CN106242251B - Float glass production method and float glass production device - Google Patents
Float glass production method and float glass production device Download PDFInfo
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- CN106242251B CN106242251B CN201610388134.4A CN201610388134A CN106242251B CN 106242251 B CN106242251 B CN 106242251B CN 201610388134 A CN201610388134 A CN 201610388134A CN 106242251 B CN106242251 B CN 106242251B
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B35/00—Transporting of glass products during their manufacture, e.g. hot glass lenses, prisms
- C03B35/14—Transporting hot glass sheets or ribbons, e.g. by heat-resistant conveyor belts or bands
- C03B35/16—Transporting hot glass sheets or ribbons, e.g. by heat-resistant conveyor belts or bands by roller conveyors
- C03B35/167—Transporting hot glass sheets or ribbons, e.g. by heat-resistant conveyor belts or bands by roller conveyors specially adapted for removing defect sheets, ribbons or parts thereof
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B18/00—Shaping glass in contact with the surface of a liquid
- C03B18/02—Forming sheets
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B18/00—Shaping glass in contact with the surface of a liquid
- C03B18/02—Forming sheets
- C03B18/14—Changing the surface of the glass ribbon, e.g. roughening
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C15/00—Surface treatment of glass, not in the form of fibres or filaments, by etching
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/50—Glass production, e.g. reusing waste heat during processing or shaping
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/50—Glass production, e.g. reusing waste heat during processing or shaping
- Y02P40/57—Improving the yield, e-g- reduction of reject rates
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- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
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Abstract
The present invention relates to a float glass production method and a float glass production apparatus. The present invention relates to a method for manufacturing float glass, which comprises the following steps: a melting step of melting a glass raw material, a fining step of fining the melted glass, a forming step of continuously supplying the fined molten glass onto a molten metal (9) in a float furnace (2) and forming a glass ribbon (5) on the molten metal (9), and a slow cooling step of pulling out the glass ribbon (5) from the float furnace (2) by a lift roller (7) and slowly cooling the glass ribbon (5) to a temperature equal to or lower than the strain point temperature of the glass while being conveyed by an annealing roller (8); the method is characterized in that the slow cooling process comprises the following steps: and a foreign matter removal step of removing foreign matter adhering to the bottom surface (5a) of the glass ribbon (5) by supplying a halogen-containing gas to the bottom surface (5a) of the glass ribbon (5) using injectors (20, 30) disposed between the annealing rollers (8) and below the glass ribbon (5).
Description
Technical Field
The present invention relates to a float glass production method and a float glass production apparatus.
Background
In the production of a glass sheet by the float process, a molten glass substrate (ground) is supplied from a glass melting furnace to a molten tin bath called a float furnace, a glass ribbon is formed on the molten tin bath, and then the glass ribbon is conveyed by conveying rolls called lift rolls and transferred to a slow cooling furnace. Generally, a defect called dross (ドロス) (tin and tin oxide) adheres to the lower surface of the glass ribbon.
In thin plate glass of less than 1.1mm used for flat panel display applications such as liquid crystal, even if the size of dross (tin and tin oxide) adhering to the surface of the glass plate is about 10 μm, the dross becomes defective according to the customer's request, and therefore even the dross defect of a size acceptable for general architectural use needs to be removed.
In patent document 1, a plate-shaped carbon removal member containing carbon, called a carbon wiper sheet (カーボンシール), is brought into contact with the lower portion of the lift roller to scrape off and remove tin or tin oxide adhering to the lift roller.
In a liquid crystal thin glass sheet produced by the float process, in order to satisfy the flatness required by customers, the lower surface of the glass sheet is polished, and therefore, dross is removed at the same time. In recent years, by taking measures for improving flatness in the melting/molding step, the amount of polishing of the glass plate in the polishing step is reduced, and productivity in the polishing step is improved.
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 11-335127
Patent document 2: japanese laid-open patent publication No. 4-202028
Disclosure of Invention
Problems to be solved by the invention
However, as the amount of glass sheet polished decreases, there is a problem that the dross adhering to the surface of the glass sheet cannot be completely removed, and therefore the dross needs to be removed at a stage prior to the polishing step. By merely improving the removing member described in patent document 1, the dross may not be completely removed.
