WO2015099157A1 - Method for producing glass substrate and glass-substrate production device - Google Patents

Method for producing glass substrate and glass-substrate production device Download PDF

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Publication number
WO2015099157A1
WO2015099157A1 PCT/JP2014/084643 JP2014084643W WO2015099157A1 WO 2015099157 A1 WO2015099157 A1 WO 2015099157A1 JP 2014084643 W JP2014084643 W JP 2014084643W WO 2015099157 A1 WO2015099157 A1 WO 2015099157A1
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WIPO (PCT)
Prior art keywords
molten glass
amount
glass
clarification
temperature
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PCT/JP2014/084643
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French (fr)
Japanese (ja)
Inventor
慎吾 藤本
諒 鈴木
Original Assignee
AvanStrate株式会社
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Application filed by AvanStrate株式会社 filed Critical AvanStrate株式会社
Priority to JP2014561667A priority Critical patent/JPWO2015099157A1/en
Priority to KR1020157002182A priority patent/KR101743375B1/en
Publication of WO2015099157A1 publication Critical patent/WO2015099157A1/en

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    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03BMANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B5/00Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
    • C03B5/16Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
    • C03B5/225Refining
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03BMANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B5/00Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
    • C03B5/16Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
    • C03B5/24Automatically regulating the melting process
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03BMANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B5/00Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
    • C03B5/16Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
    • C03B5/42Details of construction of furnace walls, e.g. to prevent corrosion; Use of materials for furnace walls
    • C03B5/43Use of materials for furnace walls, e.g. fire-bricks
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03BMANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B5/00Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
    • C03B5/04Melting in furnaces; Furnaces so far as specially adapted for glass manufacture in tank furnaces

Definitions

  • the present invention relates to a glass substrate manufacturing method and a glass substrate manufacturing apparatus.
  • a glass substrate is generally manufactured through a process of forming molten glass from a glass raw material and then forming the molten glass into a glass substrate.
  • the above process includes a process of removing minute bubbles contained in the molten glass (hereinafter also referred to as clarification).
  • the clarification is performed by passing a molten glass containing a clarifier in the clarifier tube body while heating the clarifier tube body, and removing bubbles in the molten glass by an oxidation-reduction reaction of the clarifier. More specifically, the temperature of the molten glass that has been melted further is further raised to allow the fining agent to function and the bubbles to float and defoam.
  • the glass is made to absorb.
  • clarification includes a process for floating and defoaming bubbles (hereinafter also referred to as a defoaming process or a defoaming process) and a process for absorbing small bubbles into molten glass (hereinafter also referred to as an absorption process or an absorbing process).
  • Patent Document 1 A technique for heating the clarification tube in order to heat the molten glass in the clarification treatment, for example, a pair of flange-shaped electrodes are provided in the clarification tube, and the voltage is applied to the electrode pair to energize the clarification tube.
  • a technique for heating is known (Patent Document 1).
  • the amount of heat applied to the molten glass in the clarification tube can be adjusted by the amount of current supplied to the clarification tube. For this reason, even if the flow volume of the molten glass which passes a clarification pipe
  • the viscosity of the molten glass is determined by the temperature of the molten glass, and the temperature of the molten glass is controlled by the amount of current supplied to the clarification tube. For this reason, the flow rate of the molten glass can be controlled by the energization amount to the clarifier tube outlet. However, if the temperature in the low temperature region of the clarification tube is raised and the amount of heating in the subsequent process is reduced, the amount of current supplied to the clarification tube outlet becomes small, and the flow rate of the molten glass cannot be controlled.
  • the temperature of the molten glass cannot be lowered even if, for example, the energization amount at the clarification tube outlet is zero, and the flow rate of the molten glass cannot be controlled. If it becomes impossible to control the flow rate of the molten glass, there is a concern that a problem may occur that the molten glass overflows in the processing apparatus downstream of the clarification tube. Moreover, since it becomes difficult to lower
  • An object of the present invention is to provide a glass substrate manufacturing method and a glass substrate manufacturing apparatus capable of achieving both a refining effect and a flow control of a molten glass even when the flow rate of the molten glass is large.
  • the present invention has the following forms.
  • (Form 1) A method for manufacturing a glass substrate using a processing apparatus for processing molten glass, When processing molten glass, Heating the processing device by energizing the processing device so that the temperature of the molten glass in the processing device is in a range suitable for the processing, The flow rate of the molten glass in the processing device is controlled by the amount of electric power when energizing, The amount of heat radiation from the processing device to the outside is set so that the amount of electric power is equal to or greater than the amount of electric power capable of controlling the flow rate of the molten glass, and the temperature of the molten glass is in a temperature range capable of controlling the flow rate of the molten glass. A method of manufacturing a glass substrate to be adjusted.
  • Form 2 A method for manufacturing a glass substrate using a processing apparatus for processing molten glass, When processing molten glass, Heating the processing device by energizing the processing device so that the temperature of the molten glass in the processing device is in a range suitable for the processing, The flow rate of the molten glass in the processing device is controlled by the amount of current when the current is applied, A method for producing a glass substrate, wherein the amount of heat released from the processing device to the outside is adjusted so as to be equal to or greater than an amount of current that enables flow control of the molten glass.
  • the flow rate of the molten glass indicates the moving amount (volume or mass) of the molten glass per unit time.
  • the processing apparatus includes a melting tank, a refining apparatus, a stirring tank and a forming apparatus, a transfer pipe for transferring molten glass through these apparatus tubes, and a supply pipe for supplying glass to these apparatuses.
  • the processing in the processing apparatus includes glass melting processing, molten glass clarification processing, stirring processing, molding processing, and molten glass transfer processing and supply processing.
  • the processing apparatus has a gas phase space formed by an inner wall and a molten glass liquid surface, and at least a portion of the inner wall in contact with the gas phase space is made of a material containing a platinum group metal,
  • a high temperature region and a low temperature region lower in temperature than the high temperature region are formed,
  • region may be 200 degrees C or less.
  • the platinum group metal means a metal composed of a single platinum group element and an alloy of a metal composed of a platinum group element.
  • the platinum group elements are six elements of platinum (Pt), palladium (Pd), rhodium (Rh), ruthenium (Ru), osmium (Os) and iridium (Ir).
  • the high temperature region may be a region where the temperature of the processing apparatus is in a temperature range of 1600 ° C. or higher, and the low temperature region may be a region where the temperature of the processing apparatus is in a temperature range of less than 1600 ° C.
  • the high temperature region may be a region where the temperature of the processing apparatus is in a temperature range of 1620 ° C. or higher, and the low temperature region may be a region where the temperature of the processing apparatus is in a temperature range of 1590 ° C. or lower.
  • the electrode region which is the region where the electrode provided in the processing apparatus is provided, and the region where the exhaust pipe is provided are the low temperature region, and the region other than the low temperature region or the region between the electrode and the exhaust pipe is the high temperature region. May be. It is preferable to adjust the heat radiation amount so that the maximum temperature in the high temperature region is 1600 to 1750 ° C. and the minimum temperature in the low temperature region is 1300 to 1600 ° C. By reducing the temperature difference between the high temperature region and the low temperature region, the amount of aggregation of the platinum group metal volatilized in the high temperature region in the low temperature region can be reduced.
  • the problem of mixing foreign substances derived from volatile aggregates such as the above platinum group metals into the molten glass is a display typified by a liquid crystal display whose quality requirements are becoming increasingly severe with the recent high definition. It becomes larger with the glass substrate. Therefore, the said form is suitable with the manufacturing method of the glass substrate for displays.
  • the treatment device is covered with a heat insulating material, The method for manufacturing a glass substrate according to any one of Embodiments 1 to 3, wherein the heat radiation amount is controlled by adjusting a thermal resistance from the processing apparatus to an external space by the heat insulating material.
  • the manufacturing method of the glass substrate of the form 4 which adjusts the said thermal resistance by adjusting the thermal conductivity and arrangement
  • the said processing apparatus is a clarification apparatus which clarifies molten glass.
  • the clarifier is heated by energizing the clarifier so that the maximum temperature of the molten glass in the clarifier is equal to or higher than the temperature at which the reduction reaction of tin oxide contained in the molten glass occurs.
  • the flow rate of the molten glass in the clarification device is controlled by the amount of electric power when the current is applied, and from the clarification device to the outside so that the amount of electric power is equal to or greater than the amount of electric power capable of controlling the flow rate of the molten glass.
  • the method for producing a glass substrate according to any one of embodiments 1 to 5, wherein the amount of heat radiation is adjusted.
  • the maximum temperature of the molten glass in the processing apparatus is preferably 1630 ° C to 1720 ° C.
  • the fining agent in the molten glass can exert a clarification effect, and when it is 1720 ° C. or lower, the temperature difference between the high temperature region and the low temperature region can be reduced. It is possible to achieve both reduction of bubbles and reduction of the volatilization amount of the platinum group metal.
  • the content of tin oxide in the molten glass is preferably 0.01 to 0.3 mol%. If the content of tin oxide is too small, bubbles cannot be sufficiently reduced.
  • the clarification device is discharged from the clarification tube having a gas phase space through which bubbles in the molten glass are discharged, a first transfer tube to which the molten glass supplied into the clarification tube is transferred, and the clarification tube.
  • a second transfer pipe through which the molten glass is transferred, In the first transfer pipe, the clarification pipe, and the second transfer pipe, the defoaming treatment of the molten glass by the reductive reaction of the clarifier and the absorption treatment that absorbs the bubbles in the molten glass by the oxidation reaction of the clarifier.
  • the amount of power to be applied to the first transfer pipe, the amount of power to be applied to the region for performing the defoaming process among the clarification pipe and the second transfer pipe, and the clarification pipe and the second transfer pipe The method of manufacturing a glass substrate according to mode 6, wherein the ratio of the amount of electric power applied to the region where the absorption treatment is performed is 1: 0.6 to 1: 0.1 to 0.4.
  • the clarification device is discharged from the clarification tube having a gas phase space through which bubbles in the molten glass are discharged, a first transfer tube to which the molten glass supplied into the clarification tube is transferred, and the clarification tube.
  • a second transfer pipe through which the molten glass is transferred In a partial region of the clarification tube, a defoaming treatment of the molten glass is performed by a reduction reaction of the clarifier, In the other region of the clarification tube and the second transfer tube, an absorption treatment for absorbing bubbles in the molten glass by an oxidation reaction of the clarifier is performed,
  • the ratio of the amount of power applied to the first transfer pipe, the amount of power applied to a partial area of the clarification pipe, and the amount of power supplied to the other area of the clarification pipe is from 1: 0.6 to 1:
  • the processing device is discharged from the clarification tube having a gas phase space in which bubbles in the molten glass are discharged, a first transfer tube to which the molten glass supplied into the clarification tube is transferred, and the clarification tube.
  • the ratio of the amount of power applied to the first transfer tube, the amount of power applied to the clarification tube, and the amount of power applied to the second transfer tube is 1: 0.6 to 1: 0.1 to The manufacturing method of the glass substrate of form 6 which is 0.4.
  • the region where the defoaming treatment is performed refers to a region where the temperature is 1620 ° C. or higher.
  • the maximum temperature of the molten glass in the region where the defoaming treatment is performed is preferably 1630 ° C. to 1720 ° C., and more preferably 1640 ° C. to 1720 ° C.
  • the maximum temperature of the treatment apparatus in the region where defoaming treatment is performed is preferably 1630 ° C. to 1750 ° C., and more preferably 1640 ° C. to 1750 ° C.
  • the region where the absorption treatment is performed refers to a region where the temperature is less than 1620 ° C.
  • the temperature of the molten glass in the region where the absorption treatment is performed is preferably 1450 ° C. to 1620 ° C. By setting it as this temperature range, absorption of the bubble by the oxidation reaction of a clarifying agent can be performed effectively.
  • the oxygen concentration in the gas phase space is preferably 0 to 10%.
  • the volatilization amount of the platinum group metal can be reduced.
  • the vapor pressure of the platinum group metal in the gas phase space is preferably 0.1 Pa to 15 Pa. When the vapor pressure of the platinum group metal is within this range, the reduced platinum group metal can be prevented from adhering to the inner wall surface.
  • Form 10 A processing apparatus for processing molten glass; An energizer that heats the processing apparatus by energizing the processing apparatus so that the temperature of the molten glass in the processing apparatus is in a range suitable for the processing when the molten glass is processed; A control device for controlling the flow rate of the molten glass in the processing device by the amount of electric power when energizing, The amount of heat radiation from the processing device to the outside is such that the amount of electric power is equal to or greater than the amount of electric power capable of controlling the flow rate of the molten glass, and the temperature of the molten glass is within a temperature range capable of controlling the flow rate of the molten glass. Glass substrate manufacturing equipment that is being adjusted.
  • Form 11 A processing apparatus for processing molten glass; An energizer that heats the processing apparatus by energizing the processing apparatus so that the temperature of the molten glass in the processing apparatus is in a range suitable for the processing when the molten glass is processed; A control device for controlling the flow rate of the molten glass in the processing device by the amount of current when the current is applied; The glass substrate manufacturing apparatus in which the amount of heat radiation from the processing apparatus to the outside is adjusted so as to be equal to or greater than the amount of current capable of controlling the flow rate of the molten glass.
  • the processing apparatus has a gas phase space formed from an inner wall and a molten glass liquid surface, and at least a portion of the inner wall that is in contact with the gas phase space is made of a material containing a platinum group metal, and volatilizes the platinum group metal.
  • the maximum length of the platinum group metal aggregate is 50 ⁇ m to 300 ⁇ m
  • the minimum length is 0.5 ⁇ m to 2 ⁇ m.
  • the maximum length of the platinum group metal aggregate is the maximum long side length of the circumscribed rectangle circumscribing the image of the foreign material obtained by photographing the platinum group metal aggregate.
  • the minimum length is And the length of the minimum short side of the circumscribed rectangle.
  • the aggregate generated by the aggregation of the platinum group metal volatiles has an aspect ratio of 100 or more, which is a ratio of the maximum length to the minimum length, and the maximum length of the platinum group metal aggregate is 100 ⁇ m.
  • the above may preferably be 100 ⁇ m to 300 ⁇ m.
  • Form 13 The glass substrate manufacturing method or glass substrate manufacturing apparatus according to any one of Embodiments 1 to 12, wherein the glass substrate is a glass substrate for display. Moreover, it is suitable for the glass substrate for oxide semiconductor displays or the glass substrate for LTPS displays.
  • the clarification effect and the flow rate control of the molten glass can be realized.
  • FIG. 2 is a view schematically showing an example of an apparatus for performing a melting process to a cutting process shown in FIG. It is the schematic which shows the structure of the clarification pipe
  • FIG. It is sectional drawing of the clarification pipe
  • FIG. 1 is a diagram illustrating an example of a process of a glass substrate manufacturing method according to the present embodiment.
  • the glass substrate manufacturing method includes a melting step (ST1), a clarification step (ST2), a homogenization step (ST3), a supply step (ST4), a forming step (ST5), and a slow cooling step (ST6). And a cutting step (ST7).
  • a plurality of glass substrates that have a grinding process, a polishing process, a cleaning process, an inspection process, a packing process, and the like and are stacked in the packing process are transported to a supplier.
  • the melting step (ST1) is performed in a melting tank.
  • a glass raw material is poured into the liquid surface of the molten glass stored in the melting tank and heated to make molten glass.
  • molten glass is poured toward the downstream process from the outlet provided in one bottom part of the inner side wall of the melting tank.
  • the heating of the molten glass in the melting tank can melt the glass raw material in addition to energizing heating, which is a method in which electricity flows through the molten glass itself to generate and heat itself, and supplementary flame is provided by a burner.
  • molten glass contains a clarifier.
  • the fining agent tin oxide, arsenous acid, antimony, and the like are known, but are not particularly limited.
  • tin oxide as a clarifying agent from the viewpoint of reducing environmental burden.
  • the content of tin oxide is preferably 0.01 to 0.3 mol%, and more preferably 0.03 to 0.2 mol%. If the content of tin oxide is too small, bubbles cannot be sufficiently reduced. On the other hand, when the content of tin oxide is too large, the volatilization amount of tin oxide from the molten glass increases, and there arises a problem that aggregates of volatilized tin oxide are mixed into the molten glass.
  • Tin oxide has a lower refining function than arsenous acid that has been generally used, but can be suitably used as a refining agent in terms of low environmental burden.
  • the temperature of the molten glass MG during the refining process of the molten glass MG must be made higher than before.
  • the maximum temperature of the molten glass is increased, if the temperature in the low temperature region of the processing apparatus is increased in order to suppress the aggregation of the platinum group metal, the temperature of the molten glass of the molten glass becomes too high, and the flow rate due to current is increased. There is a problem that it becomes difficult to control. Therefore, the volatilization amount of the platinum group metal from the clarification tube which will be described later increases, and as a result, the problem that the platinum group metal is mixed as a foreign substance in the glass substrate becomes remarkable.
  • the clarification step (ST2) is performed at least in the clarification tube.
  • the clarification step includes a defoaming process and an absorption process.
  • the defoaming treatment when the molten glass is heated, the bubbles containing oxygen, CO 2 or SO 2 contained in the molten glass absorb oxygen generated by the reductive reaction of the fining agent, and the volume increases. Then, it floats on the liquid surface of the molten glass and is discharged.
  • a defoaming process is performed in the area
  • a region of the processing apparatus in which the temperature of the molten glass is 1620 ° C. or higher is defined as “a region where defoaming is performed”.
  • the temperature of the region where the defoaming treatment is performed is preferably 1620 ° C. to 1750 ° C.
  • the maximum temperature of the molten glass in the region where the defoaming treatment is performed is preferably 1630 ° C. to 1720 ° C., more preferably 1640 ° C. to 1720 ° C.
  • the maximum temperature of the treatment apparatus in the region where defoaming treatment is performed is preferably 1630 ° C. to 1750 ° C., and more preferably 1640 ° C. to 1750 ° C.
  • the absorption processing by reducing the temperature of the molten glass, the reducing substance obtained by the reductive reaction of the fining agent undergoes an oxidation reaction. Thereby, gas components, such as oxygen in the bubble which remain
  • the absorption processing is performed in a region downstream of the region where the degassing processing of the processing apparatus is performed and the temperature of the molten glass is less than 1620 ° C.
  • a region of the processing apparatus in which the temperature of the molten glass is less than 1620 ° C. is referred to as “region for performing absorption treatment”.
  • the temperature of the region where the absorption treatment is performed is preferably 1450 ° C.
  • the temperature of the molten glass in the region where the absorption treatment is performed is preferably 1450 ° C. to 1620 ° C. By setting it as this temperature range, absorption of the bubble by the oxidation reaction of a clarifying agent can be performed effectively.
  • the oxidation reaction and reduction reaction by the fining agent are performed by controlling the temperature of the molten glass.
  • a clarification method using tin oxide as a clarifier will be described.
  • a reduced pressure defoaming method can be used in which a space in a reduced pressure atmosphere is formed in a clarified tube, and bubbles existing in the molten glass are grown in a reduced pressure atmosphere and defoamed. In this case, it is effective in that no clarifier is used.
  • the vacuum defoaming method complicates and enlarges the apparatus, it is preferable to employ a clarification method that uses a clarifier and raises the temperature of the molten glass.
