WO2015099136A1 - ガラス基板の製造方法およびガラス基板製造装置 - Google Patents
ガラス基板の製造方法およびガラス基板製造装置 Download PDFInfo
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- WO2015099136A1 WO2015099136A1 PCT/JP2014/084554 JP2014084554W WO2015099136A1 WO 2015099136 A1 WO2015099136 A1 WO 2015099136A1 JP 2014084554 W JP2014084554 W JP 2014084554W WO 2015099136 A1 WO2015099136 A1 WO 2015099136A1
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- temperature region
- heat transfer
- molten glass
- glass substrate
- glass
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
- C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
- C03B5/225—Refining
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
- C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
- C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
- C03B5/42—Details of construction of furnace walls, e.g. to prevent corrosion; Use of materials for furnace walls
- C03B5/43—Use of materials for furnace walls, e.g. fire-bricks
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B7/00—Distributors for the molten glass; Means for taking-off charges of molten glass; Producing the gob, e.g. controlling the gob shape, weight or delivery tact
- C03B7/02—Forehearths, i.e. feeder channels
- C03B7/06—Means for thermal conditioning or controlling the temperature of the glass
- C03B7/07—Electric means
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
- C03B5/04—Melting 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 processing the molten glass before molding, for example, a process of removing minute bubbles contained in the molten glass (hereinafter also referred to as clarification).
- Clarification is performed by passing molten glass containing a clarifier through the clarifier tube body while heating the clarifier tube body, and removing bubbles in the molten glass by 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).
- the inner wall of the member in contact with the high-temperature molten glass before forming must be made of an appropriate material according to the temperature of the molten glass in contact with the member, the required quality of the glass substrate, and the like.
- a material constituting the above-mentioned clarification tube main body is usually a simple substance or an alloy of a platinum group metal (Patent Document 1). Platinum group metals have a high melting point and are excellent in corrosion resistance against molten glass.
- the platinum group metal When the molten glass passes through the treatment apparatus in which the platinum group metal is used for the inner wall surface, the platinum group metal volatilizes as an oxide in a portion in contact with the gas phase space (atmosphere containing oxygen) on the heated inner surface. On the other hand, the oxide of the platinum group metal is reduced at a position where the temperature locally decreases in the processing apparatus, and the reduced platinum group metal adheres to the inner wall surface. The platinum group metal adhering to the inner wall surface may drop into the molten glass and enter the glass substrate as a foreign substance.
- the problem of mixing foreign substances derived from aggregates of volatiles such as 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.
- the present invention reduces the temperature difference with the surroundings of the position where the temperature of the molten glass processing apparatus has locally decreased, and is less than or equal to the reference value, so that there is little risk of foreign matter mixing into the glass substrate and high quality. It aims at providing the manufacturing method and glass substrate manufacturing apparatus of a glass substrate which can manufacture a glass substrate.
- the present invention has the following forms.
- (Form 1) A molten glass is processed using a processing apparatus having a gas phase space formed from an inner wall and a surface of the molten glass, and at least a part of the inner wall in contact with the gas phase space is made of a material containing a platinum group metal.
- a method of manufacturing a glass substrate In the region in contact with the gas phase space of the processing apparatus, a high temperature region and a low temperature region lower in temperature than the high temperature region are formed when the molten glass is processed, Outside the processing apparatus, a heat transfer medium that supports the processing apparatus and conducts heat from the high temperature region to the low temperature region is provided, The method for manufacturing a glass substrate, wherein the heat transfer amount of the heat transfer medium is adjusted so that a temperature difference between the high temperature region and the low temperature region is a reference value or less.
- the high temperature region may be a region where the temperature of the processing apparatus is in a temperature range of 1600 ° C.
- 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
- 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.
- 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 reference value can be determined by the number of aggregates of platinum noble metals in the target glass substrate.
- the heat transfer amount of the heat transfer medium is preferably adjusted 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.
- 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 vapor pressure of the platinum group metal in the gas phase space is preferably 0.1 Pa to 15 Pa.
- Form 2 The molten glass is processed using a processing apparatus having a gas phase space formed by an inner wall and a molten glass liquid surface, and at least a part of the inner wall in contact with the gas phase space is made of a material containing a platinum group metal.
- a method of manufacturing a glass substrate When the molten glass is processed in the processing device, a high temperature region and a low temperature region are formed, Outside the processing apparatus, a heat transfer medium that supports the processing apparatus and conducts heat from the high temperature region to the low temperature region is provided, A method for producing a glass substrate, wherein a heat transfer amount of the heat transfer medium is adjusted so as to reduce a temperature difference between the high temperature region and the low temperature region.
- the reference value is 200 ° C. or less
- region may be 200 degrees C or less.
- the treatment device and the heat transfer medium are covered with a fireproof insulating brick,
- the heat transfer medium is a refractory brick having a higher thermal conductivity than the refractory insulating brick,
- the method for manufacturing a glass substrate according to any one of Embodiments 1 to 4, wherein the heat transfer amount of the heat transfer medium is determined using computer simulation.