The present invention has been made in view of the above problems, and an object of the present invention is to provide a float glass production method and a float glass production apparatus, which can reduce the amount of polishing of a glass plate in a polishing step without increasing the number of steps.
Means for solving the problems
In order to solve the above problems, the present invention provides a method for manufacturing a float glass, comprising: a melting step of melting a glass raw material, a fining step of fining the melted glass, a forming step of continuously supplying the fined molten glass onto a molten metal in a float furnace and forming a glass ribbon on the molten metal, and a slow cooling step of pulling out the glass ribbon from the float furnace by a lift roller and slowly cooling the glass ribbon to a temperature equal to or lower than a strain point temperature of the glass while being conveyed by an annealing roller; the slow cooling process is characterized by comprising the following steps: and a foreign matter removal step of supplying a halogen-containing gas to the bottom surface of the glass ribbon by using an injector provided between the annealing rolls and below the glass ribbon, thereby removing foreign matter adhering to the bottom surface.
Further, the present invention provides a float glass manufacturing apparatus, comprising: a float furnace for forming a glass ribbon on a molten metal, a slag box (ドロス ボ ッ ク ス) adjacent to the float furnace and provided with a lift roller for pulling out the glass ribbon, and a slow cooling furnace adjacent to the slag box for slow cooling the glass ribbon to a temperature equal to or lower than the strain point temperature of the glass while being conveyed by an annealing roller; characterized in that the slow cooling furnace is provided with an ejector which is arranged between the annealing rollers and below the glass ribbon; and the injector supplies a gas containing halogen to a bottom surface of the glass ribbon, thereby removing foreign matter adhering to the bottom surface.
Effects of the invention
According to the float glass production method and the float glass production apparatus of the present invention, the amount of polishing of the glass sheet in the polishing step can be reduced without increasing the number of steps.
Drawings
Fig. 1 is an explanatory view of a process for manufacturing a float glass according to an embodiment of the present invention.
Fig. 2 is a view schematically showing a double flow type ejector according to an embodiment of the present invention.
Fig. 3 is a diagram schematically showing a single-flow type ejector according to an embodiment of the present invention.
Fig. 4 is a schematic diagram for explaining a test apparatus used for evaluation in experimental example 1.
Reference numerals
1 float glass manufacturing device
2 float kiln
3 slag box
4 slow cooling furnace
5 glass ribbon
5a bottom surface
5b top surface
7 lifting roller
8 annealing roller
9 molten metal
20. 30 ejector
21. 31 supply port
24. 34 flow path
25. 35 exhaust port
40 glass plate
41 carbon box
42 quartz tube
43 gas introduction nozzle
Detailed Description
The present invention is not limited to the following embodiments, and various modifications and substitutions may be made to the following embodiments without departing from the scope of the present invention.
In the present embodiment, a configuration example of the float glass production method of the present invention will be described.
FIG. 1 is an explanatory view of a process for producing float glass. Molten glass is continuously supplied onto the molten metal 9 of the float furnace 2, and the glass ribbon 5 is formed on the molten metal 9 (forming step). Although not shown, the molten glass is obtained by melting a glass raw material in a melting step on the upstream side in fig. 1 and performing a fining process in a fining step.
The glass ribbon 5 is then drawn out from the molten metal 9 in the float furnace 2 by a plurality of lift rollers 7, and the glass ribbon 5 is lifted and conveyed at the outlet of the float furnace 2. The portion where the lift roller 7 is present is referred to as a slag box 3.
In order to prevent the glass ribbon 5 drawn out of the float furnace 2 from being broken and reduced in flatness by rapid shrinkage, the glass ribbon is slowly cooled to a temperature equal to or lower than the strain point temperature of the glass while being conveyed by a plurality of annealing rolls 8 in the slow cooling furnace 4 (slow cooling step). The glass ribbon 5 after the slow cooling is cut into a desired size (cutting step).
Hereinafter, of a pair of surfaces opposed to each other in the thickness direction of the glass ribbon 5, the surface supported by the lift roller 7 or the annealing roller 8 is represented as a bottom surface 5a, and the other surface is represented as a top surface 5 b.