  • the glass component is homogenized by stirring the molten glass in the stirring tank supplied through the pipe extending from the clarification pipe using a stirrer. Thereby, the composition unevenness of the glass which is a cause of striae or the like can be reduced.
  • the supply step (ST4) the molten glass is supplied to the molding apparatus through a pipe extending from the stirring tank.
  • the molding step (ST5) and the slow cooling step (ST6) are performed by a molding apparatus.
  • the forming step (ST5) the molten glass is formed into a sheet glass to make a flow of the sheet glass.
  • An overflow downdraw method is used for molding.
  • the slow cooling step (ST6) the sheet glass that has been formed and flowed is cooled to a desired thickness, so that internal distortion does not occur and warpage does not occur.
  • the cutting step (ST7) the sheet glass supplied from the forming device is cut into a predetermined length in the cutting device to obtain a plate-like glass substrate. The cut glass substrate is further cut into a predetermined size to produce a glass substrate having a target size.
  • FIG. 2 is a diagram schematically showing an example of an apparatus for performing the melting step (ST1) to the cutting step (ST7) in the present embodiment.
  • the apparatus mainly includes a melting apparatus 100 and a molding apparatus 200.
  • the melting apparatus 100 includes a melting tank 101, a clarification pipe 120, a stirring tank 103, a first transfer pipe 104, a second transfer pipe 105, and a glass supply pipe 106.
  • the melting tank 101 shown in FIG. 2 is provided with heating means such as a burner (not shown). A glass raw material to which a fining agent is added is charged into the melting tank, and a melting process is performed. The molten glass melted in the melting tank 101 is supplied to the clarification tube 120 through the transfer tube 104.
  • the temperature of the molten glass MG is adjusted, and the clarification step of the molten glass is performed using the oxidation-reduction reaction of the clarifier.
  • the clarified molten glass is supplied to the stirring tank through the transfer pipe 105.
  • the defoaming process may be performed in the transfer pipe 104. That is, the transfer pipe 104 may have a “region for performing a defoaming process”.
  • the absorption process may be performed in the transfer pipe 105. That is, the transfer pipe 105 may have an “area for performing an absorption process”.
  • the clarification tube 120 is provided with electrodes 121a and 121b. When a voltage is applied between the electrodes 121a and 121b, an electric current flows through the clarification tube 120 between the electrodes 121a and 121b, and the clarification tube 120 is provided. Is heated by energization.
  • electrodes (not shown) are provided at both ends of the first transfer pipe 104 and the second transfer pipe 105, and when a voltage is applied between the electrodes, the first transfer pipe 104 and the second transfer pipe 104 are provided. A current flows through the first transfer pipe 105 and the first transfer pipe 104 and the second transfer pipe 105 are energized and heated.
  • the electrodes 121a and 121b have a flange shape from the viewpoint of preventing damage due to overheating.
  • the walls near the electrodes 121a and 121b are at a lower temperature than the peripheral portions of the walls.
  • the electrodes 121a and 121b are cooled with a liquid or a gas in order to suppress damage due to overheating, for example.
  • the temperature of the wall of the clarification tube 120 in contact with the gas phase space necessarily has a temperature profile along the flow direction of the molten glass. In other words, in the case of the clarification tube 120 of the present embodiment, the temperature of the clarification tube 120 does not become constant, and a temperature difference inevitably occurs.
  • the amount of power to be applied to the first transfer pipe 104, the amount of power to be supplied to the region of the clarification tube 120 to be defoamed, and the power to be supplied to the region of the clarification tube 120 and the second transfer tube 105 to be subjected to the absorption process is preferably 1: 0.6 to 1: 0.1 to 0.4, and more preferably 1: 0.7 to 1: 0.15 to 0.4.
  • the ratio of the amount of electric power applied to the second transfer pipe 105 is preferably 1: 0.6 to 1: 0.1 to 0.4, and 1: 0.7 to 1: 0.15 to It is preferable that it is 0.4.
  • the molten glass is stirred and homogenized by the stirrer 103a.
  • the molten glass homogenized in the stirring tank 103 is supplied to the forming apparatus 200 through the glass supply pipe 106.
  • sheet glass is formed from molten glass by the overflow downdraw method.
  • FIG. 3 is a schematic diagram illustrating a configuration of the clarification tube 120 according to the embodiment.
  • electrodes 121 a and 121 b are provided on the outer peripheral surfaces of both ends in the length direction of the clarification tube 120, and an exhaust pipe 127 is provided on the wall in contact with the gas phase space of the clarification tube 120. It has been.
  • the clarification tube 120 is preferably made of platinum, reinforced platinum, or a platinum alloy.
  • platinum group metal means a metal composed of a platinum group element, and is used as a term including not only a metal composed of a single platinum group element but also an alloy of the platinum group element.
  • the platinum group element refers to six elements of platinum (Pt), palladium (Pd), rhodium (Rh), ruthenium (Ru), osmium (Os), and iridium (Ir). Platinum group metals are expensive, but have a high melting point and excellent corrosion resistance against molten glass.
  • the clarification tube 120 is made of a platinum group metal will be described as a specific example. However, a part of the clarification tube 120 may be made of a refractory or other metal. .
  • the electrodes 121 a and 121 b are connected to the power supply device 122.
  • a voltage is applied between the electrodes 121a and 121b, a current flows through the clarification tube 120 between the electrodes 121a and 121b, and the clarification tube 120 is energized and heated.
  • the clarification tube 120 is heated so that the maximum temperature is, for example, 1600 ° C. to 1750 ° C., more preferably 1630 ° C. to 1750 ° C., and the maximum temperature of the molten glass supplied from the glass supply tube 104 is It is heated to a temperature suitable for the defoaming treatment, for example, 1630 ° C. to 1720 ° C.
  • the target power amount to be passed through the clarification tube 120 is more preferably 5 kW or more, and more preferably 10 kW or more.
  • the target power amount to be energized at the outlet of the clarification tube 120 is preferably 5 kW or more, and more preferably 8 kW or more.
  • the electrodes 121a and 121b may be provided with a temperature measurement device (thermocouple or the like) (not shown).
  • the temperature measuring device measures the temperature of the electrodes 121 a and 121 b and outputs the measured result to the control device 123.
  • the control device 123 is a computer including a CPU, a memory, and the like.
  • the control device 123 controls the amount of current and the amount of power that the power supply device 122 supplies to the clarification tube 120. Thereby, the control apparatus 123 can adjust the temperature and flow velocity of the molten glass in the clarification tube 120.
  • An exhaust pipe 127 is provided on the wall in contact with the gas phase space of the clarification pipe 120.
  • the exhaust pipe 127 may have a shape protruding in a chimney shape from the outer wall surface of the main body of the clarification pipe 120 toward the outside.
  • the exhaust pipe 127 communicates the gas phase space 120 a that is a part of the internal space of the clarification pipe 120 and the external space of the clarification pipe 120.
  • FIG. 4 is a cross-sectional view of the clarification tube 120 in the longitudinal direction of the main body of the clarification tube 120 and in the longitudinal direction of the exhaust pipe 127.
  • a heat insulating material 140 is provided on the outer wall surface of the main body of the clarification tube 120, the outer wall surfaces of the electrodes 121 a and 121 b, and the outer wall surface of the exhaust pipe 127.
  • the heat insulating material 140 plays a role of keeping the fining tube 120 warm while supporting the fining tube 120 so as not to deform.
  • As the heat insulating material 140 a member having excellent fire resistance and sufficiently high strength (rigidity) can be used.
  • materials having different thermal conductivities As the heat insulating material 140, a first heat insulating material having a higher thermal conductivity and a second heat insulating material having a lower thermal conductivity are used, and the first heat insulating material is disposed in a region that promotes heat dissipation of the clarification tube 120.
  • the amount of heat released from each region of the clarification tube 120 can be adjusted. It is not necessary to provide the first heat insulating material so as to contact the entire region of the clarification tube 120. It is preferable that the heat transfer medium 130 is selectively provided at least at a location that contacts the high temperature region and a location that contacts the low temperature region, and the heat transfer medium 130 is provided so as to connect both.
  • the thermal conductivity of the first heat insulating material is preferably at least twice that of the second heat insulating material, and more preferably at least five times. It is preferable to use a material having a thermal conductivity of 2 to 40 W / m ⁇ K at 1000 ° C. as the first heat insulating material.
  • an alumina electrocast refractory, a magnesia refractory, a silicon carbide refractory, or the like can be used as the first heat insulating material.
  • a material having a thermal conductivity at 1000 ° C. of 0.1 to 1 W / m ⁇ K is preferably used.
  • porous brick, ceramic fiber, or the like can be used as the second heat insulating material.
  • the amount of heat released from the clarification tube 120 to the outside can be controlled by controlling the temperature and flow rate of the molten glass while the control device 123 supplies current to the clarification tube 120 so that the current amount is greater than or equal to the target current amount. It is adjusted to.
  • This amount of heat radiation is the amount of heat radiation required when the flow rate of the molten glass passing through the clarification tube 120 is maximized.
  • the amount of heat radiation can be controlled by adjusting the thermal resistance from the clarification tube 120 to the external space. For example, the thermal resistance can be adjusted by adjusting the thermal conductivity and arrangement of the first heat insulating material and the second heat insulating material used as the heat insulating material 140.
  • the amount of power supplied to the clarified tube is equal to or greater than the amount of power that can control the flow rate of the molten glass. Can do.
  • the temperature difference between the high temperature region and the low temperature region of the clarification tube 120 is preferably 50 ° C. or more and 200 ° C. or less, and 70 ° C. or more and 150 ° C. or less from the viewpoint of achieving both suppression of volatilization of the platinum group metal and the clarification effect. It is more preferable that it is below °C.
  • the high temperature region indicates a region having a higher temperature than other regions. In the case of the clarification tube 120, for example, the high temperature region may be a region where the temperature of the clarification tube 120 is in a temperature range of 1600 ° C. or higher, or a region in a temperature range of 1620 ° C. or higher.
  • the high temperature region may include a region where the maximum temperature is reached when the clarification tube 120 processes the molten glass.
  • the low temperature region indicates a region where the temperature is lower than that of other regions, and specifically indicates a region where the temperature is lower than that of the high temperature region.
  • the low temperature region may be a region where the temperature of the clarification tube 120 is in a temperature range of less than 1600 ° C or a temperature range of 1590 ° C or less.
  • the low temperature region may include a region where the refining tube 120 is at the lowest temperature when the molten glass is processed.
  • connection portion of the clarification tube 120 with the electrodes 121a and 121b and the connection portion with the exhaust pipe 127 are radiated to the outside from the electrodes 121a and 121b and the exhaust pipe 127. It tends to be low temperature compared to the area. That is, the region of the connection portion between the electrodes 121a and 121b of the clarification tube and the connection portion with the exhaust tube 127 is a low temperature region, and the region between the electrodes 121a and 121b and the exhaust tube 127 is a high temperature region. In order to make the temperature difference between the high temperature region and the low temperature region within the above range, the minimum temperature in the low temperature region is preferably 1300 ° C. or more and 1600 ° C.
  • the temperature is more preferably 1600 ° C. or lower.
  • the maximum temperature in the high temperature region is preferably 1600 ° C. or higher and 1750 ° C. or lower, more preferably 1600 ° C. or higher and 1720 ° C. or lower, and further preferably 1610 ° C. or higher and 1700 ° C. or lower.
  • the platinum group metal is volatilized as an oxide in a portion in contact with the gas phase space (atmosphere containing oxygen) on the heated inner surface.
  • the gas phase space atmosphere containing oxygen
  • the platinum group metal is oxidized and volatilized in the gas phase space. This volatilization is particularly noticeable in the high temperature region of the clarification tube 120.
  • the oxide of the platinum group metal is reduced at a position where the temperature is locally lowered (for example, around the electrode) of the processing apparatus, and the reduced platinum group metal aggregates and adheres (aggregates) to the inner wall surface.
  • the oxygen concentration in the gas phase space is preferably 0%.
  • the oxygen concentration in the gas phase space is preferably 0.01% or more.
  • the oxygen concentration in the gas phase space becomes too small, the oxygen concentration difference between the molten glass and the gas phase space increases, so that the oxygen released from the molten glass into the gas phase space increases and the molten glass is reduced too much. As a result, there is a possibility that bubbles such as sulfur oxide and nitrogen may remain on the glass substrate after molding.
  • the oxygen concentration in the gas phase space is preferably 0 to 30%, more preferably 0.1 to 10%, and still more preferably 0.1 to 1%. .
  • the vapor pressure of the platinum group metal in the gas phase space is preferably 0.1 Pa to 15 Pa, and more preferably 3 Pa to 10 Pa. When the vapor pressure of the platinum group metal is within this range, the reduced platinum group metal aggregates can be prevented from adhering to the inner wall surface.
  • the temperature in the low temperature region is raised, the molten glass that has been cooled in the low temperature region is not cooled, so that molten glass that is higher in temperature than the target temperature flows out downstream. Since the optimum temperature for the molten glass flowing out downstream is determined, if the temperature in the low temperature region is raised, it is necessary to reduce the heating amount in the subsequent steps.
  • the temperature of the molten glass increases when the amount of current supplied to the electrodes 121a and 121b is increased to increase the temperature in the vicinity of the electrodes 121a and 121b in the low temperature region.
  • the temperature difference between the high temperature region and the low temperature region can be adjusted by adjusting the thermal conductivity, arrangement, and amount of the heat insulating material 140. Accordingly, it is possible to avoid the situation where the flow rate cannot be adjusted by increasing the energization amount to the electrodes 121a and 121b.
  • the amount of heat transfer when the thermal conductivity, arrangement, and amount of the heat insulating material 140 are changed should be calculated by, for example, computational fluid dynamic calculation (computer simulation) using a 3D model created by the finite element method or the mesh-free method. Can do. For example, a 3D model that reproduces the refining tube 120, the heat insulating material 140, the molten glass in the refining tube 120, and the gas phase space is created, and this is divided into a finite number of regions (calculation grids), and boundary conditions (the refining tube 12 The temperature of the inner glass and the gas phase space, the temperature of the external space, etc.) and the material properties (thermal conductivity, etc.). Next, the amount of heat in and out of each calculation grid is analyzed using iterative calculation by a computer. By using computer simulation, the optimum thermal conductivity, arrangement, and amount of the heat insulating material 140 can be easily calculated economically.
  • the platinum group metal aggregate to be suppressed in the present embodiment has a linear shape elongated in one direction, which is the ratio of the maximum length to the minimum length, and the aspect ratio is 100 or more.
  • the maximum length of the platinum group metal aggregate is 50 ⁇ m to 300 ⁇ m
  • the minimum length is 0.5 ⁇ m to 2 ⁇ m.
  • the maximum length of the platinum group metal aggregate is the maximum long side length of the circumscribed rectangle circumscribing the image of the foreign material obtained by photographing the platinum group metal aggregate.
  • the minimum length is And the length of the minimum short side of the circumscribed rectangle.
  • Example 1 A glass substrate having a thickness of 2270 mm ⁇ 2000 mm and a thickness of 0.5 mm was prepared using tin oxide as a fining agent and using the manufacturing apparatus of the above embodiment.
  • the glass composition of the glass substrate was as follows: SiO 2 66.6 mol%, Al 2 O 3 10.6 mol%, B 2 O 3 11.0 mol%, MgO, CaO, SrO and BaO combined 11.4 Mol%, SnO 2 0.15 mol%, Fe 2 O 3 0.05 mol%, alkali metal oxide 0.2 mol%, the strain point is 660 ° C., and the viscosity is 10 2.5 poise.
  • the temperature of the molten glass was 1570 ° C.
  • the amount of heat released from the clarification tube was 1: 0.8: 0.3.
  • a glass substrate having a number of bubbles equal to or less than the specified number could be produced without the molten glass overflowing from the processing apparatus.
  • the number of platinum group metal foreign matters mixed into the glass substrate could be suppressed to 0.001 piece / kg or less.
  • a foreign material of the platinum group metal those having an aspect ratio of 100 or more and a maximum length of 100 ⁇ m or more were counted.
  • the glass composition of the glass substrate to be manufactured was SiO 2 70 mol%, Al 2 O 3 12.9 mol%, B 2 O 3 2.5 mol%, MgO 3.5 mol%, CaO. 6 mol%, SrO 1.5 mol%, BaO 3.5 mol%, to prepare a glass substrate in the same manner as in example 1 except that the SnO 2 0.1 mol%.
  • the strain point of the glass substrate was 745 ° C.
  • the effect of this embodiment becomes remarkable when it is a non-alkali glass substrate containing tin oxide or a fine alkali glass substrate containing tin oxide.
  • the alkali-free glass or fine alkali glass has a higher glass viscosity than the alkali glass. Therefore, it is necessary to increase the melting temperature in the melting process, and many tin oxides are reduced in the melting process. Therefore, in order to obtain a clarification effect, the molten glass temperature in the clarification process is increased to reduce the tin oxide. Is required to be further promoted and the viscosity of the molten glass needs to be lowered.
  • the alkali-free glass substrate is a glass that substantially does not contain alkali metal oxides (Li 2 O, K 2 O, and Na 2 O).
  • the fine alkali glass is a glass having an alkali metal oxide content (total amount of Li 2 O, K 2 O, and Na 2 O) of more than 0 and not more than 0.8 mol%.
  • the glass substrate of the following glass compositions is illustrated. Therefore, the glass raw material is prepared so that the glass substrate has the following glass composition.
  • the glass substrate produced in the present embodiment includes, for example, SiO 2 55 to 75 mol%, Al 2 O 3 5 to 20 mol%, B 2 O 3 0 to 15 mol%, RO 5 to 20 mol% (RO is MgO, CaO, SrO and BaO total amount), R ′ 2 O 0 to 0.4 mol% (R ′ is the total amount of Li 2 O, K 2 O and Na 2 O), SnO 2 0.01 to Contains 0.4 mol%.
  • R is all elements contained in the glass substrate among Mg, Ca, Sr, and Ba
  • ((2 ⁇ SiO 2 ) + Al 2 O 3 ) / ((2 ⁇ B 2 O 3 ) + RO) may be 4.0 or more.
  • a glass having a molar ratio ((2 ⁇ SiO 2 ) + Al 2 O 3 ) / ((2 ⁇ B 2 O 3 ) + RO) of 4.0 or more is an example of a glass having a high temperature viscosity.
  • High-viscosity glass generally requires a higher molten glass temperature in the refining process, so it is difficult to control the flow rate of the molten glass by the amount of electric power when the processing device is energized, and the platinum group metal volatilizes. Cheap.
  • the flow rate of the molten glass can be controlled by the amount of electric power, and the platinum group is contained in the molten glass. It can suppress that the metal aggregate is mixed as a foreign material.
  • the smaller the alkali metal oxide content the higher the high-temperature viscosity. Therefore, a glass having an alkali metal oxide content of 0 to 0.8 mol% has an alkali metal oxide content of 0.8 mol%. High temperature viscosity is high compared to glass exceeding.
  • Glass having high viscosity at high temperature generally needs to increase the temperature of the molten glass in the refining process, so that it is difficult to control the flow rate of the molten glass by the amount of electric power supplied to the processing apparatus, and the platinum group metal is likely to volatilize. That is, when using this glass having a high temperature viscosity, the temperature of the molten glass is in a temperature range in which the flow rate of the molten glass can be controlled while suppressing the agglomeration of the platinum group metal as a foreign substance in the molten glass.
