WO2014175362A1 - Procédé de production de verre à vitre flotté - Google Patents

Procédé de production de verre à vitre flotté Download PDF

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Publication number
WO2014175362A1
WO2014175362A1 PCT/JP2014/061499 JP2014061499W WO2014175362A1 WO 2014175362 A1 WO2014175362 A1 WO 2014175362A1 JP 2014061499 W JP2014061499 W JP 2014061499W WO 2014175362 A1 WO2014175362 A1 WO 2014175362A1
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WIPO (PCT)
Prior art keywords
chlorine
glass
float
fluorine
gas containing
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PCT/JP2014/061499
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English (en)
Japanese (ja)
Inventor
興平 安田
泰夫 林
信彰 井川
竜麻 市川
聡史 宮坂
Original Assignee
旭硝子株式会社
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Application filed by 旭硝子株式会社 filed Critical 旭硝子株式会社
Priority to KR1020157030298A priority Critical patent/KR102152196B1/ko
Priority to JP2015513820A priority patent/JP6341199B2/ja
Priority to CN201480023330.0A priority patent/CN105143132B/zh
Publication of WO2014175362A1 publication Critical patent/WO2014175362A1/fr

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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
    • C03B18/20—Composition of the atmosphere above the float bath; Treating or purifying the atmosphere above the float bath
    • 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
    • C03C15/02—Surface treatment of glass, not in the form of fibres or filaments, by etching for making a smooth surface
    • 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