When the float glass to be cut is used as a glass substrate for a liquid crystal display, a polishing step of polishing the glass substrate is further provided in order to optimize the flatness of the glass substrate. The polishing step mainly performs mechanical polishing or chemical mechanical polishing on the tin contact surface of the glass substrate. From the viewpoint of improving productivity, the polishing amount is preferably 3 μm or less, more preferably 2 μm or less, still more preferably 1.5 μm or less, and particularly preferably 1.0 μm or less.
The float glass manufacturing method of the present embodiment includes: in the slow cooling step, the injector 20 or 30 provided between the annealing rollers 8 under the glass ribbon 5 is used to supply the gas containing halogen to the bottom surface 5a of the glass ribbon 5, thereby removing foreign matter such as dross adhering to the bottom surface 5 a.
Although not shown in fig. 1, the slow cooling step may include: SO is formed using a protective layer forming device disposed between annealing rollers 8 below the glass ribbon 52And a protective layer forming step of supplying the gas to the bottom surface 5a of the glass ribbon 5 to form a protective layer for preventing damage of sulfate on the bottom surface 5 a. The protective layer forming step may be provided before the foreign substance removing step or may be provided after the foreign substance removing step. In addition, in the protective layer forming step, SO may be supplied2A mixed gas of air and air.
Next, the foreign substance removal process will be specifically described with reference to fig. 2 and 3.
Fig. 2 is a diagram schematically showing a double flow type ejector 20 according to an embodiment of the present invention. Fig. 3 is a diagram schematically showing a single flow type ejector 30 according to an embodiment of the present invention.
The ejectors 20 and 30 may be used in either manner, or 2 or more ejectors may be arranged in series in the moving direction of the glass ribbon 5 to treat the surface of the glass ribbon. The dual-flow injector 20 is an injector in which the flow of gas from the supply port 21 to the exhaust port 25 is equally divided into a forward direction and a reverse direction with respect to the moving direction of the glass ribbon 5, as shown in fig. 2.
The single flow injector 30 is an injector in which the flow of gas from the supply port 31 to the exhaust port 35 is fixed in either the forward or reverse direction with respect to the moving direction of the glass ribbon 5. In the embodiment of fig. 3, the flow of gas from the supply port 31 to the exhaust port 35 is in the forward direction with respect to the moving direction of the glass ribbon 5.
The gas blown onto the bottom surface 5a of the glass ribbon 5 from the supply ports 21, 31 of the injectors 20, 30 moves through the flow paths 24, 34 in the forward or reverse direction with respect to the moving direction of the glass ribbon 5, and flows out to the exhaust ports 25, 35.
The distance D between the supply ports 21, 31 of the injectors 20, 30 and the bottom surface 5a of the glass ribbon 5 is preferably 3 to 50 mm. The distance D is more preferably 5mm or more, and still more preferably 8mm or more. The distance D is more preferably 40mm or less, and still more preferably 30mm or less. By setting the distance D to 50mm or less, diffusion of the gas into the atmosphere can be suppressed, and a sufficient amount of the gas can be made to reach the bottom surface 5a of the glass ribbon 5 with respect to a desired amount of the gas. Further, by setting the distance D to 3mm or more, even if the glass ribbon 5 between the annealing rollers 8 is bent, the contact between the bottom surface 5a of the glass ribbon 5 and the ejectors 20 and 30 can be avoided.
The distance L between the ejectors 20 and 30 in the moving direction of the glass ribbon 5 is preferably 50 to 500 mm. The distance L is more preferably 100mm or more, and still more preferably 200mm or more. The distance L is more preferably 400mm or less. By setting the distance L to 500mm or less, the distance between the annealing rollers 8 can be shortened, and therefore, the deflection of the glass ribbon 5 can be suppressed and the dross can be removed uniformly. Further, by setting the distance L to 50mm or more, the supply ports 21, 31 and the exhaust ports 25, 35 can be established. The distance L of the ejector 20 is preferably 100mm or more, and the distance L of the ejector 30 is preferably 50mm or more.