  • the effect of the present embodiment that makes it easy to control the flow rate of the molten glass by the amount of electric power when the processing apparatus is energized becomes remarkable by adjusting the amount of heat radiation from the processing apparatus to the outside.
  • the molten glass used in the present embodiment may have a glass composition in which the temperature is 1500 to 1700 ° C. when the viscosity is 10 2.5 poise.
  • glass having a high temperature viscosity generally needs to increase the temperature of the molten glass in the refining process, so that it is difficult to control the flow rate of the molten glass by the amount of electric power supplied to the processing apparatus, and the volatilization of the platinum group metal. Is likely to occur. That is, even if it is a glass composition of high temperature viscosity, the said effect of this embodiment becomes remarkable.
  • the strain point of the molten glass used in this embodiment may be 650 ° C. or higher, more preferably 660 ° C. or higher, further preferably 690 ° C. or higher, and particularly preferably 730 ° C. or higher.
  • a glass having a high strain point tends to increase the temperature of the molten glass at a viscosity of 10 2.5 poise. That is, the effect of this embodiment becomes more remarkable as the glass substrate having a higher strain point is manufactured.
  • the glass having a higher strain point is used for a high-definition display, the demand for the problem that platinum group metal aggregates are mixed as foreign substances is severe. For this reason, the glass substrate having a higher strain point is more suitable for the present embodiment, which can suppress the inclusion of platinum group metal aggregates.
  • the temperature of the molten glass when the viscosity is 10 2.5 poise is, for example, 1500 ° C. to 1700 ° C., and may be 1550 ° C. to 1650 ° C.
  • glass substrates for oxide semiconductor displays using oxide semiconductors such as IGZO (indium, gallium, zinc, oxygen) and LTPS (low temperature polysilicon) semiconductors which are more demanding for display defects on the screen.
  • oxide semiconductors such as IGZO (indium, gallium, zinc, oxygen) and LTPS (low temperature polysilicon) semiconductors
  • the glass substrate produced in the present embodiment is suitable for a glass substrate for display including a glass substrate for flat panel display. It is suitable for a glass substrate for oxide semiconductor display or a glass substrate for LTPS display.
  • the glass substrate manufactured by this embodiment is suitable for the glass substrate for liquid crystal displays by which it is calculated
  • the manufacturing method of the glass substrate of this embodiment is suitable for manufacture of the glass substrate for displays, and is especially suitable for manufacture of the glass substrate for liquid crystal displays.
  • the glass substrate manufactured by this embodiment is applicable also to a cover glass, the glass for magnetic discs, the glass substrate for solar cells, etc.
  • the amount of heat release may be adjusted by providing a refrigerant circulation pipe between the vicinity of the clarification pipe 120 and the outside of the heat insulating material 140 and circulating the refrigerant inside the circulation pipe.
  • the heat radiation amount can be adjusted by controlling the circulation amount of the refrigerant.
  • the refrigerant circulated in the circulation pipe may be a liquid such as water or a gas such as air.
  • a metal material having a high melting point can be used for the circulation pipe. Specifically, platinum, rhodium, silver, palladium, gold, or an alloy thereof can be used as a material for the circulation pipe.
  • the present invention has been described mainly with respect to the clarification tube 120.
  • the present invention is not limited to the clarification tube 120, but other parts of the melting apparatus 100 (dissolution tank 101, stirring tank 103, transfer pipes 104 and 105, glass supply).
  • the amount of heat released from the tube 106) or the molding apparatus 200 may be adjusted.

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Abstract

Provided are a method for producing a glass substrate and a glass-substrate production device which make it possible to control the flow of molten glass even when there is a lot of molten-glass flow. When treating molten glass, the present invention: heats a treatment device by electrifying the treatment device in a manner such that the temperature of the molten glass inside the treatment device is within a range suitable for the treatment; controls the flow of the molten glass inside the treatment device using an amount of power for the electrification; and adjusts the amount of heat released to the exterior from the treatment device in a manner such that the amount of power is at or above the level at which it is possible to control the flow of the molten glass, and the temperature of the molten glass is in a temperature range in which it is possible to control the flow of the molten glass.

Description

ガラス基板の製造方法およびガラス基板製造装置Glass substrate manufacturing method and glass substrate manufacturing apparatus
 本発明は、ガラス基板の製造方法およびガラス基板製造装置に関する。 The present invention relates to a glass substrate manufacturing method and a glass substrate manufacturing apparatus.
 ガラス基板は、一般的に、ガラス原料から熔融ガラスを生成させた後、熔融ガラスをガラス基板へと成形する工程を経て製造される。上記の工程中には、熔融ガラスが内包する微小な気泡を除去する工程(以下、清澄ともいう)が含まれる。清澄は、清澄管の本体を加熱しながら、この清澄管本体に清澄剤を配合させた熔融ガラスを通過させ、清澄剤の酸化還元反応により熔融ガラス中の泡が取り除かれることで行われる。より具体的には、粗熔解した熔融ガラスの温度をさらに上げて清澄剤を機能させ泡を浮上脱泡させた後、温度を下げることにより、脱泡しきれずに残った比較的小さな泡は熔融ガラスに吸収させるようにしている。すなわち、清澄は、泡を浮上脱泡させる処理(以下、脱泡処理または脱泡工程ともいう)および小泡を熔融ガラスへ吸収させる処理(以下、吸収処理または吸収工程ともいう)を含む。 A glass substrate is generally manufactured through a process of forming molten glass from a glass raw material and then forming the molten glass into a glass substrate. The above process includes a process of removing minute bubbles contained in the molten glass (hereinafter also referred to as clarification). The clarification is performed by passing a molten glass containing a clarifier in the clarifier tube body while heating the clarifier tube body, and removing bubbles in the molten glass by an oxidation-reduction reaction of the clarifier. More specifically, the temperature of the molten glass that has been melted further is further raised to allow the fining agent to function and the bubbles to float and defoam. The glass is made to absorb. That is, clarification includes a process for floating and defoaming bubbles (hereinafter also referred to as a defoaming process or a defoaming process) and a process for absorbing small bubbles into molten glass (hereinafter also referred to as an absorption process or an absorbing process).
 清澄処理において熔融ガラスを加熱するために清澄管を加熱する技術として、例えば、上記の清澄管に1対のフランジ状の電極を設け、この電極対に電圧を印加することにより、清澄管を通電加熱する技術が知られている(特許文献1)。 As a technique for heating the clarification tube in order to heat the molten glass in the clarification treatment, for example, a pair of flange-shaped electrodes are provided in the clarification tube, and the voltage is applied to the electrode pair to energize the clarification tube. A technique for heating is known (Patent Document 1).
特表2011-513173号公報Special table 2011-513173 gazette
 上記装置では、清澄管への通電量により、清澄管内の熔融ガラスに加える熱量を調整することができる。このため、清澄管を通過する熔融ガラスの流量が増加しても、流量に応じて通電量を増加させることで熔融ガラスの温度を脱泡処理に必要な温度まで上昇させることができる。 In the above apparatus, the amount of heat applied to the molten glass in the clarification tube can be adjusted by the amount of current supplied to the clarification tube. For this reason, even if the flow volume of the molten glass which passes a clarification pipe | tube increases, the temperature of a molten glass can be raised to the temperature required for a defoaming process by increasing energization according to a flow volume.
 清澄管を通過する熔融ガラスの流量を決定するひとつの要因として熔融ガラスの粘度がある。熔融ガラスの粘度は熔融ガラスの温度によって定まり、熔融ガラスの温度は清澄管への通電量により制御されている。このため、清澄管出口への通電量により熔融ガラスの流量を制御することができる。
 しかし、清澄管の低温領域の温度を上昇させ、その後の工程における加熱量を低減させると、清澄管出口への通電量が小さくなり、熔融ガラスの流量を制御することができなくなる。また、熔融ガラスの流量が多いと、例えば清澄管出口の通電量をゼロにしても熔融ガラスの温度を低下させることができなくなり、熔融ガラスの流量を制御することができなくなる。熔融ガラスの流量を制御することができなくなると、清澄管よりも下流の処理装置において熔融ガラスが溢れ出てしまうという問題が発生することが懸念される。また、熔融ガラスの温度を吸収処理に必要な温度まで低下させることが困難になるため、結果的に窒素や酸化硫黄に由来するリボイル泡が増加してしまうという問題がある。
One factor that determines the flow rate of the molten glass passing through the clarification tube is the viscosity of the molten glass. The viscosity of the molten glass is determined by the temperature of the molten glass, and the temperature of the molten glass is controlled by the amount of current supplied to the clarification tube. For this reason, the flow rate of the molten glass can be controlled by the energization amount to the clarifier tube outlet.
However, if the temperature in the low temperature region of the clarification tube is raised and the amount of heating in the subsequent process is reduced, the amount of current supplied to the clarification tube outlet becomes small, and the flow rate of the molten glass cannot be controlled. If the flow rate of the molten glass is large, the temperature of the molten glass cannot be lowered even if, for example, the energization amount at the clarification tube outlet is zero, and the flow rate of the molten glass cannot be controlled. If it becomes impossible to control the flow rate of the molten glass, there is a concern that a problem may occur that the molten glass overflows in the processing apparatus downstream of the clarification tube. Moreover, since it becomes difficult to lower | hang the temperature of a molten glass to the temperature required for an absorption process, there exists a problem that the reboyl bubble derived from nitrogen and a sulfur oxide will increase as a result.
 上記の問題を回避するためには、清澄管内において熔融ガラスの温度を低下させる必要があるが、清澄管への通電量を低下させることで熔融ガラス温度を低下させると、低温領域で白金族金属の凝集が生じるおそれがある。また、上述した脱泡処理に必要な温度まで熔融ガラス温度を上昇させることが困難となり、十分な清澄効果を得ることができなくなる。 In order to avoid the above problem, it is necessary to lower the temperature of the molten glass in the clarification tube. However, if the molten glass temperature is decreased by reducing the amount of current supplied to the clarification tube, the platinum group metal in the low temperature region. There is a risk of aggregation. Moreover, it becomes difficult to raise the molten glass temperature to the temperature required for the defoaming treatment described above, and a sufficient clarification effect cannot be obtained.
 本発明は、熔融ガラスの流量が多い場合でも、清澄効果と熔融ガラスの流量制御とを両立することができるガラス基板の製造方法およびガラス基板製造装置を提供することを目的とする。 An object of the present invention is to provide a glass substrate manufacturing method and a glass substrate manufacturing apparatus capable of achieving both a refining effect and a flow control of a molten glass even when the flow rate of the molten glass is large.
 本発明は、以下の形態を有する。
(形態1)
 熔融ガラスを処理する処理装置を用いるガラス基板の製造方法であって、
 熔融ガラスを処理する際に、
 前記処理装置内の熔融ガラスの温度が前記処理をするのに適した範囲になるように、前記処理装置に通電をすることにより前記処理装置を加熱し、
 前記処理装置内の前記熔融ガラスの流量を、前記通電をする際の電力量により制御し、
 前記電力量が前記熔融ガラスの流量制御ができる電力量以上となり、かつ、前記熔融ガラスの温度が前記熔融ガラスの流量制御ができる温度範囲となるように、前記処理装置から外部への放熱量を調節する、ガラス基板の製造方法。
The present invention has the following forms.
(Form 1)
A method for manufacturing a glass substrate using a processing apparatus for processing molten glass,
When processing molten glass,
Heating the processing device by energizing the processing device so that the temperature of the molten glass in the processing device is in a range suitable for the processing,
The flow rate of the molten glass in the processing device is controlled by the amount of electric power when energizing,
The amount of heat radiation from the processing device to the outside is set so that the amount of electric power is equal to or greater than the amount of electric power capable of controlling the flow rate of the molten glass, and the temperature of the molten glass is in a temperature range capable of controlling the flow rate of the molten glass. A method of manufacturing a glass substrate to be adjusted.
(形態2)
 熔融ガラスを処理する処理装置を用いるガラス基板の製造方法であって、
 熔融ガラスを処理する際に、
 前記処理装置内の熔融ガラスの温度が前記処理をするのに適した範囲になるように、前記処理装置に通電をすることにより前記処理装置を加熱し、
 前記処理装置内の前記熔融ガラスの流量を、前記通電をする際の電流量により制御し、
 前記熔融ガラスの流量制御ができる電流量以上となるように、前記処理装置から外部への放熱量を調節する、ガラス基板の製造方法。
(Form 2)
A method for manufacturing a glass substrate using a processing apparatus for processing molten glass,
When processing molten glass,
Heating the processing device by energizing the processing device so that the temperature of the molten glass in the processing device is in a range suitable for the processing,
The flow rate of the molten glass in the processing device is controlled by the amount of current when the current is applied,
A method for producing a glass substrate, wherein the amount of heat released from the processing device to the outside is adjusted so as to be equal to or greater than an amount of current that enables flow control of the molten glass.
 ここで、熔融ガラスの流量とは、単位時間当たりの熔融ガラスの移動量(体積又は質量)を示す。
 ここで、処理装置には、熔解槽、清澄装置、攪拌槽や成形装置、および、これらの装置管で熔融ガラスを移送する移送管、これらの装置にガラスを供給する供給管を含む。処理装置における処理には、ガラスの熔解処理、熔融ガラスの清澄処理、攪拌処理、成形処理、および、熔融ガラスの移送処理、供給処理が含まれる。
Here, the flow rate of the molten glass indicates the moving amount (volume or mass) of the molten glass per unit time.
Here, the processing apparatus includes a melting tank, a refining apparatus, a stirring tank and a forming apparatus, a transfer pipe for transferring molten glass through these apparatus tubes, and a supply pipe for supplying glass to these apparatuses. The processing in the processing apparatus includes glass melting processing, molten glass clarification processing, stirring processing, molding processing, and molten glass transfer processing and supply processing.
(形態3)
 前記処理装置は内壁と熔融ガラス液面とから形成される気相空間を有し、前記内壁の少なくとも前記気相空間と接する部分は白金族金属を含む材料で構成され、
 前記処理装置には、熔融ガラスを処理する際に高温領域と、高温領域よりも温度の低い低温領域が形成され、
 前記高温領域と前記低温領域の温度差が200℃以下となるように前記放熱量を調整する、形態1又は2に記載のガラス基板の製造方法。
 白金族金属とは、単一の白金族元素からなる金属、および、白金族元素からなる金属の合金を意味する。白金族元素は、白金(Pt)、パラジウム(Pd)、ロジウム(Rh)、ルテニウム(Ru)、オスミウム(Os)およびイリジウム(Ir)の6元素である。
 例えば、高温領域は、処理装置の温度が1600℃以上の温度範囲にある領域であり、低温領域は、処理装置の温度が1600℃未満の温度範囲にある領域であってもよい。又は、高温領域は、処理装置の温度が1620℃以上の温度範囲にある領域であり、低温領域は、処理装置の温度が1590℃以下の温度範囲にある領域であってもよい。
 あるいは、処理装置に設けられた電極が設けられる領域である電極領域及び排気管が設けられた領域が低温領域であり、低温領域以外の領域又は電極と排気管の間の領域が高温領域であってもよい。
 高温領域の最高温度が1600~1750℃となり、かつ、低温領域の最低温度が1300~1600℃となるように、放熱量を調節することが好ましい。高温領域と低温領域との温度差を低減することで、高温領域で揮発した白金族金属が低温領域で凝集する量を低下することができる。なお、上記白金族金属等の揮発物の凝集物に由来する異物の熔融ガラスへの混入の問題は、近年の高精細化に伴い、益々品質要求が厳しくなっている液晶ディスプレイに代表されるディスプレイ用ガラス基板ではより大きくなる。そのため、上記形態はディスプレイ用ガラス基板の製造方法により好適である。
(Form 3)
The processing apparatus has a gas phase space formed by an inner wall and a molten glass liquid surface, and at least a portion of the inner wall in contact with the gas phase space is made of a material containing a platinum group metal,
In the processing apparatus, when processing the molten glass, a high temperature region and a low temperature region lower in temperature than the high temperature region are formed,
The manufacturing method of the glass substrate of the form 1 or 2 which adjusts the said thermal radiation amount so that the temperature difference of the said high temperature area | region and the said low temperature area | region may be 200 degrees C or less.
The platinum group metal means a metal composed of a single platinum group element and an alloy of a metal composed of a platinum group element. The platinum group elements are six elements of platinum (Pt), palladium (Pd), rhodium (Rh), ruthenium (Ru), osmium (Os) and iridium (Ir).
For example, the high temperature region may be a region where the temperature of the processing apparatus is in a temperature range of 1600 ° C. or higher, and the low temperature region may be a region where the temperature of the processing apparatus is in a temperature range of less than 1600 ° C. Alternatively, the high temperature region may be a region where the temperature of the processing apparatus is in a temperature range of 1620 ° C. or higher, and the low temperature region may be a region where the temperature of the processing apparatus is in a temperature range of 1590 ° C. or lower.
Alternatively, the electrode region, which is the region where the electrode provided in the processing apparatus is provided, and the region where the exhaust pipe is provided are the low temperature region, and the region other than the low temperature region or the region between the electrode and the exhaust pipe is the high temperature region. May be.
It is preferable to adjust the heat radiation amount so that the maximum temperature in the high temperature region is 1600 to 1750 ° C. and the minimum temperature in the low temperature region is 1300 to 1600 ° C. By reducing the temperature difference between the high temperature region and the low temperature region, the amount of aggregation of the platinum group metal volatilized in the high temperature region in the low temperature region can be reduced. In addition, the problem of mixing foreign substances derived from volatile aggregates such as the above platinum group metals into the molten glass is a display typified by a liquid crystal display whose quality requirements are becoming increasingly severe with the recent high definition. It becomes larger with the glass substrate. Therefore, the said form is suitable with the manufacturing method of the glass substrate for displays.
(形態4)
 前記処理装置は断熱材により覆われ、
 前記断熱材により前記処理装置から外部空間への熱抵抗を調整することで、前記放熱量を制御する、形態1~3のいずれか1つに記載のガラス基板の製造方法。
(形態5)
 前記断熱材の熱伝導率および配置を調整することで、前記熱抵抗を調整する、形態4に記載のガラス基板の製造方法。
(Form 4)
The treatment device is covered with a heat insulating material,
The method for manufacturing a glass substrate according to any one of Embodiments 1 to 3, wherein the heat radiation amount is controlled by adjusting a thermal resistance from the processing apparatus to an external space by the heat insulating material.
(Form 5)
The manufacturing method of the glass substrate of the form 4 which adjusts the said thermal resistance by adjusting the thermal conductivity and arrangement | positioning of the said heat insulating material.
(形態6)
 前記処理装置は、熔融ガラスを清澄させる清澄装置であり。
 前記清澄装置を、前記清澄装置内の熔融ガラスの最高温度が、前記熔融ガラスに含まれる酸化錫の還元反応が生じる温度以上となるように、前記清澄装置に通電をすることにより加熱し、前記清澄装置内の前記熔融ガラスの流量を、前記通電をする際の電力量により制御し、前記電力量が前記熔融ガラスの流量制御ができる電力量以上となるように、前記清澄装置から外部への放熱量を調節する、形態1~5のいずれか1つに記載のガラス基板の製造方法。
(Form 6)
The said processing apparatus is a clarification apparatus which clarifies molten glass.