Definitions

  • the present invention relates to a method for producing a float glass sheet.
  • the float method which is the main manufacturing method for flat glass, is called a float bath.
  • a glass ribbon is formed by continuously flowing molten glass on the surface of a molten metal bath filled with molten metal tin, and this glass ribbon is melted. This is a method of laminating along a metal bath surface while moving forward, and is excellent in producing a large amount of flat glass with high flatness.
  • top specs due to molten metal tin may occur on the upper surface side of the glass ribbon.
  • the top spec is that the tin component evaporated from the molten metal bath condenses on the ceiling or wall, which is the upper part of the bath, and the condensate or the condensate reduced to the metallic state falls as small particles onto the glass ribbon. In other words, it adheres to the upper surface of the glass ribbon as a tin defect having a size of several ⁇ m to several tens ⁇ m.
  • the glass substrate is immersed in a treatment solution comprising a hydrofluoric acid aqueous solution or an acidic aqueous solution containing divalent chromium ions.
  • a treatment solution comprising a hydrofluoric acid aqueous solution or an acidic aqueous solution containing divalent chromium ions.
  • Patent Document 3 discloses that a minute foreign substance existing on the surface of a float plate glass is decomposed and volatilized by sublimating ammonium halide at a high temperature in the vicinity of the foreign substance or in contact with the foreign substance. There is disclosed a method for removing foreign matter on the surface of a float plate glass, which is characterized by being removed.
  • Patent Documents 1 and 2 are off-line processing, and in order to remove tin defects to the extent that the standards required for glass substrates for flat panel displays can be satisfied, the immersion time in the processing solution is reduced. It is necessary to lengthen it.
  • Patent Document 3 it is necessary to sublimate ammonium halide at a high temperature in the vicinity of minute foreign substances existing on the surface of the float plate glass or in contact with the foreign substances. It is difficult to implement in this method, and it is necessary to provide equipment for carrying out this method outside the float bath.
  • ammonium halide has a function of corroding metals, corrosion of equipment used for processing is also a problem.
  • an object of the present invention is to provide a method for producing a float plate glass, in which, when a float plate glass is produced, a tin defect is removed from the glass surface by online processing to obtain a smooth surface.
  • the present invention provides a glass ribbon surface with a chlorine-containing gas and a fluorine-containing gas on the glass ribbon surface in a reducing atmosphere at 500 to 1200 ° C. in a float bath.
  • the float plate glass manufacturing method sprayed so that the conditions shown in (2) may be satisfied.
  • c1 is the chlorine concentration [vol%] of the gas containing chlorine
  • u1 is the flow velocity (linear velocity) [cm / s] of the gas containing chlorine
  • t1 is the spraying time of the gas containing chlorine [s ]
  • T1 is the surface temperature [K] of the glass ribbon
  • r is the radius [ ⁇ m] of tin defects existing on the glass ribbon surface.
  • c2 is the fluorine concentration [vol%] of the gas containing fluorine
  • u2 is the flow velocity (linear velocity) [cm / s] of the gas containing fluorine
  • t2 is the spraying time of the gas containing fluorine [s] ]
  • T2 is the surface temperature [K] of the glass ribbon
  • r is the radius [ ⁇ m] of tin defects existing on the glass ribbon surface.
  • the gas containing chlorine is preferably hydrogen chloride (HCl).
  • the gas containing fluorine is preferably hydrogen fluoride (HF).
  • the total c1 + c2 of the chlorine concentration c1 [vol%] of the gas containing chlorine and the fluorine concentration c2 [vol%] of the gas containing fluorine is greater than 5 [vol%]. Is preferred.
  • chlorine concentration c1 [vol%] of the gas containing chlorine is 2 [vol%] or more.
  • fluorine concentration c2 [vol%] of the gas containing fluorine is preferably 2 [vol%] or more.
  • the product c1 ⁇ t1 of the chlorine concentration c1 [vol%] of the gas containing chlorine and the spraying time t1 [s] of the gas containing chlorine, and the gas containing fluorine The sum (c1 ⁇ t1) + (c2 ⁇ t2) of the product c2 ⁇ t2 of the fluorine concentration c2 [vol%] and the spray time t2 [s] of the gas containing fluorine is larger than 120 [vol% ⁇ s]. preferable.