The distance of the ejectors 20 and 30 in the direction horizontally orthogonal to the moving direction of the glass ribbon 5 is preferably a distance equal to or greater than the product area in the direction of the glass ribbon 5. Preferably 3000mm or more, more preferably 4000mm or more.
The supply ports 21, 31 and the exhaust ports 25, 35 for supplying the halogen-containing gas preferably face the bottom surface 5a of the glass ribbon 5.
In the present embodiment, the temperature of the glass ribbon 5 when the bottom surface 5a of the glass ribbon 5 being conveyed is treated by supplying the halogen-containing gas to the bottom surface 5a is preferably 400 to 900 ℃, and more preferably 500 to 800 ℃. The effect of removing tin defects by halogen-containing gas is higher at higher temperatures.
In the foreign matter removal step of the present embodiment, when the gas containing halogen is hydrogen chloride (HCl) gas, the dross (tin and tin oxide) adhering to the bottom surface 5a of the glass ribbon 5 is removed by the following reaction mechanism.
SnO2+2HCl→SnCl2+H2O+1/2O2(1)
For removing the tin oxide, it is preferable to use tin oxide (SnO) as represented by the above formula (1)2) Reaction with hydrogen chloride (HCl) to form stannic chloride (SnCl)2)。
The halogen-containing gas is preferably hydrogen chloride (HCl) gas of 0.1 vol% or more. More preferably 0.5 vol% or more of hydrogen chloride (HCl) gas.
Alternatively, hydrogen (H) gas is added to hydrogen chloride (HCl) gas2) The following reaction is carried out as the reducing gas, and the tin oxide can be more effectively removed:
SnO2+2H2→Sn+2H2O (2)
Sn+2HCI→SnCl2+H2 (3)
instead of the hydrogen gas (H) of the above formula (2)2) Carbon monoxide (CO) and methane (CH) may be used4) Ethane (C)2H6) Propane (C)3H8) Butane (C)4H10) Ethylene (C)2H4) Propylene (C)3H6) Acetylene (C)2H2) Propyne (C)3H4) Hydrogen sulfide (H)2S), sulfur dioxide (SO)2) Nitrogen monoxide (NO) or ammonia (NH)3) As a reducing gas. These reducing gases may be used alone or in combination of two or more.
The halogen-containing gas preferably contains 10 vol% or more of hydrogen (H)2) More preferably, it contains 50% by volume or more of hydrogen (H)2) More preferably, the hydrogen gas (H) is contained in an amount of 90 vol% or more2)。
The reaction temperature of the above formulae (1) and (3) is preferably 630 ℃ or higher. The reason is that tin chloride (SnCl) is formed in the above formulas (1) and (3)2) Has a boiling point of 623 ℃ so that tin chloride (SnCl) is formed from the bottom surface 5a of the glass ribbon 52) And (6) volatilizing.
In the case where the chlorine-containing gas is other than hydrogen chloride (HCl) gas, the tin defects are also removed by the same reaction mechanism as described above.
In the foreign matter removal step of the present embodiment, hydrogen chloride (HCl) or chlorine (Cl) gas may be used2) Silicon tetrachloride (SiCl)4) Sulfur dichloride (SCl)2) Disulfide dichloride (S)2Cl2) Phosphorus trichloride (PCl)3) Phosphorus pentachloride (PCl)5) Iodine trichloride (I)2Cl6) Nitrogen trichloride (NCl)3) Iodine monochloride (ICl), bromine monochloride (BrCl) or chlorine trifluoride (ClF)3) As a chlorine-containing gas. These gases may be used alone or in combination of two or more.
Among these, hydrogen chloride (HCl) gas is preferable for reasons of cost, known operation method, and the like.
In addition, fluorine (F) may be used in addition to chlorine-containing gas2) Bromine (Br)2) Hydrogen Fluoride (HF), hydrogen bromide (HBr) or Hydrogen Iodide (HI) as the halogen-containing gas.
In the foreign matter removal step of the present embodiment, the halogen-containing gas may be sprayed as a single gas or a mixed gas of two or more kinds onto the bottom surface 5a of the glass ribbon 5, but from the viewpoint of preventing corrosion of the equipment such as the supply ports 21, 31 for spraying these gases, it is preferable to use an inert gas such as nitrogen gas or a rare gas as a carrier gas and spray the inert gas as a mixed gas with these carrier gases.