The clarifier is heated by energizing the clarifier so that the maximum temperature of the molten glass in the clarifier is equal to or higher than the temperature at which the reduction reaction of tin oxide contained in the molten glass occurs. The flow rate of the molten glass in the clarification device is controlled by the amount of electric power when the current is applied, and from the clarification device to the outside so that the amount of electric power is equal to or greater than the amount of electric power capable of controlling the flow rate of the molten glass. The method for producing a glass substrate according to any one of embodiments 1 to 5, wherein the amount of heat radiation is adjusted.
 処理装置内の熔融ガラスの最高温度は1630℃~1720℃であることが好ましい。最高温度が1630℃以上であることで、熔融ガラス内の清澄剤が清澄効果を発揮することができる一方、1720℃以下であることで高温領域と低温領域との温度差を低減することができ、気泡の低減と白金族金属の揮発量の低減とを両立することができる。
 清澄剤として、酸化錫を用いることが好ましい。熔融ガラス中の酸化錫の含有量は、0.01~0.3モル%であることが好ましい。酸化錫の含有量が少なすぎると、気泡の低減を十分に行うことができない。一方、酸化錫の含有量が多すぎると、酸化錫の熔融ガラスからの揮発量が増加し、揮発した酸化錫の凝集物が熔融ガラスに混入するという問題が生ずる。また、酸化錫の含有量が多すぎると、熔融ガラスから放出される酸素が増加しすぎてしまい、気相空間の酸素濃度が上昇することで、処理装置からの白金族金属の揮発量が増加してしまうという問題が生ずる。酸化錫の含有量を0.01~0.3モル%とすることで、気泡を十分に低減しながら酸化錫又は白金族金属の凝集物が熔融ガラスに混入することを低減することができる。また、気泡を十分に低減しながら処理装置からの白金族金属の揮発量を低減することができる。
The maximum temperature of the molten glass in the processing apparatus is preferably 1630 ° C to 1720 ° C. When the maximum temperature is 1630 ° C. or higher, the fining agent in the molten glass can exert a clarification effect, and when it is 1720 ° C. or lower, the temperature difference between the high temperature region and the low temperature region can be reduced. It is possible to achieve both reduction of bubbles and reduction of the volatilization amount of the platinum group metal.
It is preferable to use tin oxide as a fining agent. The content of tin oxide in the molten glass is preferably 0.01 to 0.3 mol%. If the content of tin oxide is too small, bubbles cannot be sufficiently reduced. On the other hand, when the content of tin oxide is too large, the volatilization amount of tin oxide from the molten glass increases, and there arises a problem that aggregates of volatilized tin oxide are mixed into the molten glass. Also, if the tin oxide content is too high, the amount of oxygen released from the molten glass will increase too much, and the oxygen concentration in the gas phase space will increase, increasing the volatilization amount of platinum group metals from the processing equipment. The problem of end up occurs. By setting the content of tin oxide to 0.01 to 0.3 mol%, it is possible to reduce the mixture of tin oxide or platinum group metal aggregates into the molten glass while sufficiently reducing bubbles. Further, the volatilization amount of the platinum group metal from the processing apparatus can be reduced while sufficiently reducing bubbles.
(形態7)
 前記清澄装置は、熔融ガラス中の気泡が排出される気相空間を有する清澄管と、前記清澄管内へ供給される熔融ガラスが移送される第1の移送管と、前記清澄管から排出される熔融ガラスが移送される第2の移送管と、を有し、
 前記第1の移送管、前記清澄管および前記第2の移送管において、清澄剤の還元反応により熔融ガラスの脱泡処理、および、清澄剤の酸化反応により熔融ガラス中の気泡を吸収する吸収処理を行い、
 前記第1の移送管に通電する電力量、前記清澄管および前記第2の移送管のうち前記脱泡処理を行う領域に通電する電力量、および、前記清澄管および前記第2の移送管のうち前記吸収処理を行う領域に通電する電力量の比は、1:0.6~1:0.1~0.4である、形態6に記載のガラス基板の製造方法。
(Form 7)
The clarification device is discharged from the clarification tube having a gas phase space through which bubbles in the molten glass are discharged, a first transfer tube to which the molten glass supplied into the clarification tube is transferred, and the clarification tube. A second transfer pipe through which the molten glass is transferred,
In the first transfer pipe, the clarification pipe, and the second transfer pipe, the defoaming treatment of the molten glass by the reductive reaction of the clarifier and the absorption treatment that absorbs the bubbles in the molten glass by the oxidation reaction of the clarifier. And
The amount of power to be applied to the first transfer pipe, the amount of power to be applied to the region for performing the defoaming process among the clarification pipe and the second transfer pipe, and the clarification pipe and the second transfer pipe The method of manufacturing a glass substrate according to mode 6, wherein the ratio of the amount of electric power applied to the region where the absorption treatment is performed is 1: 0.6 to 1: 0.1 to 0.4.
(形態8)
 前記清澄装置は、熔融ガラス中の気泡が排出される気相空間を有する清澄管と、前記清澄管内へ供給される熔融ガラスが移送される第1の移送管と、前記清澄管から排出される熔融ガラスが移送される第2の移送管と、を有し、
 前記清澄管の一部の領域において、清澄剤の還元反応により熔融ガラスの脱泡処理を行い、
 前記清澄管の他の領域および前記第2の移送管において、清澄剤の酸化反応により熔融ガラス中の気泡を吸収する吸収処理を行い、
 前記第1の移送管に通電する電力量、前記清澄管の一部の領域に通電する電力量、および、前記清澄管の他の領域に通電する電力量の比は、1:0.6~1:0.1~0.4である、形態6に記載のガラス基板の製造方法。
(Form 8)
The clarification device is discharged from the clarification tube having a gas phase space through which bubbles in the molten glass are discharged, a first transfer tube to which the molten glass supplied into the clarification tube is transferred, and the clarification tube. A second transfer pipe through which the molten glass is transferred,
In a partial region of the clarification tube, a defoaming treatment of the molten glass is performed by a reduction reaction of the clarifier,
In the other region of the clarification tube and the second transfer tube, an absorption treatment for absorbing bubbles in the molten glass by an oxidation reaction of the clarifier is performed,
The ratio of the amount of power applied to the first transfer pipe, the amount of power applied to a partial area of the clarification pipe, and the amount of power supplied to the other area of the clarification pipe is from 1: 0.6 to 1: The method for producing a glass substrate according to mode 6, wherein the ratio is 0.1 to 0.4.
(形態9)
 前記処理装置は、熔融ガラス中の気泡が排出される気相空間を有する清澄管と、前記清澄管内へ供給される熔融ガラスが移送される第1の移送管と、前記清澄管から排出される熔融ガラスが移送される第2の移送管と、を有し、
 前記清澄管において、清澄剤の還元反応により熔融ガラスの脱泡処理を行い、
 前記第2の移送管において、清澄剤の酸化反応により熔融ガラス中の気泡を吸収する吸収処理を行い、
 前記第1の移送管に通電する電力量、前記清澄管に通電する電力量、および、前記第2の移送管に通電する電力量の比は、1:0.6~1:0.1~0.4である、形態6に記載のガラス基板の製造方法。
(Form 9)
The processing device is discharged from the clarification tube having a gas phase space in which bubbles in the molten glass are discharged, a first transfer tube to which the molten glass supplied into the clarification tube is transferred, and the clarification tube. A second transfer pipe through which the molten glass is transferred,
In the clarification tube, the defoaming treatment of the molten glass is performed by the reduction reaction of the clarifier,
In the second transfer pipe, an absorption treatment for absorbing bubbles in the molten glass by an oxidation reaction of a clarifying agent is performed.
The ratio of the amount of power applied to the first transfer tube, the amount of power applied to the clarification tube, and the amount of power applied to the second transfer tube is 1: 0.6 to 1: 0.1 to The manufacturing method of the glass substrate of form 6 which is 0.4.
 形態7~9において、脱泡処理を行う領域は、温度が1620℃以上となる領域を指す。脱泡処理を行う領域における熔融ガラスの最高温度は1630℃~1720℃であることが好ましく、1640℃~1720℃であることがより好ましい。脱泡処理を行う領域における処理装置の最高温度は1630℃~1750℃であることが好ましく、1640℃~1750℃であることがより好ましい。この温度範囲とすることで、清澄剤の還元反応による気泡の除去を十分に行いながら、白金族金属の揮発を低減することができる。 In Embodiments 7 to 9, the region where the defoaming treatment is performed refers to a region where the temperature is 1620 ° C. or higher. The maximum temperature of the molten glass in the region where the defoaming treatment is performed is preferably 1630 ° C. to 1720 ° C., and more preferably 1640 ° C. to 1720 ° C. The maximum temperature of the treatment apparatus in the region where defoaming treatment is performed is preferably 1630 ° C. to 1750 ° C., and more preferably 1640 ° C. to 1750 ° C. By setting it as this temperature range, volatilization of a platinum group metal can be reduced, fully performing the removal of the bubble by the reductive reaction of a clarifying agent.
 形態7~9において、吸収処理を行う領域は、温度が1620℃未満となる領域を指す。吸収処理を行う領域における熔融ガラスの温度は、1450℃~1620℃であることが好ましい。この温度範囲とすることで、清澄剤の酸化反応による気泡の吸収を効果的に行うことができる。 In Embodiments 7 to 9, the region where the absorption treatment is performed refers to a region where the temperature is less than 1620 ° C. The temperature of the molten glass in the region where the absorption treatment is performed is preferably 1450 ° C. to 1620 ° C. By setting it as this temperature range, absorption of the bubble by the oxidation reaction of a clarifying agent can be performed effectively.
 形態7~9において、気相空間中の酸素濃度は、0~10%であることが好ましい。酸素濃度を小さくすることで、白金族金属の揮発量を低減することができる。
 前記気相空間中の白金族金属の蒸気圧は0.1Pa~15Paであることが好ましい。白金族金属の蒸気圧がこの範囲であると、還元された白金族金属が内壁面に付着するのを抑制することができる。
In Embodiments 7 to 9, the oxygen concentration in the gas phase space is preferably 0 to 10%. By reducing the oxygen concentration, the volatilization amount of the platinum group metal can be reduced.
The vapor pressure of the platinum group metal in the gas phase space is preferably 0.1 Pa to 15 Pa. When the vapor pressure of the platinum group metal is within this range, the reduced platinum group metal can be prevented from adhering to the inner wall surface.
(形態10)
 熔融ガラスを処理する処理装置と、
 熔融ガラスを処理する際に、前記処理装置内の熔融ガラスの温度が前記処理をするのに適した範囲になるように、前記処理装置に通電をすることで加熱する通電装置と、
 前記処理装置内の前記熔融ガラスの流量を、前記通電をする際の電力量により制御する制御装置と、を備え、
 前記電力量が前記熔融ガラスの流量制御ができる電力量以上となり、かつ、前記熔融ガラスの温度が前記熔融ガラスの流量制御ができる温度範囲となるように、前記処理装置から外部への放熱量が調節されている、ガラス基板製造装置。
(Form 10)
A processing apparatus for processing molten glass;
An energizer that heats the processing apparatus by energizing the processing apparatus so that the temperature of the molten glass in the processing apparatus is in a range suitable for the processing when the molten glass is processed;
A control device for controlling the flow rate of the molten glass in the processing device by the amount of electric power when energizing,
The amount of heat radiation from the processing device to the outside is such that the amount of electric power is equal to or greater than the amount of electric power capable of controlling the flow rate of the molten glass, and the temperature of the molten glass is within a temperature range capable of controlling the flow rate of the molten glass. Glass substrate manufacturing equipment that is being adjusted.
(形態11)
 熔融ガラスを処理する処理装置と、
 熔融ガラスを処理する際に、前記処理装置内の熔融ガラスの温度が前記処理をするのに適した範囲になるように、前記処理装置に通電をすることで加熱する通電装置と、
 前記処理装置内の前記熔融ガラスの流量を、前記通電をする際の電流量により制御する制御装置と、を備え、
 前記熔融ガラスの流量制御ができる電流量以上となるように、前記処理装置から外部への放熱量が調節されている、ガラス基板製造装置。
(Form 11)
A processing apparatus for processing molten glass;
An energizer that heats the processing apparatus by energizing the processing apparatus so that the temperature of the molten glass in the processing apparatus is in a range suitable for the processing when the molten glass is processed;
A control device for controlling the flow rate of the molten glass in the processing device by the amount of current when the current is applied;
The glass substrate manufacturing apparatus in which the amount of heat radiation from the processing apparatus to the outside is adjusted so as to be equal to or greater than the amount of current capable of controlling the flow rate of the molten glass.
(形態12)
 前記処理装置は内壁と熔融ガラス液面とから形成される気相空間を有し、前記内壁の少なくとも前記気相空間と接する部分は白金族金属を含む材料で構成され、前記白金族金属の揮発物の凝集により生成される凝集物は、例えば、最大長さの最小長さに対する比であるアスペクト比が100以上である、形態1~11のいずれか1項に記載のガラス基板の製造方法又はガラス基板製造装置。また、例えば、白金族金属の凝集物の最大長さは50μm~300μm、最小長さは0.5μm~2μmである。ここで、白金族金属の凝集物の最大長さとは、白金族金属の凝集物を撮影して得られる異物の像に外接する外接長方形のうち最大長辺の長さをいい、最小長さとは、前記外接長方形の最小短辺の長さをいう。
 あるいは、前記白金族金属の揮発物の凝集により生成される凝集物は、最大長さの最小長さに対する比であるアスペクト比が100以上であり、白金族金属の凝集物の最大長さが100μm以上、好ましくは100μm~300μmであるものを示してもよい。
(Form 12)
The processing apparatus has a gas phase space formed from an inner wall and a molten glass liquid surface, and at least a portion of the inner wall that is in contact with the gas phase space is made of a material containing a platinum group metal, and volatilizes the platinum group metal. The method for producing a glass substrate according to any one of Embodiments 1 to 11, wherein the aggregate formed by the aggregation of the product has an aspect ratio of 100 or more, which is a ratio of the maximum length to the minimum length, for example. Glass substrate manufacturing equipment. For example, the maximum length of the platinum group metal aggregate is 50 μm to 300 μm, and the minimum length is 0.5 μm to 2 μm. Here, the maximum length of the platinum group metal aggregate is the maximum long side length of the circumscribed rectangle circumscribing the image of the foreign material obtained by photographing the platinum group metal aggregate. The minimum length is And the length of the minimum short side of the circumscribed rectangle.
Alternatively, the aggregate generated by the aggregation of the platinum group metal volatiles has an aspect ratio of 100 or more, which is a ratio of the maximum length to the minimum length, and the maximum length of the platinum group metal aggregate is 100 μm. The above may preferably be 100 μm to 300 μm.
(形態13)
 前記ガラス基板は、ディスプレイ用ガラス基板である、形態1~12のいずれか1項に記載のガラス基板の製造方法又はガラス基板製造装置。また、酸化物半導体ディスプレイ用ガラス基板又はLTPSディスプレイ用ガラス基板に好適である。
(Form 13)
The glass substrate manufacturing method or glass substrate manufacturing apparatus according to any one of Embodiments 1 to 12, wherein the glass substrate is a glass substrate for display. Moreover, it is suitable for the glass substrate for oxide semiconductor displays or the glass substrate for LTPS displays.
 本発明によれば、熔融ガラスの流量が多い場合でも清澄効果と熔融ガラスの流量制御とを実現することができる。 According to the present invention, even when the flow rate of the molten glass is large, the clarification effect and the flow rate control of the molten glass can be realized.
本実施形態のガラス基板の製造方法の工程の一例を示す図である。It is a figure which shows an example of the process of the manufacturing method of the glass substrate of this embodiment. 図1に示す熔解工程~切断工程を行う装置の一例を模式的に示す図である。FIG. 2 is a view schematically showing an example of an apparatus for performing a melting process to a cutting process shown in FIG. 清澄管120の構成を示す概略図である。It is the schematic which shows the structure of the clarification pipe | tube 120. FIG. 清澄管120の断面図である。It is sectional drawing of the clarification pipe | tube 120. FIG.
 以下、本発明のガラス基板の製造方法及びガラス基板製造装置について説明する。 Hereinafter, the glass substrate manufacturing method and glass substrate manufacturing apparatus of the present invention will be described.
 図1は、本実施形態のガラス基板の製造方法の工程の一例を示す図である。 FIG. 1 is a diagram illustrating an example of a process of a glass substrate manufacturing method according to the present embodiment.
(ガラス基板の製造方法の全体概要)
 ガラス基板の製造方法は、熔解工程(ST1)と、清澄工程(ST2)と、均質化工程(ST3)と、供給工程(ST4)と、成形工程(ST5)と、徐冷工程(ST6)と、切断工程(ST7)と、を主に有する。この他に、研削工程、研磨工程、洗浄工程、検査工程、梱包工程等を有し、梱包工程で積層された複数のガラス基板は、納入先の業者に搬送される。
(Overall overview of glass substrate manufacturing method)
The glass substrate manufacturing method includes a melting step (ST1), a clarification step (ST2), a homogenization step (ST3), a supply step (ST4), a forming step (ST5), and a slow cooling step (ST6). And a cutting step (ST7). In addition, a plurality of glass substrates that have a grinding process, a polishing process, a cleaning process, an inspection process, a packing process, and the like and are stacked in the packing process are transported to a supplier.
 熔解工程(ST1)は熔解槽で行われる。熔解槽では、ガラス原料を、熔解槽に蓄えられた熔融ガラスの液面に投入し、加熱することにより熔融ガラスを作る。さらに、熔解槽の内側側壁の1つの底部に設けられた流出口から下流工程に向けて熔融ガラスを流す。
 熔解槽の熔融ガラスの加熱は、熔融ガラス自身に電気が流れて自ら発熱し加熱する方法である通電加熱に加えて、バーナーによる火焔を補助的に与えてガラス原料を熔解することもできる。なお、熔融ガラスは、清澄剤を含有する。清澄剤として、酸化錫、亜ヒ酸、アンチモン等が知られているが、特に制限されない。しかし、環境負荷低減の点から、清澄剤として酸化錫を用いることが好ましい。酸化錫の含有量は、0.01~0.3モル%であることが好ましく、0.03~0.2モル%であることがより好ましい。酸化錫の含有量が少なすぎると、気泡の低減を十分に行うことができない。一方、酸化錫の含有量が多すぎると、酸化錫の熔融ガラスからの揮発量が増加し、揮発した酸化錫の凝集物が熔融ガラスに混入するという問題が生ずる。また、酸化錫の含有量が多すぎると、熔融ガラスから放出される酸素が増加しすぎてしまい、処理装置からの白金族金属の揮発量が増加してしまうという問題が生ずる。酸化錫の含有量を0.01~0.3モル%とすることで、気泡を十分に低減しながら酸化錫の凝集物が熔融ガラスに混入することを低減することができる。また、気泡を十分に低減しながら処理装置からの白金族金属の揮発量を低減することができる。
 酸化錫は、一般的に用いられていた亜ヒ酸に比べて清澄機能は低いが、環境負荷が低い点で清澄剤として好適に用いることができる。しかし、酸化錫は、清澄機能が亜ヒ酸に比べて低いので、酸化錫を用いた場合、熔融ガラスMGの清澄工程時の熔融ガラスMGの温度を従来よりも高くしなければならない。また、熔融ガラスの最高温度が高くなるため、白金族金属の凝集を抑えるために、処理装置の低温領域の温度を上昇させると、熔融ガラスの熔融ガラスの温度が高くなりすぎ、電流による流量の制御がしにくくなるという問題がある。そのため、後述する清澄管からの白金族金属の揮発量が増加し、結果的に白金族金属がガラス基板に異物として混入するという問題が顕著となる。
The melting step (ST1) is performed in a melting tank. In the melting tank, a glass raw material is poured into the liquid surface of the molten glass stored in the melting tank and heated to make molten glass. Furthermore, molten glass is poured toward the downstream process from the outlet provided in one bottom part of the inner side wall of the melting tank.