  • either the spraying time t1 [s] of the gas containing chlorine or the spraying time t2 [s] of the gas containing fluorine is less than 10 [s]. Is preferred.
  • the present invention also relates to a float plate glass obtained by the method of the present invention, wherein the chlorine content at a depth of 0.05 ⁇ m from the top surface facing the surface in contact with the molten metal in the float bath is Cl1 [wt%].
  • the chlorine content at a depth of 0.05 ⁇ m from the top surface facing the surface in contact with the molten metal in the float bath of the float plate glass is Cl1 [wt%], and more than 0.05 ⁇ m and 10 ⁇ m from the top surface.
  • Cl1 [wt%] the minimum value of the chlorine content at the following depth
  • Cl1> Cl2 the fluorine content at a depth of 0.05 ⁇ m from the top surface
  • F2 [wt%] the top
  • a float plate glass satisfying F1> F2 is provided.
  • the said float plate glass is the float plate glass manufactured by surface-treating by making the gas containing chlorine and the gas containing fluorine contact the glass surface of the said float plate glass in a float bath.
  • the chlorine or fluorine content at a depth of more than 0.05 ⁇ m and not more than 10 ⁇ m from the top surface includes a gas containing chlorine and a gas containing fluorine on the glass ribbon surface in the float bath. It is preferred to have a region that is higher than the chlorine or fluorine content of the float sheet glass that is not sprayed.
  • the slope of the chlorine content change at a depth of more than 0.05 ⁇ m and 10 ⁇ m or less from the top surface is [dCl] and the slope of the fluorine content change is [dHF]
  • the chlorine or fluorine content at a depth of more than 0.05 ⁇ m and not more than 10 ⁇ m from the top surface is higher than the chlorine or fluorine content in a portion deeper than 10 ⁇ m from the top surface. Is preferred.
  • tin defects can be removed from the glass surface by online processing in a float bath, and a smooth surface can be obtained. For this reason, the tin defect suitable for the glass substrate for FPD is removed, and the quality, yield, and productivity when producing a float plate glass having a smooth surface are improved.
  • FIGS. 1A and 1B are the results of observing the surface of a glass sample before and after mixed gas spraying with a laser microscope in Example 1, FIG. 1A is before gas spraying, and FIG. It is an observation result after gas spraying.
  • FIG. 2 is a graph showing profiles of chlorine content (wt%) in the depth direction from the glass sample surfaces of Examples 1 and 2 and Comparative Example 1.
  • FIG. 3 is an enlarged view of the graph of FIG. 1 from the glass sample surface to a depth of 3 ⁇ m.
  • FIG. 4 is a graph showing profiles of fluorine content (wt%) in the depth direction from the glass sample surfaces of Examples 1 and 2 and Comparative Example 1.
  • FIGS. 7A and 7B are the results of observing the surface of a glass sample before and after gas spraying with HCl diluted with nitrogen for Comparative Example 3 with a laser microscope.
  • FIG. 7 (b) is an observation result after gas spraying.
  • FIG. 8 (a) and 8 (b) show the results of observation of the surface of a glass sample before and after gas spraying in which HF was diluted with nitrogen in Comparative Example 4 with a laser microscope.
  • FIG. 8 (b) is an observation result after gas spraying.
  • 9 (a) and 9 (b) show the results of observation of the surface of a glass sample before and after gas spraying in which HF was diluted with nitrogen in Comparative Example 5 with a laser microscope.
  • FIG. 9 (b) is an observation result after gas spraying.
  • 10 (a) and 10 (b) are the results of observing the surface of the glass sample before and after the mixed gas spraying with the laser microscope in Example 2, FIG. 10 (a) is before the gas spraying, and FIG. 10 (b) is the result.
  • FIG. 11 (a) and 11 (b) are the results of observing the surface of the glass sample before and after the mixed gas spraying with the laser microscope in Example 3, FIG. 11 (a) is before the gas spraying, and FIG. 11 (b) is the result. It is an observation result after gas spraying.
  • a gas containing chlorine and a gas containing fluorine are sprayed on the surface of the glass ribbon moving in the float bath so as to satisfy the conditions described below.
  • the gas containing chlorine is hydrogen chloride (HCl) as an example
  • tin defects existing as a top spec on the glass ribbon surface are removed by the following reaction mechanism. Sn + 2HCl ⁇ SnCl 2 + H 2
  • the tin defect is removed by the same reaction mechanism as described above.
