tubular communication passages 21a along the longitudinal direction of the mist transport path 21 (supply nozzle 22), even if there is a concentration distribution in the mist material immediately after it is blown out from the communication passages 21a, the tubular shape and the provision of a plurality of communication passages 21a allows the mist material to spread concentrically. As a result, the distribution of the mist material is made uniform while it is passing through the supply nozzle 22, and the thickness of the functional layer is also made uniform.

[0043] <Method for manufacturing glass plate with functional layer> The method for manufacturing a glass plate with functional layer of the present invention will be described using an example in which a functional layer is formed on a glass plate by online mist CVD. Online mist CVD is a method in which mist CVD is performed simultaneously on a glass plate production line.

[0044] The float process, which is an example of a glass manufacturing process, will now be described. As shown in Figure 1, the float process for manufacturing sheet glass includes a melting step (#1), a forming step (#2), an annealing step (#3), and a cutting step (#4).

[0045] The melting step (#1) is a step in which raw materials for a glass sheet are melted in a melting furnace 1. The forming step (#2) is a step in which the molten raw materials supplied from the melting furnace 1 to a float bath 2 are formed on molten tin in the float bath 2. The annealing step (#3) is a step in which the glass sheet 11 formed on the molten tin is annealed in an annealing furnace 3. The cutting step (#4) is a step in which the annealed glass sheet 11 is cut to a predetermined length in a cutting device 4.

[0046] The method for producing a glass plate with a functional layer of the present invention can be carried out, for example, in the forming step (#2). As shown in Figure 4, the method for producing a glass plate with a functional layer of the present invention includes a preparation step (#21), a transport step (#22), a supply step (#24), and a functional layer formation step (#25).

[0047] The preparation step (#21) is a step of preparing a glass sheet. In this embodiment, the preparation step is a forming step (#2) of forming a molten raw material of the glass sheet 11 in the float bath 2 when producing a glass sheet by the float process.

[0048] The transport step (#22) is a step of transporting the mist-like substance for forming the functional layer to a position facing the upper surface of the glass plate by a carrier gas.

[0049] The mist-like substance contains at least one of a raw material of the functional layer and a precursor of the raw material when the functional layer is formed by mist CVD.

[0050] The source material can be selected depending on the functional layer to be formed, and is not particularly limited, but may be, for example, cobalt (III) acetylacetonate.

[0051] The mist-like substance is generated by misting an aqueous solution of the above-mentioned raw materials. Note that solutions other than aqueous solutions may also be misted. Examples of solvents that can be used other than water include toluene and methanol. Furthermore, instead of a solution, a dispersion in which powdered raw materials are dispersed in a liquid may also be misted.

[0052] The carrier gas is not particularly limited as long as it is a gas that can carry the mist-like substance, and for example, an inert gas such as helium, nitrogen, or argon can be used.

[0053] Alternatively, a gas that reacts with the mist-like substance to become part of the raw material for the functional layer may be used as the carrier gas. Examples of gases that react with the mist-like substance include hydrogen, oxygen, ozone, and ammonia. Alternatively, a mixture of an inert gas and a gas that reacts with the mist-like substance may be used as the carrier gas.

[0054] Thus, the carrier gas is not limited to an inert gas, and any gas capable of transporting the mist-like substance is considered to be a "carrier gas" in the present invention, regardless of whether it reacts with the mist-like substance or not.

[0055] The supply step (#24) is a step of supplying a mist-like substance from the opposing position toward the first main surface of the glass sheet. In this embodiment, the mist-like substance transported to the opposing position by the mist transport path 21 is supplied to the supply nozzle 22 via the communication path 21a. The mist-like substance supplied to the supply nozzle 22 is supplied to the upper surface of the glass sheet from the supply opening 22a. That is, in this embodiment, the upper surface of the glass sheet 11 floating in and being formed on the molten tin corresponds to the first main surface, and the lower surface (the surface in contact with the molten tin) corresponds to the second main surface.