- the computer simulation can be performed, for example, by creating a model of a processing device, a heat transfer medium, and a gas phase space by a finite element method or a mesh free method, and performing a heat transfer analysis using this model.
- the processing device includes a clarification device for clarifying molten glass, and the heat transfer medium abuts on a high temperature region and a low temperature region of the clarification device, and adjusts a heat transfer amount by the heat transfer medium, whereby the clarification tube
- the maximum temperature of the molten glass in the processing apparatus is preferably 1630 ° C to 1720 ° C. While the maximum temperature is 1630 ° C. or higher, the fining agent in the molten glass can exert a clarification effect, while being 1720 ° C.
- 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. By setting the content of tin oxide to 0.01 to 0.3 mol%, it is possible to suppress the aggregation of tin oxide from being mixed into the molten glass while sufficiently reducing bubbles.
- Form 7 It has a gas phase space formed from an inner wall and a molten glass surface, at least a part of the inner wall in contact with the gas phase space is made of a material containing a platinum group metal, and a high temperature region when processing the molten glass,
- a processing apparatus in which a low temperature region having a temperature lower than that of the high temperature region is formed; It is provided outside the processing apparatus, supports the processing apparatus, conducts heat from the high temperature region to the low temperature region, and transmits the temperature difference between the high temperature region and the low temperature region to a reference value or less.
- a heat transfer medium in which the amount of heat is adjusted;
- a glass substrate manufacturing apparatus comprising:
- Form 8 It has a gas phase space formed from an inner wall and a molten glass liquid surface, and at least a part of the inner wall in contact with the gas phase space is made of a material containing a platinum group metal.
- a processing apparatus in which a region and a low-temperature region are formed; The amount of heat transfer is adjusted so as to be provided outside the processing apparatus, support the processing apparatus, conduct heat from the high temperature region to the low temperature region, and reduce a temperature difference between the high temperature region and the low temperature region.
- a heat transfer medium, A glass substrate manufacturing apparatus comprising:
- 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.
- any one of the above forms it is preferable to further have an agglomerate treatment step of melting the agglomerates of platinum group metal mixed in the molten glass into the molten glass.
- concentration of the platinum group metal dissolved in the molten glass at the start of the agglomerate treatment step is preferably 0.05 to 20 ppm.
- the saturation solubility of the platinum group metal is preferably adjusted by adjusting the oxygen activity of the molten glass. For example, it is preferable to adjust the oxygen activity so that [Fe 3+ ] / ([Fe 2+ ] + [Fe 3+ ]), which is an index of oxygen activity, is in the range of 0.2 to 0.5.
- the aggregate produced 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, for example.
- the maximum length of the platinum group metal aggregate is 50 ⁇ m to 300 ⁇ m, and 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.
- the glass substrate is a glass substrate for display. Moreover, the said glass substrate is suitable for the glass substrate for oxide semiconductor displays or the glass substrate for LTPS displays.
- the present invention it is possible to reduce the possibility that foreign substances are mixed into the glass substrate, and to manufacture a high-quality glass substrate.
- 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. It is a figure which shows an example of the temperature distribution in the longitudinal direction of the upper surface of the clarification tube.
- 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).
- 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 tin oxide content of the glass substrate is preferably from 0.01 to 0.3 mol%, more preferably from 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 clarification step (ST2) is performed at least in the clarification tube.
- the bubbles containing oxygen, CO 2 or SO 2 contained in the molten glass absorb the oxygen generated by the reductive reaction of the clarifier and volume. Increases and floats to the liquid surface of the molten glass and is released.
- the reducing substance obtained by the reduction reaction of the clarifier undergoes an oxidation reaction by lowering the temperature of the molten glass. Thereby, gas components, such as oxygen in the bubble which remain
- 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.
- 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 is formed and flowed to a desired thickness, and the sheet glass is gradually cooled 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, transfer pipes 104 and 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 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 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.
- 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.
- the main body of the clarification tube 120, the electrode 121, and the exhaust pipe 127 are made of a platinum group metal.
- 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.
- 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. .
- 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 maximum temperature of the main body of the clarification tube 120 is heated to, for example, 1600 ° C. to 1750 ° C., more preferably 1630 ° C. to 1750 ° C.
- the maximum temperature of the molten glass supplied from the glass supply tube 104 Is heated to a temperature suitable for defoaming, for example, 1600 ° C. to 1720 ° C., more preferably 1620 ° C.
- the viscosity of the molten glass can be adjusted, and thereby the flow rate of the molten glass passing through the clarification tube 120 can be adjusted.
- 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 controls the amount of current that the power supply device 122 supplies to the clarification tube 120, thereby controlling the temperature and flow rate of the molten glass passing through the clarification tube 120.
- the control device 123 is a computer including a CPU, a memory, and the like.