  • the above reaction mechanism proceeds because the inside of the float bath is maintained at a high temperature. The reason is because the vapor pressure of more SnCl 2 becomes high temperature becomes high, the SnCl 2 produced by the reaction because volatilized from the glass ribbon surface.
  • the temperature in the float bath varies depending on the part, but is maintained at 500 to 1200 ° C.
  • the inside of the float bath is filled with a mixed gas of hydrogen (usually 4 to 10% by volume) and nitrogen (usually 90 to 96% by volume) to form a reducing atmosphere.
  • HCl hydrogen chloride
  • chlorine Cl 2
  • silicon tetrachloride SiCl 4
  • sulfur dichloride Cl 2 S
  • disulfur dichloride S 2 Cl 2).
  • Phosphorus trichloride PCl 3
  • phosphorus pentachloride PCl 5
  • iodine trichloride I 2 Cl 6
  • nitrogen trichloride NCl 3
  • iodine monochloride ICl
  • bromine monochloride BrCl
  • Chlorine trifluoride ClF 3
  • hydrogen chloride (HCl) is preferable for reasons such as cost and handling methods are well known.
  • the entire surface of the glass ribbon is etched by spraying a gas containing fluorine to flatten the surface of the glass ribbon.
  • the etching of the glass ribbon surface by the spray of the gas containing fluorine is fast.
  • HF hydrogen fluoride
  • flon for example, chlorofluorocarbon (CFC), fluorocarbon (FC), hydrochlorofluorocarbon (HCFC), hydrofluorocarbon (HFC)
  • Hydrofluoric acid (HF) simple fluorine (F 2 ), trifluoroacetic acid (CF 3 COOH), carbon tetrafluoride (CF 4 ), silicon tetrafluoride (SiF 4 ), phosphorus pentafluoride (PF 5 ) Phosphorus trifluoride (PF 3 ), boron trifluoride (BF 3 ), nitrogen trifluoride (NF 3 ), chlorine trifluoride (ClF 3 ), or the like
  • hydrogen fluoride (HF) is preferred for reasons such as cost and handling methods are well known.
  • a gas containing chlorine is sprayed on the surface of the glass ribbon so as to satisfy the condition represented by the following formula (1).
  • c1 is the chlorine concentration [vol%] of the gas containing chlorine
  • u1 is the flow velocity (linear velocity) of the gas containing chlorine [cm / s]
  • t1 is the spraying time of the gas containing chlorine [s].
  • T1 is the surface temperature [K] of the glass ribbon
  • r is the radius [ ⁇ m] of tin defects existing on the glass ribbon surface.
  • r is preferably 15 ⁇ m or less, more preferably 10 ⁇ m or less, and even more preferably 5 ⁇ m or less. If the spraying condition of the gas containing chlorine does not satisfy the above formula (1), there is a possibility that the tin defect existing as the top spec on the surface of the glass ribbon cannot be removed sufficiently.
  • a gas containing fluorine is sprayed on the surface of the glass ribbon so as to satisfy the condition represented by the following formula (2). (6.92u2 + 15.8) c2t2 ⁇ exp (-4303 / T2)> r (2)
  • c2 is the fluorine concentration [vol%] of the gas containing fluorine
  • u2 is the flow velocity (linear velocity) [cm / s] of the gas containing fluorine
  • t2 is the spraying time of the gas containing fluorine [s] ]
  • T2 is the surface temperature [K] of the glass ribbon
  • r is the radius [ ⁇ m] of tin defects existing on the glass ribbon surface.
  • r is preferably 15 ⁇ m or less, more preferably 10 ⁇ m or less, and even more preferably 5 ⁇ m or less.
  • the chlorine-containing gas and the fluorine-containing gas may be sprayed on the surface of the glass ribbon as individual gases, but the corrosion of equipment such as nozzles used for spraying these gases is prevented.
  • an inert gas such as nitrogen or a rare gas
  • the gas containing chlorine and the gas containing fluorine may be sprayed from separate nozzles, or may be sprayed from the same nozzle as a mixed gas of both.
  • spraying both from separate nozzles either one may be sprayed upstream from the other in the moving direction of the glass ribbon, or both may be sprayed at the same position.
  • the gas containing chlorine and the gas containing fluorine may be sprayed on the surface of the glass ribbon at any position in the float bath.
  • the temperature on the uppermost stream side in the float bath is the highest, but if gas is sprayed at this position, a new top is formed on the glass ribbon surface after the removal of tin defects. Specs may occur.
  • spraying of these gases should be performed in a reducing atmosphere of Tg + 30 ° C. to Tg + 300 ° C. in the float bath. It is preferable to spray these gases in a reducing atmosphere of Tg + 30 ° C. to Tg + 200 ° C.
  • the distance between the tip of the nozzle used for spraying the gas containing chlorine and the gas containing fluorine and the glass ribbon surface is too wide, the gas sprayed from the nozzle is diffused, The intended spray amount per unit area may not be achieved.