In addition, hydrogen (H) is added2) When the reducing gas is added to the halogen-containing gas, the halogen-containing gas and the reducing gas may be sprayed from separate supply ports (not shown), or the two gases may be mixed in advance and sprayed from the same supply ports 21 and 31 as a mixed gas.
In the case where two kinds of gases are sprayed from the respective supply ports, the reducing gas may be sprayed on the upstream side of the halogen-containing gas in the moving direction of the glass ribbon 5, or the two kinds of gases may be sprayed at the same position.
The float glass of the present invention may have a composition of glass containing an alkali metal component such as soda-lime glass, or may have an alkali-free glass composition containing substantially no alkali metal component. Particularly, it is suitable for producing float glass having an alkali-free glass composition which is widely used as a glass substrate for a liquid crystal display.
Next, a configuration example of the float glass manufacturing apparatus of the present invention will be explained.
The float glass of the present invention is manufactured using the float glass manufacturing apparatus 1 shown in fig. 1. As described above, fig. 1 includes: a float furnace 2 for continuously supplying molten glass onto molten metal 9 and forming a glass ribbon 5 on the molten metal 9. Although not shown, the molten glass is obtained by melting a glass raw material in a melting furnace on the upstream side in fig. 1 and performing a fining process. Further, a slag box 3 having a lift roller 7 for lifting the glass ribbon 5 is disposed adjacent to the float furnace 2. Further, the annealing furnace 4 is disposed adjacent to the slag box 3, and the annealing furnace 4 can perform annealing to a temperature equal to or lower than the strain point temperature of the glass while the glass ribbon 5 is being conveyed by the annealing rolls 8. Although not shown in fig. 1, the glass ribbon 5 after the slow cooling is cut to a desired size by a cutting device.
Although not shown in fig. 1, when the float glass after cutting is used as a glass substrate for a liquid crystal display, the float glass manufacturing apparatus further includes a polishing device for polishing the glass substrate in order to optimize the flatness of the glass substrate. The polishing apparatus mainly performs mechanical polishing or chemical mechanical polishing on the tin contact surface of the glass substrate. From the viewpoint of improving productivity, the polishing amount is preferably 3 μm or less, more preferably 2 μm or less, still more preferably 1.5 μm or less, and particularly preferably 1.0 μm or less.
The float glass manufacturing apparatus 1 of the present embodiment includes ejectors 20 and 30 provided between the annealing rollers 8 below the glass ribbon 5 in the annealing furnace 4. The injectors 20 and 30 supply a gas containing halogen to the bottom surface 5a of the glass ribbon 5 to remove foreign substances such as dross adhering to the bottom surface 5 a.
Although not shown in fig. 1, the float glass manufacturing apparatus 1 may have a protective layer forming device provided between the annealing rollers 8 below the glass ribbon 5 in the annealing furnace 4. The protective layer forming device is used to form SO2The gas is supplied to the bottom surface 5a of the glass ribbon 5, thereby forming a protective layer for preventing damage of sulfate on the bottom surface 5 a. The protective layer forming device may be provided upstream or downstream of the ejectors 20 and 30 in the moving direction of the glass ribbon 5. In addition, the protective layer forming apparatus may supply SO2A mixed gas of air and air.
The configuration of the injectors 20 and 30, the type of gas used in the injectors 20 and 30, and the like may be the same as those in the float glass production method, and therefore, the description thereof will be omitted.
Examples
(Experimental example 1)
(examples 1 to 11)
Fig. 4 is a schematic diagram for explaining a test apparatus used for evaluation in experimental example 1. Float glass (manufactured by Asahi glass company: AN100) was produced so that the thickness was 0.5mm, and cut into 10mm squares to obtain 10 glass sheets 40, and 1 dross was present on the tin contact surface for each 1 glass sheet 40.