The heating of the molten glass in the melting tank can melt the glass raw material in addition to energizing heating, which is a method in which electricity flows through the molten glass itself to generate and heat itself, and supplementary flame is provided by a burner. In addition, molten glass contains a clarifier. As the fining agent, tin oxide, arsenous acid, antimony, and the like are known, but are not particularly limited. However, it is preferable to use tin oxide as a clarifying agent from the viewpoint of reducing environmental burden. The content of tin oxide is preferably 0.01 to 0.3 mol%, and more preferably 0.03 to 0.2 mol%. If the content of tin oxide is too small, bubbles cannot be sufficiently reduced. On the other hand, when the content of tin oxide is too large, the volatilization amount of tin oxide from the molten glass increases, and there arises a problem that aggregates of volatilized tin oxide are mixed into the molten glass. Moreover, when there is too much content of a tin oxide, the oxygen released from molten glass will increase too much, and the problem that the volatilization amount of the platinum group metal from a processing apparatus will increase will arise. By setting the content of tin oxide to 0.01 to 0.3 mol%, it is possible to reduce the mixture of tin oxide aggregates into the molten glass while sufficiently reducing bubbles. Further, the volatilization amount of the platinum group metal from the processing apparatus can be reduced while sufficiently reducing bubbles.
Tin oxide has a lower refining function than arsenous acid that has been generally used, but can be suitably used as a refining agent in terms of low environmental burden. However, since the refining function of tin oxide is lower than that of arsenous acid, when tin oxide is used, the temperature of the molten glass MG during the refining process of the molten glass MG must be made higher than before. In addition, since the maximum temperature of the molten glass is increased, if the temperature in the low temperature region of the processing apparatus is increased in order to suppress the aggregation of the platinum group metal, the temperature of the molten glass of the molten glass becomes too high, and the flow rate due to current is increased. There is a problem that it becomes difficult to control. Therefore, the volatilization amount of the platinum group metal from the clarification tube which will be described later increases, and as a result, the problem that the platinum group metal is mixed as a foreign substance in the glass substrate becomes remarkable.
 清澄工程(ST2)は、少なくとも清澄管において行われる。清澄工程は、脱泡処理と、吸収処理とを含む。
 脱泡処理では、熔融ガラスが昇温されることにより、熔融ガラス中に含まれる酸素、CO2あるいはSO2を含んだ泡が、清澄剤の還元反応により生じた酸素を吸収して体積が増大し、熔融ガラスの液面に浮上して放出される。脱泡処理は、例えば、熔融ガラスの温度が1620℃以上となる処理装置の領域で行われる。熔融ガラスの温度が1620℃以上となる処理装置の領域を「脱泡処理を行う領域」とする。脱泡処理を行う領域の温度は、1620℃~1750℃であることが好ましい。
 脱泡処理を行う領域における熔融ガラスの最高温度は1630℃~1720℃であることが好ましく、1640℃~1720℃であることがより好ましい。脱泡処理を行う領域における処理装置の最高温度は1630℃~1750℃であることが好ましく、1640℃~1750℃であることがより好ましい。この温度範囲とすることで、清澄剤の還元反応による気泡の除去を十分に行いながら、白金族金属の揮発を低減することができる。
The clarification step (ST2) is performed at least in the clarification tube. The clarification step includes a defoaming process and an absorption process.
In the defoaming treatment, when the molten glass is heated, the bubbles containing oxygen, CO 2 or SO 2 contained in the molten glass absorb oxygen generated by the reductive reaction of the fining agent, and the volume increases. Then, it floats on the liquid surface of the molten glass and is discharged. A defoaming process is performed in the area | region of the processing apparatus from which the temperature of a molten glass becomes 1620 degreeC or more, for example. A region of the processing apparatus in which the temperature of the molten glass is 1620 ° C. or higher is defined as “a region where defoaming is performed”. The temperature of the region where the defoaming treatment is performed is preferably 1620 ° C. to 1750 ° C.
The maximum temperature of the molten glass in the region where the defoaming treatment is performed is preferably 1630 ° C. to 1720 ° C., more preferably 1640 ° C. to 1720 ° C. The maximum temperature of the treatment apparatus in the region where defoaming treatment is performed is preferably 1630 ° C. to 1750 ° C., and more preferably 1640 ° C. to 1750 ° C. By setting it as this temperature range, volatilization of a platinum group metal can be reduced, fully performing the removal of the bubble by the reductive reaction of a clarifying agent.
 吸収処理では、熔融ガラスの温度を低下させることにより、清澄剤の還元反応により得られた還元物質が酸化反応をする。これにより、熔融ガラスに残存する泡中の酸素等のガス成分が熔融ガラス中に再吸収されて、泡が消滅する。吸収処理は、処理装置の脱泡処理を行う領域よりも下流側であって、熔融ガラスの温度が1620℃未満となる領域で行われる。この熔融ガラスの温度が1620℃未満となる処理装置の領域を「吸収処理を行う領域」とする。吸収処理を行う領域の温度は、1450℃以上1620℃未満であることが好ましい。
 吸収処理を行う領域における熔融ガラスの温度は、1450℃~1620℃であることが好ましい。この温度範囲とすることで、清澄剤の酸化反応による気泡の吸収を効果的に行うことができる。
In the absorption treatment, by reducing the temperature of the molten glass, the reducing substance obtained by the reductive reaction of the fining agent undergoes an oxidation reaction. Thereby, gas components, such as oxygen in the bubble which remain | survives in molten glass, are reabsorbed in molten glass, and a bubble lose | disappears. The absorption processing is performed in a region downstream of the region where the degassing processing of the processing apparatus is performed and the temperature of the molten glass is less than 1620 ° C. A region of the processing apparatus in which the temperature of the molten glass is less than 1620 ° C. is referred to as “region for performing absorption treatment”. The temperature of the region where the absorption treatment is performed is preferably 1450 ° C. or more and less than 1620 ° C.
The temperature of the molten glass in the region where the absorption treatment is performed is preferably 1450 ° C. to 1620 ° C. By setting it as this temperature range, absorption of the bubble by the oxidation reaction of a clarifying agent can be performed effectively.
 清澄剤による酸化反応及び還元反応は、熔融ガラスの温度を制御することにより行われる。本実施形態の清澄工程では、酸化錫を清澄剤として用いる清澄方法について説明する。
 なお、清澄工程は、減圧雰囲気の空間を清澄管につくり、熔融ガラスに存在する泡を減圧雰囲気で成長させて脱泡させる減圧脱泡方式を用いることもできる。この場合、清澄剤を用いない点で有効である。しかし、減圧脱泡方式は装置が複雑化及び大型化するため、清澄剤を用い、熔融ガラス温度を上昇させる清澄方法を採用することが好ましい。
The oxidation reaction and reduction reaction by the fining agent are performed by controlling the temperature of the molten glass. In the clarification step of this embodiment, a clarification method using tin oxide as a clarifier will be described.
In the clarification step, a reduced pressure defoaming method can be used in which a space in a reduced pressure atmosphere is formed in a clarified tube, and bubbles existing in the molten glass are grown in a reduced pressure atmosphere and defoamed. In this case, it is effective in that no clarifier is used. However, since the vacuum defoaming method complicates and enlarges the apparatus, it is preferable to employ a clarification method that uses a clarifier and raises the temperature of the molten glass.
 均質化工程(ST3)では、清澄管から延びる配管を通って供給された攪拌槽内の熔融ガラスを、スターラを用いて攪拌することにより、ガラス成分の均質化を行う。これにより、脈理等の原因であるガラスの組成ムラを低減することができる。
 供給工程(ST4)では、攪拌槽から延びる配管を通して熔融ガラスが成形装置に供給される。
In the homogenization step (ST3), the glass component is homogenized by stirring the molten glass in the stirring tank supplied through the pipe extending from the clarification pipe using a stirrer. Thereby, the composition unevenness of the glass which is a cause of striae or the like can be reduced.
In the supply step (ST4), the molten glass is supplied to the molding apparatus through a pipe extending from the stirring tank.
 成形工程(ST5)及び徐冷工程(ST6)は、成形装置で行われる。
 成形工程(ST5)では、熔融ガラスをシートガラスに成形し、シートガラスの流れを作る。成形には、オーバーフローダウンドロー法が用いられる。
 徐冷工程(ST6)では、成形されて流れるシートガラスが所望の厚さになり、内部歪が生じないように、さらに、反りが生じないように冷却される。
 切断工程(ST7)では、切断装置において、成形装置から供給されたシートガラスを所定の長さに切断することで、板状のガラス基板を得る。切断されたガラス基板はさらに、所定のサイズに切断され、目標サイズのガラス基板が作られる。
The molding step (ST5) and the slow cooling step (ST6) are performed by a molding apparatus.
In the forming step (ST5), the molten glass is formed into a sheet glass to make a flow of the sheet glass. An overflow downdraw method is used for molding.
In the slow cooling step (ST6), the sheet glass that has been formed and flowed is cooled to a desired thickness, so that internal distortion does not occur and warpage does not occur.
In the cutting step (ST7), the sheet glass supplied from the forming device is cut into a predetermined length in the cutting device to obtain a plate-like glass substrate. The cut glass substrate is further cut into a predetermined size to produce a glass substrate having a target size.
 図2は、本実施形態における熔解工程(ST1)~切断工程(ST7)を行う装置の一例を模式的に示す図である。当該装置は、図2に示すように、主に熔解装置100と、成形装置200と、を有する。熔解装置100は、熔解槽101と、清澄管120と、攪拌槽103と、第1の移送管104と、第2の移送管105と、ガラス供給管106と、を有する。
 図2に示す熔解槽101には、図示されないバーナー等の加熱手段が設けられている。熔解槽には清澄剤が添加されたガラス原料が投入され、熔解工程が行われる。熔解槽101で熔融した熔融ガラスは、移送管104を介して清澄管120に供給される。
 清澄管120では、熔融ガラスMGの温度を調整して、清澄剤の酸化還元反応を利用して熔融ガラスの清澄工程が行われる。清澄後の熔融ガラスは、移送管105を介して攪拌槽に供給される。なお、清澄工程のうち、脱泡処理は、移送管104において行われてもよい。すなわち、移送管104が「脱泡処理を行う領域」を有していてもよい。また、清澄工程のうち、吸収処理は、移送管105において行われてもよい。すなわち、移送管105が「吸収処理を行う領域」を有していてもよい。
FIG. 2 is a diagram schematically showing an example of an apparatus for performing the melting step (ST1) to the cutting step (ST7) in the present embodiment. As shown in FIG. 2, the apparatus mainly includes a melting apparatus 100 and a molding apparatus 200. The melting apparatus 100 includes a melting tank 101, a clarification pipe 120, a stirring tank 103, a first transfer pipe 104, a second transfer pipe 105, and a glass supply pipe 106.
The melting tank 101 shown in FIG. 2 is provided with heating means such as a burner (not shown). A glass raw material to which a fining agent is added is charged into the melting tank, and a melting process is performed. The molten glass melted in the melting tank 101 is supplied to the clarification tube 120 through the transfer tube 104.
In the clarification tube 120, the temperature of the molten glass MG is adjusted, and the clarification step of the molten glass is performed using the oxidation-reduction reaction of the clarifier. The clarified molten glass is supplied to the stirring tank through the transfer pipe 105. In the clarification step, the defoaming process may be performed in the transfer pipe 104. That is, the transfer pipe 104 may have a “region for performing a defoaming process”. In the clarification process, the absorption process may be performed in the transfer pipe 105. That is, the transfer pipe 105 may have an “area for performing an absorption process”.
 清澄管120には、電極121a、121bが設けられており、電極121a、121bの間に電圧が印加されることにより、電極121a、121bの間の清澄管120に電流が流れて、清澄管120が通電加熱される。また、第1の移送管104および第2の移送管105の両端部には、図示しない電極が設けられており、電極間に電圧が印加されることにより、第1の移送管104および第2の移送管105に電流が流れて、第1の移送管104および第2の移送管105が通電加熱される。電極121a、121bは、過熱による破損を防止する観点からフランジ形状であることが好ましい。本実施形態の清澄管120の場合、フランジ形状を有する電極121a、121bは、高い放熱機能を有するので、電極121a、121b近傍の壁は、その壁の周辺の部分に比べて低温になる。さらに、電極121a、121bは、例えば、過熱による破損を抑制するために、液体又は気体により冷却されている。このため、気相空間と接する清澄管120の壁の温度は、熔融ガラスの流れ方向に沿って必然的に温度プロファイルを持つ。言い換えると、本実施形態の清澄管120の場合、清澄管120の温度が一定になることはなく、不可避的に温度差が生じる。 The clarification tube 120 is provided with electrodes 121a and 121b. When a voltage is applied between the electrodes 121a and 121b, an electric current flows through the clarification tube 120 between the electrodes 121a and 121b, and the clarification tube 120 is provided. Is heated by energization. In addition, electrodes (not shown) are provided at both ends of the first transfer pipe 104 and the second transfer pipe 105, and when a voltage is applied between the electrodes, the first transfer pipe 104 and the second transfer pipe 104 are provided. A current flows through the first transfer pipe 105 and the first transfer pipe 104 and the second transfer pipe 105 are energized and heated. It is preferable that the electrodes 121a and 121b have a flange shape from the viewpoint of preventing damage due to overheating. In the case of the clarification tube 120 of this embodiment, since the electrodes 121a and 121b having a flange shape have a high heat dissipation function, the walls near the electrodes 121a and 121b are at a lower temperature than the peripheral portions of the walls. Furthermore, the electrodes 121a and 121b are cooled with a liquid or a gas in order to suppress damage due to overheating, for example. For this reason, the temperature of the wall of the clarification tube 120 in contact with the gas phase space necessarily has a temperature profile along the flow direction of the molten glass. In other words, in the case of the clarification tube 120 of the present embodiment, the temperature of the clarification tube 120 does not become constant, and a temperature difference inevitably occurs.
 第1の移送管104に通電する電力量、清澄管120のうち脱泡処理を行う領域に通電する電力量、清澄管120および第2の移送管105のうち吸収処理を行う領域に通電する電力量の比は、1:0.6~1:0.1~0.4であることが好ましく、1:0.7~1:0.15~0.4であることが好ましい。 The amount of power to be applied to the first transfer pipe 104, the amount of power to be supplied to the region of the clarification tube 120 to be defoamed, and the power to be supplied to the region of the clarification tube 120 and the second transfer tube 105 to be subjected to the absorption process The amount ratio is preferably 1: 0.6 to 1: 0.1 to 0.4, and more preferably 1: 0.7 to 1: 0.15 to 0.4.
 また、清澄管120の一部の領域において脱泡処理が行われ、清澄管120の他の領域および第2の移送管105において吸収処理が行われる場合、第1の移送管104に通電する電力量、清澄管120の脱泡処理が行われる領域に通電する電力量、および、清澄管120の吸収処理が行われる領域に通電する電力量の比は、1:0.6~1:0.1~0.4であることが好ましく、1:0.7~1:0.15~0.4であることが好ましい。 In addition, when defoaming processing is performed in a part of the clarification tube 120 and absorption processing is performed in another region of the clarification tube 120 and the second transfer tube 105, electric power to be supplied to the first transfer tube 104 The ratio of the amount of electric power applied to the region where the defoaming treatment of the clarification tube 120 is performed and the amount of electric power applied to the region where the absorption treatment of the clarification tube 120 is performed is 1: 0.6 to 1: 0. It is preferably 1 to 0.4, and preferably 1: 0.7 to 1: 0.15 to 0.4.
 また、清澄管120にて脱泡処理が行われ、第2の移送管105においてのみ吸収処理が行われる場合、第1の移送管104に通電する電力量、清澄管120に通電する電力量、および、第2の移送管105に通電する電力量の比は、1:0.6~1:0.1~0.4であることが好ましく、1:0.7~1:0.15~0.4であることが好ましい。 In addition, when the defoaming process is performed in the clarification tube 120 and the absorption process is performed only in the second transfer pipe 105, the amount of power to be supplied to the first transfer pipe 104, the amount of power to be supplied to the clarification pipe 120, In addition, the ratio of the amount of electric power applied to the second transfer pipe 105 is preferably 1: 0.6 to 1: 0.1 to 0.4, and 1: 0.7 to 1: 0.15 to It is preferable that it is 0.4.
 攪拌槽103では、スターラ103aによって熔融ガラスが攪拌されて均質化される。攪拌槽103で均質化された熔融ガラスは、ガラス供給管106を介して成形装置200に供給される。
 成形装置200では、オーバーフローダウンドロー法により、熔融ガラスからシートガラスが成形される。
In the stirring vessel 103, the molten glass is stirred and homogenized by the stirrer 103a. The molten glass homogenized in the stirring tank 103 is supplied to the forming apparatus 200 through the glass supply pipe 106.
In the forming apparatus 200, sheet glass is formed from molten glass by the overflow downdraw method.
(清澄管の構成)
 次に、図3を参照して、清澄管120の構成について説明する。図3は、実施の形態の清澄管120の構成を示す概略図である。
 図3に示すように、清澄管120の長さ方向の両端の外周面には、電極121a、121bが設けられており、清澄管120の気相空間と接する壁には、排気管127が設けられている。なお、清澄管120は、白金、強化白金又は白金合金製であることが好ましい。
(Configuration of clarification tube)
Next, the configuration of the clarification tube 120 will be described with reference to FIG. FIG. 3 is a schematic diagram illustrating a configuration of the clarification tube 120 according to the embodiment.
As shown in FIG. 3, electrodes 121 a and 121 b are provided on the outer peripheral surfaces of both ends in the length direction of the clarification tube 120, and an exhaust pipe 127 is provided on the wall in contact with the gas phase space of the clarification tube 120. It has been. The clarification tube 120 is preferably made of platinum, reinforced platinum, or a platinum alloy.
 なお、本明細書において、「白金族金属」は、白金族元素からなる金属を意味し、単一の白金族元素からなる金属のみならず白金族元素の合金を含む用語として使用する。ここで、白金族元素とは、白金(Pt)、パラジウム(Pd)、ロジウム(Rh)、ルテニウム(Ru)、オスミウム(Os)、イリジウム(Ir)の6元素を指す。白金族金属は高価ではあるが、融点が高く、熔融ガラスに対する耐食性にも優れている。
 なお、本実施例では、清澄管120が白金族金属から構成されている場合を具体例として説明するが、清澄管120の一部が、耐火物や他の金属などから構成されていてもよい。
In this specification, the “platinum group metal” means a metal composed of a platinum group element, and is used as a term including not only a metal composed of a single platinum group element but also an alloy of the platinum group element. Here, the platinum group element refers to six elements of platinum (Pt), palladium (Pd), rhodium (Rh), ruthenium (Ru), osmium (Os), and iridium (Ir). Platinum group metals are expensive, but have a high melting point and excellent corrosion resistance against molten glass.