  • the distance between the tip of the nozzle used for spraying these gases and the glass ribbon surface is preferably 50 mm or less, more preferably 20 mm or less, and even more preferably 10 mm or less.
  • the composition of the float plate glass produced by the method of the present invention is not particularly limited, and may be a glass containing an alkali metal component such as soda lime glass, or a non-alkali glass substantially free of an alkali metal component. There may be. However, it is suitable for the production of float glass with a non-alkali glass composition widely used as a glass substrate for FPD because the top spec is removed and a flat glass with a smooth surface is obtained.
  • the float glass obtained by the method of the present invention chlorine and fluorine intrude into the glass ribbon surface because a gas containing chlorine and a gas containing fluorine are sprayed on the glass ribbon surface in the manufacturing process. Therefore, the chlorine content and the fluorine content at a predetermined depth from the top surface of the float glass sheet are higher than those at a predetermined depth deeper from the top surface of the glass sheet.
  • the top surface of the float plate glass refers to a surface that faces the bottom surface in contact with the molten metal in the float bath in the manufacturing process.
  • the float glass sheet obtained by the method of the present invention has a chlorine content of Cl1 [wt%] at a depth of 0.05 ⁇ m from the top surface facing the surface in contact with the molten metal in the float bath.
  • Cl2 [wt%] When the minimum chlorine content at a depth of more than 0.05 ⁇ m and not more than 10 ⁇ m from the surface is Cl2 [wt%], Cl1> Cl2, and the fluorine content at a depth of 0.05 ⁇ m from the top surface is F1 [Wt%]
  • F2 [wt% When the minimum value of fluorine content at a depth of more than 0.05 ⁇ m and 20 ⁇ m or less from the top surface is F2 [wt%], it is a float plate glass where F1> F2.
  • chlorine and fluorine may be added to a glass raw material as a clarifier. In such a case, that is, even when chlorine or fluorine is contained as a fining agent, the above relations Cl1> Cl2 and F1> F2 are satisfied.
  • Example 1 a glass sample having a tin defect on its surface was placed in an experimental apparatus that simulated the atmosphere in the float bath, and removal of the tin defect was attempted by the following procedure.
  • Example 1 It was confirmed by a laser microscope that a tin defect having a radius of 5 ⁇ m was present on the surface of the glass sample to be used (FIG. 1 (a)).
  • the experimental condition was that the inside of the experimental apparatus was maintained in a reducing atmosphere filled with a mixed gas of 10 volume% hydrogen and 90 volume% nitrogen, and the temperature in the experimental apparatus was raised to 900 ° C. .
  • a mixed gas diluted with nitrogen gas so that HCl and HF each have a concentration of 500 ppm is sprayed on the surface of the glass sample for 80 minutes (4800 s) at a flow rate (linear velocity) of 0.5 cm / s.
  • the spray condition of HCl satisfies the formula (1). (6.92u1 + 15.8) c1t1 ⁇ exp (-4303 / T1)> r (1)
  • c1 is the chlorine concentration [vol%] of the gas containing chlorine
  • u1 is the flow velocity (linear velocity) of the gas containing chlorine [cm / s]
  • t1 is the spraying time of the gas containing chlorine [s].
  • T1 is the surface temperature [K] of the glass ribbon
  • r is the radius [ ⁇ m] of tin defects existing on the glass ribbon surface.
  • the spraying condition of HF satisfies the formula (2). (6.92u2 + 15.8) c2t2 ⁇ exp (-4303 / T2)> r (2)
  • c2 is the fluorine concentration [vol%] of the gas containing fluorine
  • u2 is the flow velocity (linear velocity) [cm / s] of the gas containing fluorine
  • t2 is the spraying time [s] of the gas containing fluorine.
  • T2 is the surface temperature [K] of the glass ribbon
  • r is the radius [ ⁇ m] of tin defects existing on the glass ribbon surface.
  • Example 2 The same procedure as in Example 1 was performed except that the spraying of HCl and HF was performed under the conditions described in Table 1.
  • Example 3 The same procedure as in Example 1 was performed except that the spraying of HCl and HF was performed under the conditions described in Table 1.
  • spraying is performed using a mixed gas obtained by diluting HCl and HF with nitrogen gas, but gas obtained by diluting HCl and HF with nitrogen gas may be sprayed separately.