- An exhaust pipe 127 is provided on the wall in contact with the gas phase space of the clarification pipe 120. Even if the exhaust pipe 127 has 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 transfer medium 130 is provided on the outer wall surface of the main body of the clarification tube 120, the outer wall surfaces of the electrodes 121a and 121b, and the outer wall surface of the exhaust pipe 127, and a heat insulating material 140 is provided outside the heat transfer medium 130. ing.
- the heat transfer medium 130 is made of a material having a higher thermal conductivity than the heat insulating material 140, abuts on the high temperature region and the low temperature region of the clarification tube 120, and conducts heat from the high temperature region to the low temperature region via the heat transfer medium 130. This serves to reduce the temperature difference between the high temperature region and the low temperature region.
- the heat transfer amount of the heat transfer medium 130 By adjusting the heat transfer amount of the heat transfer medium 130, the temperature difference between the high temperature region and the low temperature region can be adjusted, and the temperature difference can be made equal to or less than a preset reference value. It is not necessary to provide the heat transfer medium 130 so as to contact the entire region of the clarification tube 120.
- 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 heat transfer medium 130 is preferably at least twice that of the heat insulating material 140, and more preferably at least five times.
- a material having a thermal conductivity of 2 to 40 W / m ⁇ K at 1000 ° C. is preferably used as the heat transfer medium 130.
- a member having excellent fire resistance and high strength (rigidity) can be used.
- the heat transfer medium 130 an alumina electrocast refractory, a magnesia refractory, a silicon carbide refractory, or the like can be used. By using such a material for the heat transfer medium 130, deformation of the clarification tube 120 can be prevented.
- the amount of heat transferred from the high temperature region to the low temperature region via the heat transfer medium 130 is preferably 0.3 kW to 20 kW, and more preferably 0.5 kW to 15 kW.
- the heat insulating material 140 is made of a material having a lower thermal conductivity than the heat transfer medium 130, and plays a role of adjusting the amount of heat released from the fining tube 120 and the heat transfer medium 130 to the outside.
- a material having a thermal conductivity at 1000 ° C. of 0.1 to 1 W / m ⁇ K is preferably used as the heat insulating material 140.
- porous bricks, ceramic fibers, or the like can be used as the heat insulating material 140. Since the heat transfer property of the heat transfer medium 130 is low, the clarification tube 120 cannot be sufficiently warmed only by the heat transfer medium 130.
- the heat insulating material 140 provided on the outer side of the heat transfer medium 130 has excellent heat insulating properties, but tends to have low strength.
- the higher the porosity of the heat-insulating refractory brick the higher the heat insulating property, but the lower the strength. Therefore, deformation of the refining device 120 cannot be prevented only with the heat-insulating refractory brick.
- the two-layer structure of the heat transfer medium 130 and the heat insulating material 140 achieves the support of the clarification tube 120 by the heat transfer medium 130 and the heat insulation by the heat insulating material 140.
- the high temperature region indicates a region where the temperature is higher than other regions.
- 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. 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.
- the areas near the electrodes 121a and 121b of the clarification tube and the vicinity of the exhaust pipe 127 are low-temperature areas, and the area between the electrodes 121a and 121b and the exhaust pipe 127 is a high-temperature area. It becomes.
- FIG. 5 is a diagram showing an example of the temperature distribution in the longitudinal direction of the upper surface of the clarification tube 120.
- the solid line is the clarification tube 120 of this embodiment, and the broken line is the temperature distribution of the conventional clarification tube.
- heat is radiated from the electrodes 121a and 121b and the exhaust pipe 127 to the outside. It is easy to become.
- the electrodes 121a and 121b having a flange shape have a high heat dissipation function, and therefore the wall near the electrodes 121a and 121b is compared with the peripheral portion of the wall. It becomes low temperature.
- the electrodes 121a and 121b are cooled with a liquid or a gas in order to suppress damage due to overheating, for example.
- the exhaust pipe 127 also has a shape protruding from the clarification pipe 120, the wall of the clarification pipe 120 in contact with the gas phase space 41c in the vicinity of the exhaust pipe 127 is also lower in temperature than the periphery of the wall.
- 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 heat transfer medium 130 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, so that the clarification tube is interposed via the heat transfer medium 130. Heat is conducted from the high temperature region of 120 to the low temperature region. Thereby, the temperature difference between the high temperature region and the low temperature region of the clarification tube 120 can be suppressed to a predetermined range.
- the local temperature fall can be relieved with the heat-transfer medium 130, and the temperature difference of a high temperature area
- region can be suppressed to a predetermined
- 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 volatilized platinum group metal oxide is reduced in a region where the temperature is locally lowered, and the solidified platinum group metal aggregates and adheres to the inner wall surface. Aggregates of platinum group metals adhering to the inner wall surface may fall into the molten glass during the refining process and be mixed as foreign matter, leading to a decrease in the quality of the glass substrate.
- 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.
- the oxygen concentration in the gas phase space is 0%, volatilization of the platinum group metal can be prevented.
- the oxygen concentration in the gas phase space is preferably 0%.