In the present embodiment, a case where the clarification tube 120 is made of a platinum group metal will be described as a specific example. However, a part of the clarification tube 120 may be made of a refractory or other metal. .
 電極121a、121bは、電源装置122に接続されている。電極121a、121bの間に電圧が印加されることにより、電極121a、121bの間の清澄管120に電流が流れて、清澄管120が通電加熱される。この通電加熱により、清澄管120の最高温度が例えば、1600℃~1750℃、より好ましくは1630℃~1750℃となるように加熱され、ガラス供給管104から供給された熔融ガラスの最高温度は、脱泡処理に適した温度、例えば、1630℃~1720℃に加熱される。
 また、通電加熱によって熔融ガラスの温度を制御することで、清澄管120内の熔融ガラスの粘度を調節し、これにより清澄管120を通過する熔融ガラスの流速を調節することができる。熔融ガラスの流速を調節するために、清澄管120に通電する目標電力量は5kW以上とすることがより好ましく、10kW以上とすることが好ましい。特に、清澄管120の出口に通電する目標電力量を、5kW以上とすることが好ましく、8kW以上とすることがより好ましい。電力量を上記範囲とすることで、熔融ガラスの流量を電力量にて調整することができる。
The electrodes 121 a and 121 b are connected to the power supply device 122. When a voltage is applied between the electrodes 121a and 121b, a current flows through the clarification tube 120 between the electrodes 121a and 121b, and the clarification tube 120 is energized and heated. By this energization heating, the clarification tube 120 is heated so that the maximum temperature is, for example, 1600 ° C. to 1750 ° C., more preferably 1630 ° C. to 1750 ° C., and the maximum temperature of the molten glass supplied from the glass supply tube 104 is It is heated to a temperature suitable for the defoaming treatment, for example, 1630 ° C. to 1720 ° C.
Further, by controlling the temperature of the molten glass by energization heating, the viscosity of the molten glass in the clarification tube 120 can be adjusted, and thereby the flow rate of the molten glass passing through the clarification tube 120 can be adjusted. In order to adjust the flow rate of the molten glass, the target power amount to be passed through the clarification tube 120 is more preferably 5 kW or more, and more preferably 10 kW or more. In particular, the target power amount to be energized at the outlet of the clarification tube 120 is preferably 5 kW or more, and more preferably 8 kW or more. By setting the power amount within the above range, the flow rate of the molten glass can be adjusted by the power amount.
 また、電極121a、121bには、図示しない温度計測装置(熱電対等)が設けられていてもよい。温度計測装置は電極121a、121bの温度を計測し、計測した結果を、制御装置123に出力する。
 制御装置123は、CPU、メモリ等を含むコンピュータである。制御装置123は電源装置122が清澄管120に通電させる電流量及び電力量を制御する。これにより、制御装置123は、清澄管120内の熔融ガラスの温度および流速を調節することができる。
The electrodes 121a and 121b may be provided with a temperature measurement device (thermocouple or the like) (not shown). The temperature measuring device measures the temperature of the electrodes 121 a and 121 b and outputs the measured result to the control device 123.
The control device 123 is a computer including a CPU, a memory, and the like. The control device 123 controls the amount of current and the amount of power that the power supply device 122 supplies to the clarification tube 120. Thereby, the control apparatus 123 can adjust the temperature and flow velocity of the molten glass in the clarification tube 120.
 清澄管120の気相空間と接する壁には、排気管127が設けられている。排気管127は、清澄管120の本体外壁面から外側に向かって煙突状に突出する形状であってもよい。排気管127は、清澄管120の内部空間の一部である気相空間120aと、清澄管120の外部空間とを連通している。 An exhaust pipe 127 is provided on the wall in contact with the gas phase space of the clarification pipe 120. The exhaust pipe 127 may have a shape protruding in a chimney shape from the outer wall surface of the main body of the clarification pipe 120 toward the outside. The exhaust pipe 127 communicates the gas phase space 120 a that is a part of the internal space of the clarification pipe 120 and the external space of the clarification pipe 120.
 図4は清澄管120の本体の長手方向および排気管127の長手方向における清澄管120の断面図である。清澄管120の本体の外壁面、電極121a、121bの外壁面および排気管127の外壁面には、断熱材140が設けられている。 FIG. 4 is a cross-sectional view of the clarification tube 120 in the longitudinal direction of the main body of the clarification tube 120 and in the longitudinal direction of the exhaust pipe 127. A heat insulating material 140 is provided on the outer wall surface of the main body of the clarification tube 120, the outer wall surfaces of the electrodes 121 a and 121 b, and the outer wall surface of the exhaust pipe 127.
 断熱材140は、清澄管120が変形しないように支持するとともに、清澄管120を保温する役割を果たす。断熱材140には、優れた耐火性を有し、かつ、強度(剛性)が充分に高い部材を用いることができる。
 清澄管120からの放熱量を精度よく制御するために、断熱材140として、熱伝導率の異なる材料を用いることが好ましい。例えば、熱伝導率がより高い第1の断熱材と、熱伝導率がより低い第2の断熱材を用い、清澄管120の放熱を促進する領域に第1の断熱材を配置し、その他の領域に第2の断熱材を用いることで、清澄管120の各領域からの放熱量を調整することができる。
 第1の断熱材は、清澄管120の全領域と当接するように設ける必要はない。少なくとも高温領域と当接する箇所、および、低温領域と当接する箇所に伝熱媒体130を選択的に設けるとともに、両者を接続するように伝熱媒体130を設けることが好ましい。
 第1の断熱材の熱伝導率は、第2の断熱材の熱伝導率の2倍以上であることが好ましく、5倍以上であることがより好ましい。
 第1の断熱材には、1000℃における熱伝導率が2~40W/m・Kである材料を用いることが好ましい。具体的には、第1の断熱材として、アルミナ電鋳耐火物、マグネシア質耐火物、炭化ケイ素耐火物等を用いることができる。
 第2の断熱材には、1000℃における熱伝導率が0.1~1W/m・Kである材料を用いることが好ましい。具体的には、第2の断熱材として、多孔質レンガ、セラミックファイバー等を用いることができる。
The heat insulating material 140 plays a role of keeping the fining tube 120 warm while supporting the fining tube 120 so as not to deform. As the heat insulating material 140, a member having excellent fire resistance and sufficiently high strength (rigidity) can be used.
In order to accurately control the amount of heat released from the clarification tube 120, it is preferable to use materials having different thermal conductivities as the heat insulating material 140. For example, a first heat insulating material having a higher thermal conductivity and a second heat insulating material having a lower thermal conductivity are used, and the first heat insulating material is disposed in a region that promotes heat dissipation of the clarification tube 120. By using the second heat insulating material for the region, the amount of heat released from each region of the clarification tube 120 can be adjusted.
It is not necessary to provide the first heat insulating material so as to contact the entire region of the clarification tube 120. It is preferable that the heat transfer medium 130 is selectively provided at least at a location that contacts the high temperature region and a location that contacts the low temperature region, and the heat transfer medium 130 is provided so as to connect both.
The thermal conductivity of the first heat insulating material is preferably at least twice that of the second heat insulating material, and more preferably at least five times.
It is preferable to use a material having a thermal conductivity of 2 to 40 W / m · K at 1000 ° C. as the first heat insulating material. Specifically, an alumina electrocast refractory, a magnesia refractory, a silicon carbide refractory, or the like can be used as the first heat insulating material.
As the second heat insulating material, a material having a thermal conductivity at 1000 ° C. of 0.1 to 1 W / m · K is preferably used. Specifically, porous brick, ceramic fiber, or the like can be used as the second heat insulating material.
 清澄管120から外部への放熱量は、制御装置123が目標電流量以上又は目標電力量以上となるように電流を清澄管120に通電しながら熔融ガラスの温度および流量を制御することができるように調節されている。この放熱量は、清澄管120を通過する熔融ガラスの流量が最大となるときに必要な放熱量である。放熱量は、清澄管120から外部空間への熱抵抗を調整することで、制御することができる。例えば、断熱材140として用いる第1の断熱材および第2の断熱材の熱伝導率や配置を調整することで、熱抵抗を調整することができる。 The amount of heat released from the clarification tube 120 to the outside can be controlled by controlling the temperature and flow rate of the molten glass while the control device 123 supplies current to the clarification tube 120 so that the current amount is greater than or equal to the target current amount. It is adjusted to. This amount of heat radiation is the amount of heat radiation required when the flow rate of the molten glass passing through the clarification tube 120 is maximized. The amount of heat radiation can be controlled by adjusting the thermal resistance from the clarification tube 120 to the external space. For example, the thermal resistance can be adjusted by adjusting the thermal conductivity and arrangement of the first heat insulating material and the second heat insulating material used as the heat insulating material 140.
 清澄管120から外部空間への熱抵抗を低下させることで、断熱材140を介して清澄管120から外部空間への熱伝導が促進される。これにより、清澄管へ通電する電力量が、熔融ガラスの流量制御ができる電力量以上となり、清澄管120を通過する熔融ガラスの流量が多い場合でも、電力量により熔融ガラスの流量制御をすることができる。 By reducing the thermal resistance from the clarification tube 120 to the external space, heat conduction from the clarification tube 120 to the external space through the heat insulating material 140 is promoted. As a result, the amount of power supplied to the clarified tube is equal to or greater than the amount of power that can control the flow rate of the molten glass. Can do.
 なお、清澄管120の高温領域と低温領域との温度差は、白金族金属の揮発の抑制と清澄効果とを両立する観点から、50℃以上200℃以下であることが好ましく、70℃以上150℃以下であることがより好ましい。ここで、高温領域とは、他の領域よりも温度が高い領域を示す。清澄管120の場合、例えば、高温領域は、清澄管120の温度が1600℃以上の温度範囲にある領域、あるいは、1620℃以上の温度範囲にある領域であってもよい。また、例えば、高温領域は清澄管120が熔融ガラスを処理する際に最高温度となる領域を含んでもよい。低温領域とは、他の領域よりも温度が低い領域を示し、具体的には、高温領域よりも温度が低い領域を示す。清澄管120の場合、低温領域とは、清澄管120の温度が1600℃未満の温度範囲にある領域、あるいは1590℃以下の温度範囲にある領域であってもよい。また、例えば、低温領域は清澄管120が熔融ガラスを処理する際に最低温度となる領域を含んでもよい。例えば、清澄管120の電極121a、121bとの接続部分、および、排気管127との接続部分は、電極121a、121bおよび排気管127から外部への放熱が行われるため、清澄管120の他の領域と比較して低温となりやすい。すなわち、清澄管の電極121a、121bとの接続部分、および、排気管127との接続部分の領域は、低温領域となり、電極121a、121bと排気管127の間の領域は、高温領域となる。
 高温領域と低温領域との温度差を上記範囲とするために、低温領域の最低温度は1300℃以上1600℃以下であることが好ましく、1400℃以上1600℃以下であることがより好ましく、1500℃以上1600℃以下であることがさらに好ましい。また、高温領域の最高温度は1600℃以上1750℃以下であることが好ましく、1600℃以上1720℃以下であることがより好ましく、1610℃以上1700℃以下であることがさらに好ましい。
In addition, the temperature difference between the high temperature region and the low temperature region of the clarification tube 120 is preferably 50 ° C. or more and 200 ° C. or less, and 70 ° C. or more and 150 ° C. or less from the viewpoint of achieving both suppression of volatilization of the platinum group metal and the clarification effect. It is more preferable that it is below ℃. Here, the high temperature region indicates a region having a higher temperature than other regions. In the case of the clarification tube 120, for example, the high temperature region may be a region where the temperature of the clarification tube 120 is in a temperature range of 1600 ° C. or higher, or a region in a temperature range of 1620 ° C. or higher. Further, for example, the high temperature region may include a region where the maximum temperature is reached when the clarification tube 120 processes the molten glass. The low temperature region indicates a region where the temperature is lower than that of other regions, and specifically indicates a region where the temperature is lower than that of the high temperature region. In the case of the clarification tube 120, the low temperature region may be a region where the temperature of the clarification tube 120 is in a temperature range of less than 1600 ° C or a temperature range of 1590 ° C or less. Further, for example, the low temperature region may include a region where the refining tube 120 is at the lowest temperature when the molten glass is processed. For example, the connection portion of the clarification tube 120 with the electrodes 121a and 121b and the connection portion with the exhaust pipe 127 are radiated to the outside from the electrodes 121a and 121b and the exhaust pipe 127. It tends to be low temperature compared to the area. That is, the region of the connection portion between the electrodes 121a and 121b of the clarification tube and the connection portion with the exhaust tube 127 is a low temperature region, and the region between the electrodes 121a and 121b and the exhaust tube 127 is a high temperature region.
In order to make the temperature difference between the high temperature region and the low temperature region within the above range, the minimum temperature in the low temperature region is preferably 1300 ° C. or more and 1600 ° C. or less, more preferably 1400 ° C. or more and 1600 ° C. or less, and 1500 ° C. The temperature is more preferably 1600 ° C. or lower. The maximum temperature in the high temperature region is preferably 1600 ° C. or higher and 1750 ° C. or lower, more preferably 1600 ° C. or higher and 1720 ° C. or lower, and further preferably 1610 ° C. or higher and 1700 ° C. or lower.
 ところで、白金族金属が内壁面に用いられた処理装置を熔融ガラスが通過すると、加熱された内部表面の気相空間(酸素を含む雰囲気)に接する部分において白金族金属が酸化物として揮発する。例えば、白金族金属からなる清澄管120では、気相空間において白金族金属が酸化され揮発する。この揮発は特に清澄管120の高温領域で顕著である。一方、白金族金属の酸化物は、処理装置の局所的に温度が低下した位置(例えば電極の周辺)で還元され、還元された白金族金属が凝集し内壁面に付着(凝集)する。内壁面に付着した白金族金属の凝集物は熔融ガラス中に落下し異物として混入し、ガラス基板の品質の低下を招くおそれがある。特に清澄剤として酸化錫を用いる場合には清澄効果を得るために必要な最高温度が高くなるため、揮発および付着の問題が一層顕著となる。このため、処理装置の局所的に温度が低下する領域(低温領域)の温度を上昇させることで、白金族金属の凝集を防ぐことが考えられる。高温領域と低温領域との温度差が200℃以下、好ましくは150℃以下であると、高温領域で酸化された白金族金属の酸化物が低温領域で還元されることを低減でき、固化した白金族金属の凝集物が熔融ガラスに混入することがほとんどない。
 気相空間中の酸素濃度を0%にすれば、白金族金属の揮発を防ぐことができる。このため、白金族金属の揮発を防ぐ観点からは、気相空間中の酸素濃度を0%にすることが好ましい。しかし、気相空間の酸素濃度を常に0%に保つためには清澄剤の含有量を極めて減らすことや、コストがかかるという問題がある。このため、泡低減、低コスト及び白金族金属の揮発の低減を両立するために、気相空間の酸素濃度は、0.01%以上であることが好ましい。気相空間の酸素濃度が小さくなり過ぎると、熔融ガラスと気相空間の酸素濃度差が大きくなることで熔融ガラスから気相空間に放出される酸素が増加し、熔融ガラスが還元され過ぎてしまうことで、結果的に成形後のガラス基板に硫黄酸化物や窒素等の気泡が残存するおそれがある。一方、酸素濃度が大きすぎると、白金族金属の揮発が促進され、揮発した白金族金属の析出量が増大するおそれがある。以上のことから、気相空間中の酸素濃度は、0~30%であることが好ましく、0.1~10%であることがより好ましく、0.1~1%であることがさらにより好ましい。
 気相空間中の白金族金属の蒸気圧は0.1Pa~15Paであることが好ましく、3Pa~10Paであることがより好ましい。白金族金属の蒸気圧がこの範囲であると、還元された白金族金属の凝集物が内壁面に付着するのを抑制することができる。
By the way, when the molten glass passes through the processing apparatus in which the platinum group metal is used for the inner wall surface, the platinum group metal is volatilized as an oxide in a portion in contact with the gas phase space (atmosphere containing oxygen) on the heated inner surface. For example, in the clarification tube 120 made of a platinum group metal, the platinum group metal is oxidized and volatilized in the gas phase space. This volatilization is particularly noticeable in the high temperature region of the clarification tube 120. On the other hand, the oxide of the platinum group metal is reduced at a position where the temperature is locally lowered (for example, around the electrode) of the processing apparatus, and the reduced platinum group metal aggregates and adheres (aggregates) to the inner wall surface. Aggregates of platinum group metals adhering to the inner wall surface fall into the molten glass and enter as foreign substances, which may cause a deterioration in the quality of the glass substrate. In particular, when tin oxide is used as a fining agent, the maximum temperature necessary for obtaining a fining effect is increased, so that the problem of volatilization and adhesion becomes more prominent. For this reason, it is conceivable to prevent aggregation of the platinum group metal by increasing the temperature of the region (low temperature region) where the temperature locally decreases in the processing apparatus. When the temperature difference between the high temperature region and the low temperature region is 200 ° C. or less, preferably 150 ° C. or less, the reduction of the oxide of the platinum group metal oxidized in the high temperature region can be reduced, and solidified platinum Group metal agglomerates rarely enter molten glass.
If the oxygen concentration in the gas phase space is 0%, volatilization of the platinum group metal can be prevented. For this reason, from the viewpoint of preventing volatilization of the platinum group metal, the oxygen concentration in the gas phase space is preferably 0%. However, in order to always keep the oxygen concentration in the gas phase space at 0%, there are problems that the content of the fining agent is extremely reduced and costs are increased. For this reason, in order to achieve both foam reduction, low cost, and reduction of platinum group metal volatilization, the oxygen concentration in the gas phase space is preferably 0.01% or more. If the oxygen concentration in the gas phase space becomes too small, the oxygen concentration difference between the molten glass and the gas phase space increases, so that the oxygen released from the molten glass into the gas phase space increases and the molten glass is reduced too much. As a result, there is a possibility that bubbles such as sulfur oxide and nitrogen may remain on the glass substrate after molding. On the other hand, if the oxygen concentration is too high, volatilization of the platinum group metal is promoted, and the amount of volatilized platinum group metal deposited may increase. From the above, the oxygen concentration in the gas phase space is preferably 0 to 30%, more preferably 0.1 to 10%, and still more preferably 0.1 to 1%. .
The vapor pressure of the platinum group metal in the gas phase space is preferably 0.1 Pa to 15 Pa, and more preferably 3 Pa to 10 Pa. When the vapor pressure of the platinum group metal is within this range, the reduced platinum group metal aggregates can be prevented from adhering to the inner wall surface.