  • FIG. 1B As a result of observing the glass sample surfaces of Examples 1 to 3 with a laser microscope, tin defects were almost removed, and the glass sample surfaces were almost flat (FIG. 1B, FIG. 10B and FIG. 11 (b)). Further, when the surface of the glass sample was confirmed with a scanning electron microscope (SEM-EDX), it was confirmed that tin defects were almost removed.
  • SEM-EDX scanning electron microscope
  • FIGS. 3 is the figure which expanded from the glass sample surface to the depth of 3 micrometers in FIG.
  • the chlorine content (Cl1) at a depth of 0.05 ⁇ m from the glass sample surface, and the minimum chlorine content (Cl2) at a depth of more than 0.05 ⁇ m and 10 ⁇ m or less from the glass sample surface. Satisfies the relationship Cl1> Cl2.
  • the fluorine content (F1) at a depth of 0.05 ⁇ m from the glass sample surface and the minimum fluorine content (F2) at a depth of more than 0.05 ⁇ m and 20 ⁇ m or less from the glass sample surface are F1> F2 Meet the relationship. 2 to 4 also show the measurement results of the glass sample of Comparative Example 1 in which nitrogen gas is sprayed instead of the mixed gas containing HCl and HF.
  • Comparative Example 1 the relationship is Cl1 ⁇ Cl2 and F1 ⁇ F2. Further, the content of chlorine or fluorine at a depth of more than 0.05 ⁇ m and 10 ⁇ m or less from the top surface of Examples 1 and 2 is higher than that of Comparative Example 1. At this time, Comparative Example 1 corresponds to a float plate glass in which a gas containing chlorine and a gas containing fluorine are not sprayed on the glass ribbon surface in the float bath in the present invention.
  • the slope of the chlorine content change at a depth of more than 0.05 ⁇ m and 10 ⁇ m or less from the top surface of Examples 1 and 2 is [dCl]
  • the slope of the fluorine content change is [dHF], [dCl] Or it has a region where [dHF] is negative.
  • the slope of the change in chlorine content and the slope of the change in fluorine content in Comparative Example 1 are always positive, that is, the chlorine content and the fluorine content increase monotonously from the top surface in the depth direction. is doing.
  • the chlorine or fluorine content at a depth of more than 0.05 ⁇ m and not more than 10 ⁇ m from the top surface is higher than the chlorine or fluorine content in a portion deeper than 10 ⁇ m from the top surface. .
  • Example 1 (Comparative Example 1) Implementation was performed except that nitrogen gas was sprayed at a flow rate (linear velocity) of 0.5 cm / s for 80 minutes (4800 s) instead of a mixed gas obtained by diluting HCl and HF with nitrogen gas so that each concentration became 500 ppm. The same procedure as in Example 1 was performed. After completion of gas spraying, the glass sample surface was cooled to room temperature and then confirmed with a laser microscope. As a result, tin defects were not removed (FIGS. 5A and 5B).
  • Example 2 A procedure similar to that in Example 1 was performed, except that a gas diluted with nitrogen gas so that the concentration was 5% was sprayed at a flow rate (linear velocity) of 20 cm / s for 10 seconds.
  • the spray condition of HCl satisfies the above formula (1).
  • the surface of the glass sample was confirmed with a laser microscope. As a result, the tin defect was removed, but a recess was confirmed at the site where the tin defect existed (FIG. 6 ( a), (b)).
  • Example 3 The same procedure as in Example 1 was carried out except that only HCl was diluted with nitrogen gas so as to have a concentration of 0.1% and sprayed at a flow rate (linear velocity) of 0.5 cm / s for 60 seconds. did. The spray condition of HCl does not satisfy the above formula (1). After the gas spraying was finished, the glass sample surface was confirmed with a laser microscope after cooling to room temperature. As a result, tin defects were not removed (FIGS. 7A and 7B).
  • Example 4 The same procedure as in Example 1 was carried out except that HF alone was sprayed with a gas diluted with nitrogen gas to a concentration of 0.1% at a flow rate (linear velocity) of 0.5 cm / s for 60 seconds. did. This HF spraying condition does not satisfy the above formula (2). After the gas spraying was finished, the glass sample surface was confirmed with a laser microscope after cooling to room temperature. As a result, tin defects were not removed (FIGS. 8A and 8B).
  • Example 5 The same as in Example 1 except that HF alone was sprayed with nitrogen gas diluted to a concentration of 0.1% for 20 minutes (1200 s) at a flow rate (linear velocity) of 0.5 cm / s. The procedure was carried out. This HF spraying condition satisfies the above formula (2). After the gas spraying was finished, the glass sample surface was confirmed with a laser microscope after cooling to room temperature. As a result, tin defects were not removed (FIGS. 9A and 9B).