- the oxygen concentration in the gas phase space 41c is 0.01% or more in order to achieve both foam reduction, low cost, and reduction of platinum group metal volatilization. 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 120a 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.
- the oxygen concentration in the gas phase space is preferably 0 to 30%, preferably 0.01 to 10%, and more preferably 0.01 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 reference value of the temperature difference between the high temperature region and the low temperature region is preferably 50 ° C. or more and 200 ° C. or less, and preferably 70 ° C. or more and 150 ° C. from the viewpoint of achieving both the suppression of volatilization of the platinum group metal and the refining effect.
- the following is more preferable.
- the temperature difference between the high temperature region and the low temperature region is 200 ° C. or less, preferably 150 ° C. or less, more preferably 100 ° C. or less, the oxide of the platinum group metal oxidized in the high temperature region is reduced in the low temperature region. It is possible to suppress the mixing of the solidified or aggregated platinum group metal into the molten glass.
- the temperature difference between the high temperature region and the low temperature region is 50 ° C. or more, more preferably 70 ° C. or more, the temperature of the molten glass can be made a temperature range suitable for fining, and the number of bubbles can be reduced. it can.
- the temperature difference between the high temperature region and the low temperature region may be a temperature difference between the maximum temperature in the high temperature region and the minimum temperature in the low temperature region.
- 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.
- the temperature difference between the high temperature region and the low temperature region can be adjusted by adjusting the amount of heat transfer by the heat transfer medium 130.
- the amount of heat transfer can be adjusted by adjusting the thermal conductivity of the heat transfer medium 130 or the amount of the heat transfer medium 130.
- the temperature difference between the high temperature region and the low temperature region can be controlled by adjusting the arrangement of the firebrick.
- the amount of heat transfer when the heat conductivity, arrangement, and amount of the heat transfer medium 130 are changed is calculated by, for example, numerical fluid dynamic calculation (computer simulation) using a 3D model created by a finite element method or a mesh-free method. be able to.
- a 3D model that reproduces the clarification tube 120, the heat transfer medium 130, the heat insulating material 140, the molten glass in the clarification tube 120 and the gas phase space is created, and this is divided into a finite number of regions (calculation grids)
- the conditions (the temperature of the molten glass in the clarification tube 12, the heat dissipation of the clarification tube 12, etc.) and the material properties (thermal conductivity, etc.) are defined.
- 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 transfer medium 130 and the heat insulating material 140 can be calculated.
- the platinum group metal aggregates to be suppressed in the present embodiment have a linear shape elongated in one direction, and the aspect ratio, which is the ratio of the maximum length to the minimum length, is 100 or more.
- the maximum length of the platinum group metal aggregate is 50 ⁇ m to 300 ⁇ m, and 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 of platinum group metal mixes into a molten glass as a foreign material.
- the agglomerate treatment step described below is preferably performed in a state where the concentration of the platinum group metal dissolved in the molten glass is 0.05 to 20 ppm. That is, the concentration of the platinum group metal dissolved in the molten glass at the start of the aggregate treatment process is preferably 0.05 to 20 ppm. The lower the concentration of the platinum group metal dissolved in the molten glass at the start of the aggregation treatment step, the greater the amount of dissolution of the platinum group metal aggregates in the molten glass. On the other hand, if the concentration of the platinum group metal is too low, the platinum group metal may be eluted from the wall of the processing apparatus in contact with the molten glass into the molten glass, and the processing apparatus may be melted. The concentration of the platinum group metal in the molten glass can be determined, for example, by sampling the molten glass in the clarification tube, crushing after cooling, and measuring using ICP quantitative analysis.
- the saturation solubility of the platinum group metal in the molten glass is adjusted by setting the temperature of the molten glass to 1660 ° C. to 1750 ° C. By raising the temperature of the molten glass, the saturation solubility of the platinum group metal in the molten glass can be increased, and the aggregate of the platinum group metal mixed in the molten glass can be dissolved. On the other hand, if the temperature of the molten glass is too high, the volatilization amount of the glass component (for example, B 2 O 3 ) increases, the glass composition changes locally, and the glass properties such as the thermal expansion coefficient and viscosity of the glass become local. There is a possibility that streaks such as striae are generated on the glass substrate.
- the volatilization amount of the glass component for example, B 2 O 3
- the volatilization amount of the platinum group metal from the wall surface of the processing apparatus of molten glass will increase. Furthermore, if the temperature of the molten glass is too high, the wall of the processing apparatus may be melted. In addition, if the temperature of the molten glass is too high, the defoaming is excessive, so that the oxygen activity of the molten glass is lowered. In this state, when the absorption treatment step is performed, SO 3 and CO 3 dissolved in the molten glass are reduced to generate SO 2 and CO 2 . Since SO 2 and CO 2 are less likely to be dissolved in the molten glass than SO 3 and CO 3 , they tend to remain as bubbles and cause bubble defects that occur in the manufactured glass substrate.
- the saturation solubility of the platinum group metal may be adjusted by adjusting the pressure of the gas phase space facing the molten glass.