In example 1, as shown in FIG. 4, a glass plate 40 was placed with its tin contact surface facing upward and having an opening into which a gas introduction nozzle 43 was insertedA carbon box 41 having a volume of 25mL, and the carbon box 41 was put into a quartz tube 42 having a volume of 4L, and then the quartz tube 42 was heated for 2 minutes by an electric heater, thereby raising the temperature of the glass plate 40 to 600 ℃. The glass plate 40 after the temperature rise was kept at 600 ℃ for 1 minute, and nitrogen gas (N) was supplied to the carbon box 41 with the inlet of the gas inlet nozzle 43 having an inner diameter of 6mm facing the wall surface2) A gas treatment was performed by blowing a gas having a linear velocity of 40 cm/sec onto the glass plate 40 by introducing 5.0 vol% of hydrogen chloride (HCl) gas as a carrier gas at a flow rate of 2.5L/min for 3 seconds. Then, nitrogen gas (N) is introduced through the gas introduction nozzle 432) The glass plate 40 was cooled to room temperature over 30 minutes while being introduced at a flow rate of 2.5L/min.
Then, a polishing pad made of foamed polyurethane (D hardness 30 degrees) and cerium oxide as a polishing agent were used, and a predetermined polishing load (50 g/cm) was applied by a 4B single-side polishing machine2) The tin contact surface of the glass plate 40 after the gas treatment was chemically mechanically polished so that the polishing amount was 0.8 μm on average. Here, 4B indicates that the size of the carrier put into the grinder is 4 inches. The dross of the 10 glass sheets 40 was removed entirely. The rate of residue remaining in the glass sheet after the chemical mechanical polishing was 0%.
In examples 2 to 10, the hydrogen chloride (HCl) gas concentration, the glass plate temperature, or the hydrogen gas (H) gas were changed as shown in Table 1 by the same evaluation method as in example 12) The condition of concentration.
Table 1 shows the evaluation results of examples 1 to 11, examples 1 to 10 being examples, and example 11 being comparative examples. It can be confirmed that: if hydrogen chloride (HCl) gas of 0.1 vol% or more is used, the dross residual rate is reduced.
TABLE 1
Examples 21 to 28
In example 21, chemical mechanical polishing was performed so that the polishing amount was 0.5 μm on average. Except for this, the same procedure as in example 1 was carried out to carry out gas treatment and chemical mechanical polishing, whereby all the dross in 10 glass sheets 40 was removedThe portions are removed. The rate of residue remaining in the glass sheet after the chemical mechanical polishing was 0%. In examples 22 to 28, the hydrogen chloride (HCl) gas concentration or the hydrogen gas (H) gas concentration was changed as shown in Table 2 in the same evaluation method as in example 212) The condition of concentration.
Table 2 shows the evaluation results of examples 21 to 28, examples 21 to 27 being examples and example 28 being comparative examples. It can be confirmed that: if hydrogen chloride (HCl) gas of 0.1 vol% or more is used, the dross residual rate is reduced.
TABLE 2
(Experimental example 2)
Examples 31 to 36
In example 31, as shown in FIGS. 1 and 2, a dual-flow type injector 20 was inserted between annealing rolls 8 in a slow cooling furnace 4 at a position 660 ℃ of a glass ribbon 5 having a thickness of 0.7 mm. The distance D between the supply port 21 of the injector 20 and the bottom surface 5a of the glass ribbon 5 was set to 10 mm. Further, the distance L of the injector 20 in the moving direction of the glass ribbon 5 was set to 300 mm. Using the ejector 20, with nitrogen (N)2) As a carrier gas, 10 vol% of hydrogen (H) was added2) Is blown onto the bottom surface 5a of the glass ribbon 5 at a linear velocity of 100 cm/sec.
Float glass (manufactured by Asahi glass company: AN100) produced by slowly cooling and cutting a glass ribbon 5 was cut into 50mm squares to obtain 5 glass sheets, and 1 dross was present on the tin contact surface for each 1 glass sheet.
Next, a polishing pad made of foamed polyurethane (D hardness: 30 degrees) and cerium oxide as a polishing agent were used, and a predetermined polishing load (50 g/cm) was applied by a 4B single-side polishing machine2) The gas-treated surface was subjected to chemical mechanical polishing so that the polishing amount was 0.3 μm on average. Dross was removed from 4 of the 5 glass sheets. The rate of residue remaining in the glass sheet after the chemical mechanical polishing was 20%.