 一方、低温領域の温度を上昇させると、低温領域で冷却されていた熔融ガラスが冷却されなくなることにより、目標とする温度よりも高温の熔融ガラスが下流に流出することとなる。下流に流出させる熔融ガラスとして最適な温度は決まっているため、低温領域の温度を上昇させると、その後の工程における加熱量を低減させる必要がある。
 清澄管120においては、白金の還元を防止するために、電極121a、121bへの通電量を上昇させて低温領域である電極121a、121bの近傍の温度を上昇させると、熔融ガラスの温度が高くなりすぎてしまい、清澄管120よりも下流側での加熱量が小さくなるために流量の調整ができなくなるという問題が生じる。
 本実施形態によれば、高温領域と低温領域との温度差を、断熱材140の熱伝導率や配置、量を調節することにより調整することができる。これにより、電極121a、121bへの通電量を上昇させることで流量の調整ができなくなることを回避することができる。
On the other hand, when the temperature in the low temperature region is raised, the molten glass that has been cooled in the low temperature region is not cooled, so that molten glass that is higher in temperature than the target temperature flows out downstream. Since the optimum temperature for the molten glass flowing out downstream is determined, if the temperature in the low temperature region is raised, it is necessary to reduce the heating amount in the subsequent steps.
In the clarification tube 120, in order to prevent the reduction of platinum, the temperature of the molten glass increases when the amount of current supplied to the electrodes 121a and 121b is increased to increase the temperature in the vicinity of the electrodes 121a and 121b in the low temperature region. As a result, the amount of heating on the downstream side of the clarification tube 120 becomes small, so that the flow rate cannot be adjusted.
According to this embodiment, the temperature difference between the high temperature region and the low temperature region can be adjusted by adjusting the thermal conductivity, arrangement, and amount of the heat insulating material 140. Accordingly, it is possible to avoid the situation where the flow rate cannot be adjusted by increasing the energization amount to the electrodes 121a and 121b.
 断熱材140の熱伝導率や配置、量を変えたときの伝熱量は、例えば、有限要素法やメッシュフリー法により作成した3Dモデルを用いた数値流体力学的計算(コンピュータシミュレーション)により算出することができる。例えば、清澄管120、断熱材140、清澄管120内の熔融ガラスおよび気相空間を再現した3Dモデルを作成し、これを有限多数の領域(計算格子)に分割し、境界条件(清澄管12内の熔融ガラスおよび気相空間の温度、外部空間の温度等)および材料特性(熱伝導率等)を規定する。次に、コンピュータによる反復計算を用いて各計算格子における熱量の出入りを解析する。コンピュータシミュレーションを用いることにより、断熱材140の最適な熱伝導率や配置、量を経済的に容易に算出することができる。 The amount of heat transfer when the thermal conductivity, arrangement, and amount of the heat insulating material 140 are changed should be calculated by, for example, computational fluid dynamic calculation (computer simulation) using a 3D model created by the finite element method or the mesh-free method. Can do. For example, a 3D model that reproduces the refining tube 120, the heat insulating material 140, the molten glass in the refining tube 120, and the gas phase space is created, and this is divided into a finite number of regions (calculation grids), and boundary conditions (the refining tube 12 The temperature of the inner glass and the gas phase space, the temperature of the external space, etc.) and the material properties (thermal conductivity, etc.). Next, the amount of heat in and out of each calculation grid is analyzed using iterative calculation by a computer. By using computer simulation, the optimum thermal conductivity, arrangement, and amount of the heat insulating material 140 can be easily calculated economically.
 なお、本実施形態で抑制しようとしている白金族金属の凝集物は、一方向に細長い線状の形状をなし、最大長さの最小長さに対する比であり、アスペクト比が100以上である。例えば、白金族金属の凝集物の最大長さは50μm~300μm、最小長さは0.5μm~2μmである。ここで、白金族金属の凝集物の最大長さとは、白金族金属の凝集物を撮影して得られる異物の像に外接する外接長方形のうち最大長辺の長さをいい、最小長さとは、前記外接長方形の最小短辺の長さをいう。 In addition, the platinum group metal aggregate to be suppressed in the present embodiment has a linear shape elongated in one direction, which is the ratio of the maximum length to the minimum length, and the aspect ratio is 100 or more. For example, the maximum length of the platinum group metal aggregate is 50 μm to 300 μm, and the minimum length is 0.5 μm to 2 μm. Here, the maximum length of the platinum group metal aggregate is the maximum long side length of the circumscribed rectangle circumscribing the image of the foreign material obtained by photographing the platinum group metal aggregate. The minimum length is And the length of the minimum short side of the circumscribed rectangle.
(実験例1)
 清澄剤として酸化錫を用い、かつ上記実施形態の製造装置を用いて、2270mm×2000mm、厚さが0.5mmのガラス基板を作成した。また、ガラス基板のガラス組成は、SiO 66.6モル%、Al 10.6モル%、B 11.0モル%、MgO,CaO,SrO及びBaOの合量 11.4モル%、SnO 0.15モル%、Fe 0.05モル%、アルカリ金属酸化物 0.2モル%であり、歪点は660℃、粘度が102.5ポアズであるときの熔融ガラスの温度は1570℃であった。また、清澄管から外部への放熱量を調節することで、第1の移送管104に通電する電力量、清澄管120に通電する電力量、および、第2の移送管105に通電する電力量の比は、1:0.8:0.3とした。その結果、泡数が規定数以下であるガラス基板を、熔融ガラスが処理装置から溢れ出すことなく製造することができた。また、白金族金属の異物のガラス基板への混入数を0.001個/kg以下に抑えることができた。なお、白金族金属の異物として、アスペクト比が100以上であり、最大長さが100μm以上のあるものをカウントした。
(Experimental example 1)
A glass substrate having a thickness of 2270 mm × 2000 mm and a thickness of 0.5 mm was prepared using tin oxide as a fining agent and using the manufacturing apparatus of the above embodiment. The glass composition of the glass substrate was as follows: SiO 2 66.6 mol%, Al 2 O 3 10.6 mol%, B 2 O 3 11.0 mol%, MgO, CaO, SrO and BaO combined 11.4 Mol%, SnO 2 0.15 mol%, Fe 2 O 3 0.05 mol%, alkali metal oxide 0.2 mol%, the strain point is 660 ° C., and the viscosity is 10 2.5 poise. The temperature of the molten glass was 1570 ° C. In addition, by adjusting the amount of heat released from the clarification tube to the outside, the amount of power applied to the first transfer tube 104, the amount of power applied to the clarification tube 120, and the amount of power applied to the second transfer tube 105 The ratio was 1: 0.8: 0.3. As a result, a glass substrate having a number of bubbles equal to or less than the specified number could be produced without the molten glass overflowing from the processing apparatus. Moreover, the number of platinum group metal foreign matters mixed into the glass substrate could be suppressed to 0.001 piece / kg or less. In addition, as a foreign material of the platinum group metal, those having an aspect ratio of 100 or more and a maximum length of 100 μm or more were counted.
(実験例2)
 実験例1に対して、製造するガラス基板のガラス組成を、SiO 70モル%、Al 12.9モル%、B 2.5モル%、MgO 3.5モル%、CaO 6モル%、SrO 1.5モル%、BaO 3.5モル%、SnO 0.1モル%に変更した以外実施例1と同様の方法でガラス基板を作製した。このとき、ガラス基板の歪点は745℃であった。
 その結果、歪点が高く、清澄温度が実験例1よりも高くなるガラス基板を製造しても、実験例1と同様に、泡数が規定数以下であるガラス基板を、熔融ガラスが処理装置から溢れ出すことなく製造することができることがわかった。また、白金族金属のガラス基板への混入数を0.001個/kg以下に抑えることができることがわかった。
(Experimental example 2)
With respect to Experimental Example 1, the glass composition of the glass substrate to be manufactured was SiO 2 70 mol%, Al 2 O 3 12.9 mol%, B 2 O 3 2.5 mol%, MgO 3.5 mol%, CaO. 6 mol%, SrO 1.5 mol%, BaO 3.5 mol%, to prepare a glass substrate in the same manner as in example 1 except that the SnO 2 0.1 mol%. At this time, the strain point of the glass substrate was 745 ° C.
As a result, even if a glass substrate having a high strain point and a fining temperature higher than that of Experimental Example 1 is manufactured, a glass substrate having a number of bubbles equal to or less than a specified number is treated by the molten glass as in Experimental Example 1. It was found that it can be manufactured without overflowing. It was also found that the number of platinum group metals mixed into the glass substrate can be suppressed to 0.001 piece / kg or less.
(比較例)
 清澄管から外部への放熱量を調節しなかった点を除き、実験例1と同様の方法でガラス基板を作製した。このとき、このときの第1の移送管104に通電する電力量、清澄管120に通電する電力量、および、第2の移送管105に通電する電力量の比は、1:1.5:0.05であった。その結果、窒素又は酸化硫黄を含む泡数が規定数以上となった。
(Comparative example)
A glass substrate was produced in the same manner as in Experimental Example 1 except that the amount of heat released from the clarification tube to the outside was not adjusted. At this time, the ratio of the amount of power applied to the first transfer tube 104, the amount of power applied to the clarification tube 120, and the amount of power applied to the second transfer tube 105 is 1: 1.5: 0.05. As a result, the number of bubbles containing nitrogen or sulfur oxide became a specified number or more.
(ガラス組成)
 酸化錫を含む無アルカリガラス基板、又は、酸化錫を含む微アルカリガラス基板であると、本実施形態の効果は顕著となる。無アルカリガラス又は微アルカリガラスは、アルカリガラスと比較してガラス粘度が高い。そのため、熔解工程で熔融温度を高くする必要があり、多くの酸化錫が熔解工程で還元されてしまうので、清澄効果を得るためには清澄工程における熔融ガラス温度を高くして、酸化錫の還元をさらに促進し、かつ熔融ガラス粘度を低下させる必要がある。つまり、酸化錫を含む無アルカリガラス基板、又は、酸化錫を含む微アルカリガラス基板を製造する場合には、清澄工程における熔融ガラス温度を高くする必要があるので、熔融ガラスの流量を処理装置に通電する際の電力量により制御しにくく、かつ、白金族金属(例えば、白金または白金合金)の揮発が生じやすい。ここで、本明細書において、無アルカリガラス基板とは、アルカリ金属酸化物(Li2O、K2O、及びNa2O)を実質的に含有しないガラスである。また、微アルカリガラスとは、アルカリ金属酸化物の含有量(Li2O、K2O、及びNa2Oの合量)が0超0.8モル%以下のガラスである。
(Glass composition)
The effect of this embodiment becomes remarkable when it is a non-alkali glass substrate containing tin oxide or a fine alkali glass substrate containing tin oxide. The alkali-free glass or fine alkali glass has a higher glass viscosity than the alkali glass. Therefore, it is necessary to increase the melting temperature in the melting process, and many tin oxides are reduced in the melting process. Therefore, in order to obtain a clarification effect, the molten glass temperature in the clarification process is increased to reduce the tin oxide. Is required to be further promoted and the viscosity of the molten glass needs to be lowered. In other words, when producing a non-alkali glass substrate containing tin oxide or a fine alkali glass substrate containing tin oxide, it is necessary to increase the molten glass temperature in the refining step. It is difficult to control by the amount of electric power when energized, and the volatilization of platinum group metal (for example, platinum or platinum alloy) is likely to occur. Here, in the present specification, the alkali-free glass substrate is a glass that substantially does not contain alkali metal oxides (Li 2 O, K 2 O, and Na 2 O). The fine alkali glass is a glass having an alkali metal oxide content (total amount of Li 2 O, K 2 O, and Na 2 O) of more than 0 and not more than 0.8 mol%.
 本実施形態で製造されるガラス基板として、以下のガラス組成のガラス基板が例示される。したがって、以下のガラス組成をガラス基板が有するようにガラス原料は調合される。本実施形態で製造されるガラス基板は、例えば、SiO2 55~75モル%、Al23 5~20モル%、B23 0~15モル%、RO 5~20モル%(ROはMgO、CaO、SrO及びBaOの合量)、 R’2O 0~0.4モル%(R’はLi2O、K2O、及びNa2Oの合量)、SnO2 0.01~0.4モル%、含有する。
 このとき、SiO2、Al23、B23、及びRO(Rは、Mg、Ca、Sr及びBaのうち前記ガラス基板に含有される全元素)の少なくともいずれかを含み、モル比((2×SiO2)+Al23)/((2×B23)+RO)は4.0以上であってもよい。モル比((2×SiO2)+Al23)/((2×B23)+RO)は4.0以上であるガラスは、高温粘性の高いガラスの一例である。高温粘性の高いガラスは、一般的に清澄工程における熔融ガラス温度を高くする必要があるので、熔融ガラスの流量を処理装置に通電する際の電力量により制御しにくく、白金族金属の揮発が生じやすい。つまり、このような組成を有するガラス基板を製造する場合には、熔融ガラスの温度が熔融ガラスの流量制御ができる温度範囲となるように、処理装置から外部への放熱量を調節することで、熔融ガラスの流量を処理装置に通電する際の電力量により制御しやすくすること、熔融ガラス中に白金族金属の凝集物が異物として混入することの抑制と電力量による熔融ガラスの流量調整の両立といった本実施形態の効果は顕著になる。なお、高温粘性とは、熔融ガラスが高温になるときのガラスの粘性を示し、ここでいう高温とは、例えば、1300℃以上を示す。
As a glass substrate manufactured by this embodiment, the glass substrate of the following glass compositions is illustrated. Therefore, the glass raw material is prepared so that the glass substrate has the following glass composition. The glass substrate produced in the present embodiment includes, for example, SiO 2 55 to 75 mol%, Al 2 O 3 5 to 20 mol%, B 2 O 3 0 to 15 mol%, RO 5 to 20 mol% (RO is MgO, CaO, SrO and BaO total amount), R ′ 2 O 0 to 0.4 mol% (R ′ is the total amount of Li 2 O, K 2 O and Na 2 O), SnO 2 0.01 to Contains 0.4 mol%.
At this time, at least one of SiO 2 , Al 2 O 3 , B 2 O 3 , and RO (R is all elements contained in the glass substrate among Mg, Ca, Sr, and Ba) is included in a molar ratio. ((2 × SiO 2 ) + Al 2 O 3 ) / ((2 × B 2 O 3 ) + RO) may be 4.0 or more. A glass having a molar ratio ((2 × SiO 2 ) + Al 2 O 3 ) / ((2 × B 2 O 3 ) + RO) of 4.0 or more is an example of a glass having a high temperature viscosity. High-viscosity glass generally requires a higher molten glass temperature in the refining process, so it is difficult to control the flow rate of the molten glass by the amount of electric power when the processing device is energized, and the platinum group metal volatilizes. Cheap. In other words, when manufacturing a glass substrate having such a composition, by adjusting the amount of heat released from the processing apparatus to the outside so that the temperature of the molten glass is in a temperature range in which the flow rate of the molten glass can be controlled, Makes it easy to control the flow rate of the molten glass by the amount of power when energizing the processing device, suppresses the inclusion of platinum group metal agglomerates as foreign matter in the molten glass, and adjusts the flow rate of the molten glass by the amount of power The effect of this embodiment becomes remarkable. In addition, high temperature viscosity shows the viscosity of glass when molten glass becomes high temperature, and high temperature here shows 1300 degreeC or more, for example.
 本実施形態によれば、ガラス基板におけるアルカリ金属酸化物の含有率が0~0.8モル%であっても、電力量によって熔融ガラスの流量を制御することができ、熔融ガラス中に白金族金属の凝集物が異物として混入することを抑制することができる。アルカリ金属酸化物の含有率が小さいほど、高温粘性が高くなるので、アルカリ金属酸化物の含有率が0~0.8モル%のガラスは、アルカリ金属酸化物の含有率が0.8モル%を超えるガラスと比較して高温粘性が高い。高温粘性の高いガラスは、一般的に清澄工程における熔融ガラス温度を高くする必要があるので、処理装置に通電する電力量による熔融ガラスの流量制御をしにくく、白金族金属の揮発が生じやすい。つまり、この高温粘性の高いガラスを用いるときには、熔融ガラス中に白金族金属の凝集物が異物として混入することを抑制しつつ、熔融ガラスの温度が熔融ガラスの流量制御ができる温度範囲となるように、処理装置から外部への放熱量を調節することで、熔融ガラスの流量を処理装置に通電する際の電力量による制御を行いやすくするという本実施形態の効果は顕著になる。 According to this embodiment, even if the content of the alkali metal oxide in the glass substrate is 0 to 0.8 mol%, the flow rate of the molten glass can be controlled by the amount of electric power, and the platinum group is contained in the molten glass. It can suppress that the metal aggregate is mixed as a foreign material. The smaller the alkali metal oxide content, the higher the high-temperature viscosity. Therefore, a glass having an alkali metal oxide content of 0 to 0.8 mol% has an alkali metal oxide content of 0.8 mol%. High temperature viscosity is high compared to glass exceeding. Glass having high viscosity at high temperature generally needs to increase the temperature of the molten glass in the refining process, so that it is difficult to control the flow rate of the molten glass by the amount of electric power supplied to the processing apparatus, and the platinum group metal is likely to volatilize. That is, when using this glass having a high temperature viscosity, the temperature of the molten glass is in a temperature range in which the flow rate of the molten glass can be controlled while suppressing the agglomeration of the platinum group metal as a foreign substance in the molten glass. In addition, the effect of the present embodiment that makes it easy to control the flow rate of the molten glass by the amount of electric power when the processing apparatus is energized becomes remarkable by adjusting the amount of heat radiation from the processing apparatus to the outside.
 本実施形態で用いる熔融ガラスは、粘度が102.5ポアズであるときの温度は1500~1700℃であるガラス組成であってもよい。このように、高温粘性の高いガラスは、一般的に清澄工程における熔融ガラス温度を高くする必要があるので、処理装置に通電する電力量による熔融ガラスの流量制御をしにくく、白金族金属の揮発が生じやすい。すなわち、高温粘性のガラス組成であっても、本実施形態の上記効果は顕著になる。 The molten glass used in the present embodiment may have a glass composition in which the temperature is 1500 to 1700 ° C. when the viscosity is 10 2.5 poise. As described above, glass having a high temperature viscosity generally needs to increase the temperature of the molten glass in the refining process, so that it is difficult to control the flow rate of the molten glass by the amount of electric power supplied to the processing apparatus, and the volatilization of the platinum group metal. Is likely to occur. That is, even if it is a glass composition of high temperature viscosity, the said effect of this embodiment becomes remarkable.
 本実施形態で用いる熔融ガラスの歪点は650℃以上であってもよく、660℃以上であることがより好ましく、690℃以上であることがさらに好ましく、730℃以上が特に好ましい。また、歪点が高いガラスは、粘度が102.5ポアズにおける熔融ガラスの温度が高くなる傾向にある。つまり、歪点が高いガラス基板を製造する場合ほど、本実施形態の上記効果は顕著になる。また、歪点が高いガラスほど、高精細ディスプレイに使用されるため、白金族金属の凝集物が異物として混入する問題に対する要求が厳しい。そのため、高歪点のガラス基板ほど、白金族金属の凝集物混入を抑制できる本実施形態が好適となる。 The strain point of the molten glass used in this embodiment may be 650 ° C. or higher, more preferably 660 ° C. or higher, further preferably 690 ° C. or higher, and particularly preferably 730 ° C. or higher. Further, a glass having a high strain point tends to increase the temperature of the molten glass at a viscosity of 10 2.5 poise. That is, the effect of this embodiment becomes more remarkable as the glass substrate having a higher strain point is manufactured. In addition, since the glass having a higher strain point is used for a high-definition display, the demand for the problem that platinum group metal aggregates are mixed as foreign substances is severe. For this reason, the glass substrate having a higher strain point is more suitable for the present embodiment, which can suppress the inclusion of platinum group metal aggregates.