- the pressure in the gas phase space means the total pressure of the gas contained in the gas phase space.
- the pressure in the gas phase space can be adjusted, for example, by the amount of gas discharged from the gas phase space to the outside of the clarification tube 120 through the exhaust pipe 127 (discharge amount) or the gas into the clarification tube 120, for example, This can be done by adjusting the amount of active gas supplied and the amount of gas released from the molten glass.
- the amount of discharge can be determined by, for example, connecting the outlet of the exhaust pipe 127 of the clarification pipe 120 to a suction device or narrowing the outlet, so that the pressure difference between the gas phase space and the atmosphere outside the clarification pipe 120 is reduced. It can be adjusted by adjusting.
- the amount of gas released from the molten glass can be adjusted, for example, by adjusting the amount of fining agent contained in the molten glass and the mixing ratio of the glass components.
- the fact that the pressure in the gas phase space is higher or lower than the atmospheric pressure outside the clarification tube 120 can be determined by, for example, the amount of gas released from the exhaust pipe 127. When the pressure in the gas phase space is increased, the dissolution amount of the platinum group metal aggregates increases.
- the saturation solubility of the platinum group metal may be adjusted by adjusting the oxygen activity of the molten glass.
- the oxygen activity of the molten glass means the amount of oxygen dissolved in the molten glass (excluding those present in the molten glass as bubbles).
- [Fe 3+ ] / ([Fe 2+ ] + [Fe 3+ ]) may be used as an index of the oxygen activity.
- [Fe 2+ ] and [Fe 3+ ] are the activities of Fe 2+ and Fe 3+ contained in the molten glass, and specifically, the mass percentage display content.
- [Fe 2+ ] and [Fe 3+ ] can be measured using spectrophotometry.
- the dissolution amount of the platinum group metal aggregate can be increased.
- the oxygen activity is too high, the amount of oxygen released from the molten glass increases, and the platinum group metal is easily oxidized and volatilized.
- the oxygen activity is preferable to adjust the oxygen activity so that [Fe 3+ ] / ([Fe 2+ ] + [Fe 3+ ]) is in the range of 0.2 to 0.5.
- the oxygen activity of the molten glass can be adjusted, for example, by adjusting the amount of the fining agent contained in the molten glass and the oxide of the glass raw material in the melting step. Further, in the clarification step, the temperature can be adjusted by adjusting the temperature of the molten glass before the start of the aggregate treatment step or by bubbling an oxygen-containing gas into the molten glass before the start of the aggregate treatment step.
- Example 4 the clarification apparatus shown in FIG. 4 was used to clarify the molten glass for 1 hour using tin oxide as a clarifier.
- the clarified molten glass was 2270 mm ⁇ 2000 mm and the thickness was 0.5 mm.
- the sheet glass was formed into 100 glass substrates.
- the heat conductivity of the heat transfer medium 130 and the heat insulating material 140 the amount of heat transfer from the region of the highest temperature of the clarification tube to the region around the electrodes 121a and 121b and the exhaust tube 127 was adjusted. Thereby, the temperature difference between the temperature around the electrodes 121a and 121b and the exhaust pipe 127 and the maximum temperature of the clarification pipe could be maintained at the temperature shown in Table 1.
- the heat transfer amount in Example 4 was 2 kW, and the heat transfer amounts in Examples 1 to 3 were 2 kW or more.
- the glass composition of the glass substrate is SiO 2 66.6 mol%, Al 2 O 3 10.6 mol%, B 2 O 3 11.0 mol%, MgO, CaO, SrO and
- the total amount of BaO is 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 at one time was 1570 ° C.
- the allowable level per unit mass of the number of defects due to this aggregate is, for example, 0.02 piece / kg or less.
- the number of defects in the platinum group metal aggregates was at an acceptable level.
- the number of defects of the platinum group metal foreign matter was out of the allowable level.
- 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 0.8 mol% or less.
- 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, Total amount of SrO and BaO), 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 0.4 mol%, contains.
- 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.
- Glass having high viscosity at high temperature generally needs to raise the temperature of the molten glass in the refining process, and thus volatilization of platinum group metals (for example, platinum or platinum alloys) is likely to occur. That is, when manufacturing the glass substrate which has such a composition, the effect of this embodiment which suppresses that the aggregate of a platinum group metal mixes in a molten glass as a foreign material becomes remarkable.
- high temperature viscosity shows the viscosity of glass when molten glass becomes high temperature
- high temperature here shows 1300 degreeC or more, for example.
- the glass with an alkali metal oxide content of 0 to 0.8 mol% has an alkali metal oxide content of more than 0.8 mol%.
- High temperature viscosity compared to glass. Glass with high viscosity at high temperature generally needs to raise the temperature of the molten glass in the refining process, and thus volatilization of platinum group metals is likely to occur. That is, when this glass having a high temperature viscosity is used, the effect of the present embodiment that suppresses the mixture of platinum group metal aggregates as a foreign substance in the molten glass becomes remarkable.