[0056] In the present embodiment, in the preparation step (#21), the glass sheet 11 is prepared in a position along the horizontal direction. Note that the "position along the horizontal direction" is not limited to a horizontal position, and it is sufficient that the first and second main surfaces of the glass sheet 11 are aligned with the installation floor surface of the glass sheet production line 100. In other words, the "position along the horizontal direction" includes, for example, a horizontal position and a position inclined from the horizontal position by 15° or less.

[0057] In addition, in the supply step (#24), a protective gas for protecting the mist-like substance is supplied along the inner wall surface of the supply nozzle 22 in the direction of the first main surface (upper surface).

[0058] The protective gas is not particularly limited, and may be, for example, an inert gas such as helium, nitrogen, or argon. Alternatively, a gas that reacts with the mist-like substance to become part of the raw material of the functional layer may be used as the protective gas. Examples of gases that react with the mist-like substance include hydrogen, oxygen, ozone, and ammonia. Alternatively, the protective gas may be a mixture of an inert gas and a gas that reacts with the mist-like substance. The protective gas may be the same gas as the carrier gas, or a different gas.

[0059] In addition to the above steps, the method for manufacturing a glass plate with this functional layer also includes a temperature adjustment step (#23). The temperature adjustment step (#23) is a step of cooling the mist-like substance in the transport step (#22). In this embodiment, the mist transport path 21 is covered with a water-cooling jacket 24, and the mist-like substance is cooled as it is transported through the mist transport path 21, thereby suppressing a temperature rise. Note that if the supply step (#22) is performed at a low temperature, the mist-like substance may be heated in the temperature adjustment step (#23).

[0060] The functional layer forming step (#25) is a step of forming a functional layer on the first main surface (upper surface) of the glass plate. In this embodiment, the functional film is formed by mist CVD. That is, the raw material in the mist material reacts with other raw material to form the functional film on the first main surface. That is, in this embodiment, the functional layer forming step (#25) includes a functional film forming step of forming the functional film.

[0061] Examples of the functional film formed in this embodiment include optical control films such as light-absorbing films, infrared-reflecting films, UV-cutting films, high-reflecting films, low-reflecting films, light-diffusing films, transparent conductive films, etc. Further examples of the functional film include functional films (functional layers) such as semiconductor layers, solar cell electricity transport layers, hole transport layers, band alignment layers, buffer layers, mechanically durable films, and chemically durable films.

[0062] Thereafter, as shown in FIG. 1, the glass plate 10 with functional layers is manufactured through the above-mentioned slow cooling step (#3), cutting step (#4), and the like.

[0063] [Other Embodiments] Although one embodiment of the present invention has been described above, the present invention is not limited to the above embodiment, and various modifications are possible without departing from the spirit of the present invention. Note that the following other embodiments can be combined as appropriate.

[0064] (1) In the above embodiment, a functional film (functional layer) is formed on the first main surface of a glass plate by mist CVD, but this is not limiting. For example, a method other than mist CVD may be used as long as the functional film (functional layer) is formed on the first main surface using a mist-like substance such as a sol-gel method.

[0065] (2) In the above embodiment, a functional film serving as a functional layer is formed on the first principal surface using a mist-like substance. However, this is not limiting. For example, a portion of the first principal surface of the glass plate may be modified to form a functional layer using a mist-like substance. For example, a mist of hydrofluoric acid solution may be used as the mist-like substance to modify a portion of the first principal surface of the glass plate to form a functional layer. That is, in this embodiment, the functional layer forming step (#25) includes a modification step of modifying a portion of the first principal surface of the glass plate to form a functional layer.

[0066] (3) In the above embodiment, the functional layer is formed in the float bath 2 (forming step) in the glass manufacturing process using the float method. However, the present invention is not limited to this. For example, the functional layer may be formed in a step other than the forming step, such as the annealing step (annealing furnace 3).