In examples 32 to 36, the same evaluation methods as in example 31 were carried out, as shown in Table 3The concentration of hydrogen chloride (HCl) gas, the temperature of the glass plate or the hydrogen gas (H) is changed2) The condition of concentration.
Table 3 shows the evaluation results of examples 31 to 36, examples 31, 32, 34 and 35 being examples, and examples 33 and 36 being comparative examples. It can be confirmed that: if hydrogen chloride (HCl) gas of 0.5 vol% or more is used, the dross residual rate is reduced. In addition, it was confirmed that: by increasing the glass sheet temperature from 660 ℃ to 680 ℃, the rate of dross residue is reduced.
TABLE 3
Examples 41 to 49
In example 41, as shown in FIGS. 1 and 2, a dual-flow type injector 20 was inserted between annealing rolls 8 in a slow cooling furnace 4 at a position where a glass ribbon 5 having a thickness of 0.5mm was 680 ℃. The distance D between the supply port 21 of the injector 20 and the bottom surface 5a of the glass ribbon 5 was set to 10 mm. Further, the distance L of the injector 20 in the moving direction of the glass ribbon 5 was set to 300 mm. Using the injector 20, 0.5 vol% of hydrogen chloride (HCl) gas and 99.5 vol% of hydrogen gas (H) were introduced2) The mixed gas (2) is blown onto the bottom surface 5a of the glass ribbon 5 at a linear velocity of 50 cm/sec.
Float glass (manufactured by Asahi glass company: AN100) produced by slowly cooling and cutting a glass ribbon 5 was cut into 50mm squares to obtain 7 glass sheets, and 1 dross was present on the tin contact surface for each 1 glass sheet.
Next, a polishing pad made of foamed polyurethane (D hardness: 30 degrees) and cerium oxide as a polishing agent were used, and a predetermined polishing load (50 g/cm) was applied by a 4B single-side polishing machine2) The gas-treated surface was subjected to chemical mechanical polishing so that the polishing amount was 0.5 μm on average. Dregs of 6 glass plates out of 7 glass plates were removed. The rate of residue remaining in the glass sheet after the chemical mechanical polishing was 14%.
In examples 42 to 49, the hydrogen chloride (HCl) gas concentration or the hydrogen gas (H) gas concentration was changed as shown in Table 4 in the same evaluation method as in example 412) The condition of concentration. Examples 42,43. 46, 47, 49, nitrogen (N) was used2) As a carrier gas.
Table 4 shows the evaluation results of examples 41 to 49, examples 41 to 48 being examples and example 49 being comparative examples. It can be confirmed that: if hydrogen chloride (HCl) gas of 0.5 vol% or more is used, the dross residual rate is reduced. In addition, it was confirmed that: by increasing hydrogen (H)2) The concentration and the residue rate are reduced.
TABLE 4
As described above, although the float glass production method and the float glass production apparatus have been described in detail with reference to the specific embodiments, the present invention is not limited to the above-described embodiments, and it is apparent to those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the present invention.
The present application is based on japanese patent application 2015-114395, filed on 5.6.2015, the contents of which are incorporated herein by reference.
Claims (7)
1. A float glass production method comprising: a melting step of melting a glass raw material, a fining step of fining the melted glass, a forming step of continuously supplying the fined molten glass onto a molten metal in a float furnace and forming a glass ribbon on the molten metal, and a slow cooling step of pulling out the glass ribbon from the float furnace by a lift roller and slowly cooling the glass ribbon to a temperature equal to or lower than a strain point temperature of the glass while being conveyed by an annealing roller; it is characterized in that the preparation method is characterized in that,
the slow cooling process comprises the following steps: a halogen-containing gas and hydrogen (H) gas using an injector disposed between the annealing rollers and below the glass ribbon2) A foreign matter removing step of supplying the mixed gas to the bottom surface of the glass ribbon to remove foreign matters adhering to the bottom surface, wherein the halogen-containing gas is only a chlorine-containing gas,
the hydrogen (H)2) The concentration of (A) is 10% by volume or more,
the ejector has a supply port and an exhaust port,
the distance between the supply port of the ejector and the bottom surface of the glass ribbon is 3-50 mm, and
the distance of the ejector in the moving direction of the glass ribbon is 50-500 mm.