- the temperature at a viscosity of 10 2.5 poise 1500 ⁇ 1700 ° C. may be a glass composition is 1600 ⁇ 1700 ° C..
- glass having high viscosity at high temperature generally needs to raise the molten glass temperature in the refining process, and thus 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.
- an oxide semiconductor display glass substrate using an oxide semiconductor such as IGZO and an LTPS display glass substrate using an LTPS semiconductor 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.
- a refrigerant circulation pipe may be provided between the high temperature region and the low temperature region, and the refrigerant may be circulated inside the circulation pipe, whereby the refrigerant may be used as the heat transfer medium.
- the amount of heat transfer between the high temperature region and the low temperature region can be adjusted by controlling the circulation amount of the refrigerant, and the temperature difference between the high temperature region and the low temperature region can be adjusted.
- 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 heat transfer medium 130 and the heat insulating material 140 may be provided in the tube 106) and the molding apparatus 200.
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Abstract
Description
また、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。
(形態1)
内壁と熔融ガラス表面とから形成される気相空間を有し、前記気相空間と接する前記内壁の少なくとも一部は白金族金属を含む材料で構成される処理装置を用いて熔融ガラスを処理するガラス基板の製造方法であって、
前記処理装置の前記気相空間と接する領域には、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と、が形成され、
前記処理装置の外部には、前記処理装置を支持し、前記高温領域から前記低温領域へ熱を伝導させる伝熱媒体が設けられ、
前記伝熱媒体の伝熱量は、前記高温領域と前記低温領域との温度差が基準値以下となるように調整される、ガラス基板の製造方法。
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。
高温領域と低温領域との温度差を基準値以下にするとは、伝熱媒体の伝熱量により高温領域と低温領域との温度差を調整し、当該温度差を予め設定された基準値以下にすることをいう。なお、基準値は、目標となるガラス基板中の白金貴金属の凝集物数によって定めることができる。伝熱媒体の伝熱量は、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、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し、基準値以下にすることで、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減することができる。
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。
気相空間における白金族金属の蒸気圧は、0.1Pa~15Paであることが好ましい。
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、前記気相空間と接する前記内壁の少なくとも一部は白金族金属を含む材料で構成される処理装置を用いて熔融ガラスを処理するガラス基板の製造方法であって、
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低温領域が形成され、
前記処理装置の外部には、前記処理装置を支持し、前記高温領域から前記低温領域へ熱を伝導させる伝熱媒体が設けられ、
前記高温領域と前記低温領域との温度差を低減するように、前記伝熱媒体の伝熱量が調整されている、ガラス基板の製造方法。
前記基準値は、200℃以下であり、
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伝熱媒体による伝熱量を調整する、形態1又は2に記載のガラス基板の製造方法。
前記処理装置および前記伝熱媒体は耐火断熱レンガにより覆われ、
前記伝熱媒体は前記耐火断熱レンガよりも熱伝導率が高い耐火レンガであり、
前記伝熱媒体の伝熱量は、前記伝熱媒体の熱伝導率及び配置の何れかを用いて調整される、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)
前記伝熱媒体の伝熱量は、コンピュータシミュレーションを用いて決定される、形態1~4のいずれか1つに記載のガラス基板の製造方法。
コンピュータシミュレーションは、例えば、有限要素法やメッシュフリー法により、処理装置、伝熱媒体および気相空間のモデルを作成し、このモデルを使用して伝熱解析をすることにより行うことができる。
前記処理装置は、熔融ガラスを清澄させる清澄装置を含み、前記伝熱媒体は、前記清澄装置の高温領域および低温領域と当接し、前記伝熱媒体による伝熱量を調整することで、前記清澄管の高温領域と低温領域の温度差を調整する、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。
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し、基準値以下にすることができ、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、0.01~0.3mol%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。酸化錫の含有量を0.01~0.3mol%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抑制することができる。
内壁と熔融ガラス表面とから形成される気相空間を有し、前記気相空間と接する前記内壁の少なくとも一部は白金族金属を含む材料で構成され、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と、が形成される処理装置と、
前記処理装置の外部に設けられ、前記処理装置を支持し、前記高温領域から前記低温領域へ熱を伝導させ、前記高温領域と前記低温領域との温度差が基準値以下となるように、伝熱量が調整されている伝熱媒体と、