[0067] (4) In the above embodiment, the functional layer is formed in the glass manufacturing process using the float method, but the present invention is not limited to this. For example, the functional layer may be formed in a glass manufacturing process other than the float method, such as a roll-out method or a fusion method.

[0068] (5) In the above embodiment, a functional layer is formed on a glass plate oriented along the horizontal direction, but this is not limited to this. For example, a functional layer may be formed on a glass plate oriented along the vertical direction. For example, when manufacturing a glass plate using the fusion method, the glass plate is formed in a vertical direction. Therefore, by forming a functional layer on a glass plate oriented along the vertical direction, the functional layer can be preferably formed in the manufacturing process using the fusion method.

[0069] (6) In the above embodiment, the functional layer is formed during the manufacturing process of the glass sheet, such as by online mist CVD, but the present invention is not limited to this. The functional layer may be formed on the glass sheet after the glass sheet is manufactured.

[0070] INDUSTRIAL APPLICABILITY The present invention can be widely applied to a method for producing a glass plate with a functional layer and an apparatus for forming a functional layer.

[0071] 10: Glass plate with functional layer 11: Glass plate 12: Functional layer 20: Functional layer forming device 21: Header pipe (transport flow path) 22: Supply nozzle 22a: Supply opening 23: Protective gas supply pipe (protective gas supply means) 24: Water cooling jacket (heat medium jacket) #21: Preparation step #22: Transport step #23: Temperature adjustment step #24: Supply step #25: Functional layer forming step

Claims

1. A method for manufacturing a glass plate with a functional layer, which forms a functional layer on the first main surface of a glass plate having a first main surface and a second main surface, comprising: a preparation step for preparing the glass plate; a transport step for transporting a mist-like substance for forming the functional layer to a position facing the first main surface using a carrier gas; a supply step for supplying the mist-like substance from the facing position toward the first main surface; and a functional layer formation step for forming a functional layer on the first main surface.

2. A method for manufacturing a glass plate with a functional layer as described in claim 1, wherein in the supply step, the mist-like substance is supplied from a supply nozzle arranged from the opposing position toward the first main surface, and a protective gas for protecting the mist-like substance is supplied along the inner wall surface of the supply nozzle from the opposing position toward the first main surface.

3. The method for manufacturing a glass plate with a functional layer according to claim 1, wherein the preparation step is a shaping step of shaping the molten raw material of the glass plate in a float bath when manufacturing a glass plate by a float method, and in the supply step, the mist-like substance is supplied toward the first main surface of the glass plate during the shaping step.

4. The method for manufacturing a glass plate according to claim 3, wherein a temperature adjusting step of adjusting the temperature of the mist-like substance is carried out in the transporting step.

5. A method for manufacturing a glass plate with a functional layer described in any one of claims 1 to 4, wherein the functional layer formation step includes a film formation step of forming a functional film on the first main surface using the mist-like substance as at least a part of a raw material or a precursor of the raw material.

6. The method for producing a glass plate with a functional layer according to claim 5, wherein the film forming step is carried out by mist CVD.

7. A method for manufacturing a glass plate with a functional layer described in any one of claims 1 to 4, wherein the functional layer forming step includes a modification step in which a portion of the first main surface of the glass plate is modified with the mist-like substance to form the functional layer.

8. A functional layer forming device used in the method for manufacturing a glass plate with a functional layer according to any one of claims 1 to 4, comprising: a transport flow path that transports a mist-like substance for forming the functional layer to a position facing the first main surface using a carrier gas; and a supply nozzle that communicates with the transport flow path and supplies the mist-like substance from the facing position towards the first main surface.

9. The functional layer forming apparatus according to claim 8, wherein the supply nozzle has a supply opening that spans the entire width direction perpendicular to the direction of relative movement between the glass plate and the supply nozzle.

10. The functional layer forming device according to claim 8, further comprising a protective gas supply means for supplying a protective gas to protect the mist-like substance along the inner wall surface of the supply nozzle.

11. The functional layer forming apparatus according to claim 8, further comprising a heat medium jacket covering the transport flow path.

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