2. The float glass manufacturing method according to claim 1, wherein the halogen-containing gas is selected from the group consisting of hydrogen chloride (HCl) and chlorine (Cl)2) Silicon tetrachloride (SiCl)4) Sulfur dichloride (SCl)2) Disulfide dichloride (S)2Cl2) Phosphorus trichloride (PCl)3) Phosphorus pentachloride (PCl)5) Iodine trichloride, nitrogen trichloride (NCl)3) At least one gas from the group consisting of iodine monochloride (ICl) and bromine monochloride (BrCl).
3. The float glass production method according to claim 1, wherein the halogen-containing gas is hydrogen chloride (HCl) gas in an amount of 0.1 vol% or more.
4. The float glass production method according to any one of claims 1 to 3, wherein the halogen-containing gas and hydrogen (H) are supplied when the temperature of the glass ribbon is 500 to 800 ℃2) The mixed gas of (1).
5. The float glass production method according to any one of claims 1 to 3, wherein the foreign matter adhering to the bottom surface is dross.
6. The float glass production method according to any one of claims 1 to 3, wherein the slow cooling step comprises: SO was formed using a protective layer forming device disposed between annealing rolls and below the glass ribbon2Gas is supplied to the bottom surface of the glass ribbon, thereby forming a sulfate damage prevention film on the bottom surfaceAnd a protective layer forming step of forming a protective layer.
7. A float glass manufacturing apparatus, comprising: a float furnace for forming a glass ribbon on a molten metal, a slag box adjacent to the float furnace and including a lift roller for pulling out the glass ribbon, and a slow cooling furnace adjacent to the slag box and for slow cooling the glass ribbon to a temperature equal to or lower than a strain point temperature of the glass while being conveyed by an annealing roller; it is characterized in that the preparation method is characterized in that,
the annealing furnace is provided with an ejector which is arranged between the annealing rollers and below the glass ribbon;
the injector injects a halogen-containing gas and hydrogen (H)2) Is supplied to the bottom surface of the glass ribbon, the halogen-containing gas being only a chlorine-containing gas,
the hydrogen (H)2) The concentration of (A) is 10% by volume or more,
the ejector has a supply port and an exhaust port,
the distance between the supply port of the ejector and the bottom surface of the glass ribbon is 3-50 mm, and
the distance of the ejector in the moving direction of the glass ribbon is 50-500 mm.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015114395A JP2017001899A (en) | 2015-06-05 | 2015-06-05 | Manufacturing method of float glass, and manufacturing apparatus of float glass |
| JP2015-114395 | 2015-06-05 |
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| CN106242251A CN106242251A (en) | 2016-12-21 |
| CN106242251B true CN106242251B (en) | 2022-01-04 |
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| JP (1) | JP2017001899A (en) |
| KR (1) | KR20160143549A (en) |
| CN (1) | CN106242251B (en) |
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| JP6584289B2 (en) * | 2015-11-04 | 2019-10-02 | 東京エレクトロン株式会社 | Substrate mounting table and substrate processing apparatus |
| CN106746578B (en) * | 2016-12-21 | 2019-05-24 | 重庆重玻节能玻璃有限公司 | Float glass equipment |
| JP6838530B2 (en) * | 2017-09-01 | 2021-03-03 | Ａｇｃ株式会社 | Float glass manufacturing equipment and float glass manufacturing method |
| TWI829673B (en) * | 2018-03-07 | 2024-01-21 | 美商康寧公司 | Glass substrate adhesion control |
| JP7275801B2 (en) * | 2018-04-25 | 2023-05-18 | Ａｇｃ株式会社 | glass substrate |
| JP2020026358A (en) * | 2018-08-09 | 2020-02-20 | Ａｇｃ株式会社 | Cooling structure, production apparatus of float glass, and production method of float glass |
| WO2020105236A1 (en) | 2018-11-20 | 2020-05-28 | 三井金属鉱業株式会社 | Multilayer body |
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| CN106242251A (en) | 2016-12-21 |
| KR20160143549A (en) | 2016-12-14 |
| JP2017001899A (en) | 2017-01-05 |
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