を備えるガラス基板製造装置。
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、前記気相空間と接する前記内壁の少なくとも一部は白金族金属を含む材料で構成され、熔融ガラスを処理する際に、高温領域と低温領域が形成される処理装置と、
前記処理装置の外部に設けられ、前記処理装置を支持し、前記高温領域から前記低温領域へ熱を伝導させ、前記高温領域と前記低温領域との温度差を低減するように、伝熱量が調整されている伝熱媒体と、
を備えるガラス基板製造装置。
上記いずれかの形態において、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。
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。
上記いずれかの形態において、熔融ガラスに混入した白金族金属の凝集物を熔融ガラスに熔解させる凝集物処理工程をさらに有することが好ましい。
凝集物処理工程の開始時における熔融ガラスに溶けている白金族金属の濃度を、0.05~20ppmとすることが好ましい。
凝集物処理工程では、熔融ガラスの温度を1660℃~1750℃にすることで、熔融ガラスにおける白金族金属の飽和溶解度を調整することが好ましい。
白金族金属の飽和溶解度は、熔融ガラスの酸素活量を調整することにより調整することが好ましい。例えば、酸素活量の指標である[Fe3+]/([Fe2+]+[Fe3+])が0.2~0.5の範囲となるように酸素活量を調整することが好ましい。
上記いずれかの形態において、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。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。
上記いずれかの形態において、前記ガラス基板は、ディスプレイ用ガラス基板である。また、前記ガラス基板は、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。
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。
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。ガラス基板の酸化錫の含有量は、0.01~0.3mol%であることが好ましく、0.03~0.2mol%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、熔融ガラスから気相空間に放出される酸素が増加し、気相空間の酸素濃度が上昇し過ぎてしまい、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0.01~0.3mol%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。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。
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。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。
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。
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、シートガラスを徐冷する。
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。
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。
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。
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。
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。
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、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。
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を制御し、これにより清澄管120を通過する熔融ガラスの温度および流速を制御する。制御装置123は、CPU、メモリ等を含むコンピュータである。
伝熱媒体130の熱伝導率は、断熱材140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。1000℃における熱伝導率が2~40W/m・Kである材料を伝熱媒体130として用いることが好ましい。伝熱媒体130には、優れた耐火性を有し、かつ、強度(剛性)が高い部材を用いることができる。具体的には、伝熱媒体130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。このような材料を伝熱媒体130に用いることで、清澄管120の変形を防止することができる。
伝熱媒体130を介して高温領域から低温領域に移動する熱量は、0.3kW~20kWであることが好ましく、0.5kW~15kWであることがより好ましい。
伝熱媒体130の断熱性は低いため、伝熱媒体130のみでは清澄管120を十分に保温することができない。一方、伝熱媒体130の外側に設けられた断熱材140は、断熱性は優れているが、強度が低い傾向がある。例えば、断熱耐火レンガは気孔率が高いほど、断熱性が高くなるが、強度が低くなる。そのため、断熱耐火レンガのみでは、清澄装置120の変形を防止することはできない。
本実施形態においては、伝熱媒体130と断熱材140の2層構造にすることによって、伝熱媒体130による清澄管120の支持と断熱材140による保温が達成される。
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41c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120a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、0.01~10%であることが好ましく、0.01~1%であることがより好ましい。
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。
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。
また、伝熱媒体130が耐火レンガである場合には、耐火レンガの配置を調整することで、高温領域と低温領域の温度差を制御することができる。
熔融ガラスの白金族金属の濃度は、例えば、清澄管内の熔融ガラスをサンプリングし、冷却後粉砕してICP定量分析を用いた測定により求めることができる。
また、熔融ガラスの温度を高くしすぎると、過剰に脱泡されるため、熔融ガラスの酸素活量は低くなる。この状態で、吸収処理工程が行われると、熔融ガラスに溶存しているSO3、CO3が還元されることでSO2、CO2が生成される。SO2、CO2はSO3、CO3に比べて熔融ガラスに溶存されにくいため気泡として残りやすく、製造されるガラス基板に生じる泡欠陥の原因となる。
気相空間の圧力の調整は、例えば、気相空間内の気体が排気管127を通って清澄管120の外側に排出される量(排出量)や、清澄管120内へのガス、例えば不活性ガスの供給量、熔融ガラスから放出されるガスの放出量を調整することによって行うことができる。排出量は、例えば、清澄管120の排気管127の出口を吸引装置と接続したり、上記出口を狭める等して、気相空間と清澄管120の外側の大気との圧力差の大きさを調節することで調整できる。熔融ガラスから放出されるガスの放出量は、例えば、熔融ガラスに含まれる清澄剤の量、ガラス成分の配合比を調整することで調整できる。なお、気相空間の圧力が、清澄管120の外側の大気圧より高いまたは低いことは、例えば、排気管127から放出されるガス量によって求めることができる。