 また、酸化錫を含み、粘度が102.5ポアズであるときの熔融ガラスの温度が1500℃以上となるガラスになるようにガラス原料を熔解した場合、より本実施形態の上記効果は顕著になり、粘度が102.5ポアズであるときの熔融ガラスの温度は、例えば1500℃~1700℃であり、1550℃~1650℃であってもよい。 Further, when the glass raw material is melted so that the temperature of the molten glass containing tin oxide and the viscosity of 10 2.5 poise becomes 1500 ° C. or more, the above effect of the present embodiment is more remarkable. Thus, the temperature of the molten glass when the viscosity is 10 2.5 poise is, for example, 1500 ° C. to 1700 ° C., and may be 1550 ° C. to 1650 ° C.
 ガラス基板の表面に位置する白金族金属の凝集物は、ガラス基板を用いたパネル製造工程において離脱すると、離脱した部分が凹部となり、ガラス基板上に形成される薄膜が均一に形成されず、画面の表示欠陥を引き起こすという問題がある。さらに、ガラス基板中に白金族金属の凝集物が存在すると、徐冷工程において、ガラスと白金族金属の熱膨張率差により歪が生じるため、画面の表示欠陥を引き起こすという問題がある。そのため、本実施形態は、画面の表示欠陥に対する要求が厳しいディスプレイ用ガラス基板の製造に好適である。特に、画面の表示欠陥に対する要求のさらに厳しい、IGZO(インジウム、ガリウム、亜鉛、酸素)等の酸化物半導体を使用した酸化物半導体ディスプレイ用ガラス基板及びLTPS(低温度ポリシリコン)半導体を使用したLTPSディスプレイ用ガラス基板等の高精細ディスプレイ用ガラス基板に好適である。
 以上のことから、本実施形態で製造されるガラス基板は、フラットパネルディスプレイ用ガラス基板を含むディスプレイ用ガラス基板に好適である。酸化物半導体ディスプレイ用ガラス基板又はLTPSディスプレイ用ガラス基板に好適である。また、本実施形態で製造されるガラス基板は、アルカリ金属酸化物の含有量が極めて少ないことが求められる液晶ディスプレイ用ガラス基板に好適である。また、有機ELディスプレイ用ガラス基板にも好適である。言い換えると、本実施形態のガラス基板の製造方法は、ディスプレイ用ガラス基板の製造に好適であり、特に、液晶ディスプレイ用ガラス基板の製造に好適である。
 また、本実施形態で製造されるガラス基板は、カバーガラス、磁気ディスク用ガラス、太陽電池用ガラス基板などにも適用することが可能である。
When the aggregate of platinum group metals located on the surface of the glass substrate is detached in the panel manufacturing process using the glass substrate, the detached portion becomes a recess, and the thin film formed on the glass substrate is not uniformly formed, and the screen Cause a display defect. Furthermore, if a platinum group metal aggregate is present in the glass substrate, distortion occurs due to the difference in thermal expansion coefficient between the glass and the platinum group metal in the slow cooling step, causing a display defect on the screen. For this reason, this embodiment is suitable for manufacturing a glass substrate for a display, which has severe demands for display defects on the screen. In particular, glass substrates for oxide semiconductor displays using oxide semiconductors such as IGZO (indium, gallium, zinc, oxygen) and LTPS (low temperature polysilicon) semiconductors, which are more demanding for display defects on the screen. It is suitable for glass substrates for high-definition displays such as display glass substrates.
From the above, the glass substrate produced in the present embodiment is suitable for a glass substrate for display including a glass substrate for flat panel display. It is suitable for a glass substrate for oxide semiconductor display or a glass substrate for LTPS display. Moreover, the glass substrate manufactured by this embodiment is suitable for the glass substrate for liquid crystal displays by which it is calculated | required that content of an alkali metal oxide is very small. Moreover, it is suitable also for the glass substrate for organic EL displays. In other words, the manufacturing method of the glass substrate of this embodiment is suitable for manufacture of the glass substrate for displays, and is especially suitable for manufacture of the glass substrate for liquid crystal displays.
Moreover, the glass substrate manufactured by this embodiment is applicable also to a cover glass, the glass for magnetic discs, the glass substrate for solar cells, etc.
 以上、本発明のガラス基板の製造方法について詳細に説明したが、本発明は上記実施形態に限定されず、本発明の主旨を逸脱しない範囲において、種々の改良や変更をしてもよいのはもちろんである。 As mentioned above, although the manufacturing method of the glass substrate of this invention was demonstrated in detail, this invention is not limited to the said embodiment, In the range which does not deviate from the main point of this invention, you may make various improvement and a change. Of course.
 例えば、図示しないが、清澄管120の近傍と断熱材140の外部との間に冷媒の循環管を設け、循環管の内部で冷媒を循環させることで、放熱量を調節してもよい。この場合、冷媒の循環量を制御することで放熱量を調整することができる。
 循環管に循環させる冷媒は、水などの液体であってもよいし、空気などの気体であってもよい。
 循環管には、融点が高い金属材料を用いることができる。具体的には、白金、ロジウム、銀、パラジウム、金、またはこれらの合金を循環管の材料として用いることができる。
For example, although not shown in the figure, the amount of heat release may be adjusted by providing a refrigerant circulation pipe between the vicinity of the clarification pipe 120 and the outside of the heat insulating material 140 and circulating the refrigerant inside the circulation pipe. In this case, the heat radiation amount can be adjusted by controlling the circulation amount of the refrigerant.
The refrigerant circulated in the circulation pipe may be a liquid such as water or a gas such as air.
A metal material having a high melting point can be used for the circulation pipe. Specifically, platinum, rhodium, silver, palladium, gold, or an alloy thereof can be used as a material for the circulation pipe.
 上記説明においては、清澄管120を中心に本発明の説明をしたが、清澄管120に限らず、熔解装置100の他の部分(熔解槽101、攪拌槽103、移送管104、105、ガラス供給管106)や成形装置200からの放熱量を調節してもよい。 In the above description, the present invention has been described mainly with respect to the clarification tube 120. However, the present invention is not limited to the clarification tube 120, but other parts of the melting apparatus 100 (dissolution tank 101, stirring tank 103, transfer pipes 104 and 105, glass supply). The amount of heat released from the tube 106) or the molding apparatus 200 may be adjusted.
101 熔解槽
103 攪拌槽
104、105 移送管
105 ガラス供給管
120 清澄管(清澄装置)
121a、121b 電極
122 電源装置
123 制御装置
127 排気管
140 断熱材
200 成形装置
101 melting tank 103 stirring tank 104, 105 transfer pipe 105 glass supply pipe 120 clarification pipe (clarification apparatus)
121a, 121b Electrode 122 Power supply device 123 Control device 127 Exhaust pipe 140 Heat insulation material 200 Molding device

Claims (11)

  1.  熔融ガラスを処理する処理装置を用いるガラス基板の製造方法であって、
     熔融ガラスを処理する際に、
     前記処理装置内の熔融ガラスの温度が前記処理をするのに適した範囲になるように、前記処理装置に通電をすることにより前記処理装置を加熱し、
     前記処理装置内の前記熔融ガラスの流量を、前記通電をする際の電力量により制御し、
     前記電力量が前記熔融ガラスの流量制御ができる電力量以上となり、かつ、前記熔融ガラスの温度が前記熔融ガラスの流量制御ができる温度範囲となるように、前記処理装置から外部への放熱量を調節する、ガラス基板の製造方法。
    A method for manufacturing a glass substrate using a processing apparatus for processing molten glass,
    When processing molten glass,
    Heating the processing device by energizing the processing device so that the temperature of the molten glass in the processing device is in a range suitable for the processing,
    The flow rate of the molten glass in the processing device is controlled by the amount of electric power when energizing,
    The amount of heat radiation from the processing device to the outside is set so that the amount of electric power is equal to or greater than the amount of electric power capable of controlling the flow rate of the molten glass, and the temperature of the molten glass is in a temperature range capable of controlling the flow rate of the molten glass. A method of manufacturing a glass substrate to be adjusted.
  2.  熔融ガラスを処理する処理装置を用いるガラス基板の製造方法であって、
     熔融ガラスを処理する際に、
     前記処理装置内の熔融ガラスの温度が前記処理をするのに適した範囲になるように、前記処理装置に通電をすることにより前記処理装置を加熱し、
     前記処理装置内の前記熔融ガラスの流量を、前記通電をする際の電流量により制御し、
     前記熔融ガラスの流量制御ができる電流量以上となるように、前記処理装置から外部への放熱量を調節する、ガラス基板の製造方法。
    A method for manufacturing a glass substrate using a processing apparatus for processing molten glass,
    When processing molten glass,
    Heating the processing device by energizing the processing device so that the temperature of the molten glass in the processing device is in a range suitable for the processing,
    The flow rate of the molten glass in the processing device is controlled by the amount of current when the current is applied,
    A method for producing a glass substrate, wherein the amount of heat released from the processing device to the outside is adjusted so as to be equal to or greater than an amount of current that enables flow control of the molten glass.
  3.  前記処理装置は内壁と熔融ガラス液面とから形成される気相空間を有し、前記内壁の少なくとも前記気相空間と接する部分は白金族金属を含む材料で構成され、
     前記処理装置には、熔融ガラスを処理する際に高温領域と、熔融ガラスを処理する際に高温領域よりも温度の低い低温領域が形成され、
     前記高温領域と前記低温領域の温度差が200℃以下となるように前記放熱量を調整する、請求項1又は2に記載のガラス基板の製造方法。
    The processing apparatus has a gas phase space formed by an inner wall and a molten glass liquid surface, and at least a portion of the inner wall in contact with the gas phase space is made of a material containing a platinum group metal,
    In the processing apparatus, a high temperature region is formed when the molten glass is processed, and a low temperature region lower in temperature than the high temperature region is formed when the molten glass is processed,
    The manufacturing method of the glass substrate of Claim 1 or 2 which adjusts the said thermal radiation amount so that the temperature difference of the said high temperature area | region and the said low temperature area | region will be 200 degrees C or less.
  4.  前記処理装置は断熱材により覆われ、
     前記断熱材により前記処理装置から外部空間への熱抵抗を調整することで、前記放熱量を制御する、請求項1~3のいずれか一項に記載のガラス基板の製造方法。
    The treatment device is covered with a heat insulating material,
    The method for producing a glass substrate according to any one of claims 1 to 3, wherein the heat radiation amount is controlled by adjusting a thermal resistance from the processing apparatus to an external space by the heat insulating material.
  5.  前記断熱材の熱伝導率および配置を調整することで、前記熱抵抗を調整する、請求項4に記載のガラス基板の製造方法。 The method for producing a glass substrate according to claim 4, wherein the thermal resistance is adjusted by adjusting a thermal conductivity and an arrangement of the heat insulating material.
  6.  前記処理装置は、熔融ガラスを清澄させる清澄装置であり、
     前記清澄装置を、前記清澄装置内の熔融ガラスの最高温度が、前記熔融ガラスに含まれる酸化錫の還元反応が生じる温度以上となるように、前記清澄装置に通電をすることにより加熱し、
     前記清澄装置内の前記熔融ガラスの流量を、前記通電をする際の電力量により制御し、
     前記電力量が前記熔融ガラスの流量制御ができる電力量以上となるように、前記清澄装置から外部への放熱量を調節する、請求項1~5のいずれか一項に記載のガラス基板の製造方法。
    The processing device is a clarification device for clarifying molten glass,
    The clarifier is heated by energizing the clarifier so that the maximum temperature of the molten glass in the clarifier is equal to or higher than the temperature at which the reduction reaction of tin oxide contained in the molten glass occurs.
    The flow rate of the molten glass in the clarification device is controlled by the amount of power when energizing,
    The production of a glass substrate according to any one of claims 1 to 5, wherein an amount of heat released from the clarifier to the outside is adjusted so that the amount of electric power is equal to or greater than an amount of electric power capable of controlling the flow rate of the molten glass. Method.
  7.  前記清澄装置は、熔融ガラス中の気泡が排出される気相空間を有する清澄管と、前記清澄管内へ供給される熔融ガラスが移送される第1の移送管と、前記清澄管から排出される熔融ガラスが移送される第2の移送管と、を有し、
     前記第1の移送管、前記清澄管および前記第2の移送管において、清澄剤の還元反応により熔融ガラスの脱泡処理、および、清澄剤の酸化反応により熔融ガラス中の気泡を吸収する吸収処理を行い、
     前記第1の移送管に通電する電力量、前記清澄管のうち前記脱泡処理を行う領域に通電する電力量、および、前記清澄管および前記第2の移送管のうち前記吸収処理を行う領域に通電する電力量の比は、1:0.6~1:0.1~0.4である、請求項6に記載のガラス基板の製造方法。
    The clarification device is discharged from the clarification tube having a gas phase space through which bubbles in the molten glass are discharged, a first transfer tube to which the molten glass supplied into the clarification tube is transferred, and the clarification tube. A second transfer pipe through which the molten glass is transferred,
    In the first transfer pipe, the clarification pipe, and the second transfer pipe, the defoaming treatment of the molten glass by the reductive reaction of the clarifier and the absorption treatment that absorbs the bubbles in the molten glass by the oxidation reaction of the clarifier. And
    The amount of power to be applied to the first transfer pipe, the amount of power to be supplied to the area for performing the defoaming process in the clarification pipe, and the area for performing the absorption process among the clarification pipe and the second transfer pipe. The method for manufacturing a glass substrate according to claim 6, wherein the ratio of the amount of electric power applied to the current is 1: 0.6 to 1: 0.1 to 0.4.
  8.  前記清澄装置は、熔融ガラス中の気泡が排出される気相空間を有する清澄管と、前記清澄管内へ供給される熔融ガラスが移送される第1の移送管と、前記清澄管から排出される熔融ガラスが移送される第2の移送管と、を有し、
     前記清澄管の一部の領域において、清澄剤の還元反応により熔融ガラスの脱泡処理を行い、
     前記清澄管の他の領域および前記第2の移送管において、清澄剤の酸化反応により熔融ガラス中の気泡を吸収する吸収処理を行い、
     前記第1の移送管に通電する電力量、前記清澄管の一部の領域に通電する電力量、および、前記清澄管の他の領域に通電する電力量の比は、1:0.6~1:0.05~0.4である、請求項6に記載のガラス基板の製造方法。
    The clarification device is discharged from the clarification tube having a gas phase space through which bubbles in the molten glass are discharged, a first transfer tube to which the molten glass supplied into the clarification tube is transferred, and the clarification tube. A second transfer pipe through which the molten glass is transferred,
    In a partial region of the clarification tube, a defoaming treatment of the molten glass is performed by a reduction reaction of the clarifier,
    In the other region of the clarification tube and the second transfer tube, an absorption treatment for absorbing bubbles in the molten glass by an oxidation reaction of the clarifier is performed,
    The ratio of the amount of power applied to the first transfer pipe, the amount of power applied to a partial area of the clarification pipe, and the amount of power supplied to the other area of the clarification pipe is from 1: 0.6 to The method for producing a glass substrate according to claim 6, wherein the ratio is 1: 0.05 to 0.4.
  9.  前記処理装置は、熔融ガラス中の気泡が排出される気相空間を有する清澄管と、前記清澄管内へ供給される熔融ガラスが移送される第1の移送管と、前記清澄管から排出される熔融ガラスが移送される第2の移送管と、を有し、
     前記清澄管において、清澄剤の還元反応により熔融ガラスの脱泡処理を行い、
     前記第2の移送管において、清澄剤の酸化反応により熔融ガラス中の気泡を吸収する吸収処理を行い、
     前記第1の移送管に通電する電力量、前記清澄管に通電する電力量、および、前記第2の移送管に通電する電力量の比は、1:0.6~1:0.1~0.4である、請求項6に記載のガラス基板の製造方法。
    The processing device is discharged from the clarification tube having a gas phase space in which bubbles in the molten glass are discharged, a first transfer tube to which the molten glass supplied into the clarification tube is transferred, and the clarification tube. A second transfer pipe through which the molten glass is transferred,
    In the clarification tube, the defoaming treatment of the molten glass is performed by the reduction reaction of the clarifier,
    In the second transfer pipe, an absorption treatment for absorbing bubbles in the molten glass by an oxidation reaction of a clarifying agent is performed.
    The ratio of the amount of power applied to the first transfer tube, the amount of power applied to the clarification tube, and the amount of power applied to the second transfer tube is 1: 0.6 to 1: 0.1 to The manufacturing method of the glass substrate of Claim 6 which is 0.4.
  10.  熔融ガラスを処理する処理装置と、
     熔融ガラスを処理する際に、前記処理装置内の熔融ガラスの温度が前記処理をするのに適した範囲になるように、前記処理装置に通電をすることで加熱する通電装置と、
     前記処理装置内の前記熔融ガラスの流量を、前記通電をする際の電力量により制御する制御装置と、を備え、
     前記電力量が前記熔融ガラスの流量制御ができる電力量以上となり、かつ、前記熔融ガラスの温度が前記熔融ガラスの流量制御ができる温度範囲となるように、前記処理装置から外部への放熱量が調節されている、ガラス基板製造装置。
    A processing apparatus for processing molten glass;
    An energizer that heats the processing apparatus by energizing the processing apparatus so that the temperature of the molten glass in the processing apparatus is in a range suitable for the processing when the molten glass is processed;
    A control device for controlling the flow rate of the molten glass in the processing device by the amount of electric power when energizing,
    The amount of heat radiation from the processing device to the outside is such that the amount of electric power is equal to or greater than the amount of electric power capable of controlling the flow rate of the molten glass, and the temperature of the molten glass is within a temperature range capable of controlling the flow rate of the molten glass. Glass substrate manufacturing equipment that is being adjusted.
  11.  熔融ガラスを処理する処理装置と、
     熔融ガラスを処理する際に、前記処理装置内の熔融ガラスの温度が前記処理をするのに適した範囲になるように、前記処理装置に通電をすることで加熱する通電装置と、
     前記処理装置内の前記熔融ガラスの流量を、前記通電をする際の電流量により制御する制御装置と、を備え、
     前記熔融ガラスの流量制御ができる電流量以上となるように、前記処理装置から外部への放熱量が調節されている、ガラス基板製造装置。
     
    A processing apparatus for processing molten glass;
    An energizer that heats the processing apparatus by energizing the processing apparatus so that the temperature of the molten glass in the processing apparatus is in a range suitable for the processing when the molten glass is processed;
    A control device for controlling the flow rate of the molten glass in the processing device by the amount of current when the current is applied;
    The glass substrate manufacturing apparatus in which the amount of heat radiation from the processing apparatus to the outside is adjusted so as to be equal to or greater than the amount of current capable of controlling the flow rate of the molten glass.
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JP2013216531A (en) * 2012-04-06 2013-10-24 Avanstrate Inc Manufacturing method of glass plate and manufacturing apparatus of glass plate

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JP2017178733A (en) * 2016-03-31 2017-10-05 AvanStrate株式会社 Production method of glass sheet

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