気相空間の圧力を高くすると、白金族金属の凝集物の溶解量が大きくなる。一方、気相空間の圧力を高くしすぎると、脱泡処理工程において、熔融ガラス中に発生した泡が熔融ガラスの表面から放出され難くなり、清澄不良を招く場合がある。また、気相空間の圧力を高くしすぎると、清澄管120の外側の大気との圧力差が大きくなって、気相空間内の気流の流速が上昇する。このため、気相空間内の白金族金属の濃度が上昇せず飽和状態になり難いため、清澄管120の壁からの白金族金属の揮発量が増加する。
実施例1~4では、図4に示す清澄装置を用いて、清澄剤として酸化錫を用いて熔融ガラスの清澄を1時間行い、清澄後の熔融ガラスを、2270mm×2000mm、厚さ0.5mmのシートガラスに成形し、100枚のガラス基板を作成した。このとき、伝熱媒体130および断熱材140の熱伝導率を調整することで、清澄管の最高温度の領域から電極121a、121b及び排気管127の周辺の領域への伝熱量を調整した。これにより、電極121a、121b及び排気管127の周辺の温度と清澄管の最高温度との温度差を表1に示す温度に保つことができた。なお、実施例4における伝熱量は2kWであり、実施例1~3の伝熱量は2kW以上であった。
伝熱媒体及び断熱材の熱伝導率を調整し、清澄管の最高温度の領域から電極121a、121b及び排気管127の周辺の領域への伝熱量を調整しなかったことを除いて実施例と同様の方法で、100枚のガラス基板を作成した。この結果、電極121a、121b及び排気管127の周辺の温度と清澄管の最高温度との温度差は、表1に示す温度となった。
実施例1~6および比較例において作製したガラス基板中を光学顕微鏡で観察し、ガラス基板中の白金族金属の凝集物の個数を計数した。なお、最高温度と最低温度の温度差が120℃である場合の1kgあたりの白金族金属の凝集物の個数を1として、夫々の条件における白金族金属の凝集物の個数を比率で示した。温度差が250℃である場合(比較例)に対し、温度差が50℃、80℃、100℃、120℃、170℃、200℃、である場合(実施例1~6)には、ガラス基板中の白金族金属の凝集物の量を抑制できたことを明らかである。なお、白金族金属の凝集物としては、アスペクト比が100以上であり、最大長さが100μm以上の白金異物をカウントした。
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、白金または白金合金等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0.8mol%以下のガラスである。
このとき、SiO2、Al2O3、B2O3、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)+Al2O3)/((2×B2O3)+RO)は4.0以上であってもよい。モル比((2×SiO2)+Al2O3)/((2×B2O3)+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、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。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。
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。IGZO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半導体を使用した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。
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。
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
130 伝熱媒体
140 断熱材
200 成形装置
Claims (8)
- 内壁と熔融ガラス表面とから形成される気相空間を有し、前記気相空間と接する前記内壁の少なくとも一部は白金族金属を含む材料で構成される処理装置を用いて熔融ガラスを処理するガラス基板の製造方法であって、
前記処理装置の前記気相空間と接する領域には、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と、が形成され、
前記処理装置の外部には、前記処理装置を支持し、前記高温領域から前記低温領域へ熱を伝導させる伝熱媒体が設けられ、
前記伝熱媒体の伝熱量は、前記高温領域と前記低温領域との温度差が基準値以下となるように調整される、ガラス基板の製造方法。 - 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、前記気相空間と接する前記内壁の少なくとも一部は白金族金属を含む材料で構成される処理装置を用いて熔融ガラスを処理するガラス基板の製造方法であって、
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低温領域が形成され、
前記処理装置の外部には、前記処理装置を支持し、前記高温領域から前記低温領域へ熱を伝導させる伝熱媒体が設けられ、
前記高温領域と前記低温領域との温度差を低減するように、前記伝熱媒体の伝熱量が調整されている、ガラス基板の製造方法。 - 前記基準値は、200℃以下であり、
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伝熱媒体による伝熱量を調整する、請求項1又は2に記載のガラス基板の製造方法。 - 前記処理装置および前記伝熱媒体は耐火断熱レンガにより覆われ、
前記伝熱媒体は前記耐火断熱レンガよりも熱伝導率が高い耐火レンガであり、
前記伝熱媒体の伝熱量は、前記伝熱媒体の熱伝導率及び配置の何れかを用いて調整される、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。 - 前記伝熱媒体の伝熱量は、コンピュータシミュレーションを用いて決定される、請求項1~4のいずれか一項に記載のガラス基板の製造方法。
- 前記処理装置は、熔融ガラスを清澄させる清澄装置を含み、
前記伝熱媒体は、前記清澄装置の高温領域および低温領域と当接し、
前記伝熱媒体による伝熱量を調整することで、前記清澄装置の高温領域と低温領域の温度差を調整する、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。 - 内壁と熔融ガラス表面とから形成される気相空間を有し、前記気相空間と接する前記内壁の少なくとも一部は白金族金属を含む材料で構成され、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と、が形成される処理装置と、
前記処理装置の外部に設けられ、前記処理装置を支持し、前記高温領域から前記低温領域へ熱を伝導させ、前記高温領域と前記低温領域との温度差が基準値以下になるように、伝熱量が調整されている伝熱媒体と、
を備えるガラス基板製造装置。 - 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、前記気相空間と接する前記内壁の少なくとも一部は白金族金属を含む材料で構成され、熔融ガラスを処理する際に、高温領域と低温領域が形成される処理装置と、
前記処理装置の外部に設けられ、前記処理装置を支持し、前記高温領域から前記低温領域へ熱を伝導させ、前記高温領域と前記低温領域との温度差を低減するように、伝熱量が調整されている伝熱媒体と、
を備えるガラス基板製造装置。
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