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Abstract

Cette invention concerne un procédé permettant de produire un verre à vitre flotté ayant une surface de verre dépourvue d'imperfections d'étain et une surface lisse qui est obtenue par un procédé en-ligne quand le verre à vitre est produit par un procédé "float". Un procédé de production de verre à vitre flotté selon l'invention est en outre décrit, le procédé consistant à pulvériser un gaz contenant du chlore et un gaz contenant du fluor sur la surface d'un ruban de verre sous atmosphère réductrice dans un bain de flottage à 500-1200°C, de façon à satisfaire les conditions prescrites respectives.
PCT/JP2014/061499 2013-04-24 2014-04-23 Procédé de production de verre à vitre flotté WO2014175362A1 (fr)

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KR1020157030298A KR102152196B1 (ko) 2013-04-24 2014-04-23 플로트 판유리 제조 방법
JP2015513820A JP6341199B2 (ja) 2013-04-24 2014-04-23 フロート板ガラス製造方法
CN201480023330.0A CN105143132B (zh) 2013-04-24 2014-04-23 浮法平板玻璃制造方法

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Cited By (6)

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WO2015045405A1 (fr) * 2013-09-30 2015-04-02 日本板硝子株式会社 Procédé de fabrication d'une feuille de verre
WO2015115100A1 (fr) * 2014-01-31 2015-08-06 日本板硝子株式会社 Procédé de production de plaque de verre et plaque de verre
CN106242251A (zh) * 2015-06-05 2016-12-21 旭硝子株式会社 浮法玻璃制造方法和浮法玻璃制造装置
JPWO2015029455A1 (ja) * 2013-09-02 2017-03-02 日本板硝子株式会社 ガラス板の製造方法及びガラス板
KR20180077166A (ko) * 2015-10-29 2018-07-06 아사히 가라스 가부시키가이샤 디스플레이용 유리 기판, 및 디스플레이용 유리 기판의 제조 방법
JP2022542479A (ja) * 2020-06-08 2022-10-03 蚌埠中光▲電▼科技有限公司 高世代ｔｆｔ－ｌｃｄガラス基板生産ライン

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Publication number Priority date Publication date Assignee Title
CN106946474B (zh) * 2017-04-10 2019-06-28 蚌埠玻璃工业设计研究院 一种电子显示用浮法平板玻璃粘锡在线去除方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1085684A (ja) * 1996-09-11 1998-04-07 Asahi Glass Co Ltd フロートガラス基板表面の異物除去方法
JP2007308331A (ja) * 2006-05-18 2007-11-29 Nippon Sheet Glass Co Ltd フロートバス

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09295833A (ja) 1996-04-26 1997-11-18 Seimi Chem Co Ltd フロートガラス基板の平坦化方法
JPH09295832A (ja) 1996-04-26 1997-11-18 Asahi Glass Co Ltd ガラス基板表面の異物除去方法
WO2008007676A1 (fr) * 2006-07-13 2008-01-17 Asahi Glass Company, Limited substrat de verre sans alcalin, son processus de fabrication et panneaux d'affichage à cristaux liquides
KR101245278B1 (ko) * 2009-08-07 2013-03-19 주식회사 엘지화학 전도성 기판 및 이의 제조 방법
WO2013011980A1 (fr) * 2011-07-20 2013-01-24 旭硝子株式会社 Procédé de production de verre flotté
US20150122319A1 (en) * 2011-07-28 2015-05-07 David A. Strickler Apcvd of doped titanium oxide and the coated article made thereby

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1085684A (ja) * 1996-09-11 1998-04-07 Asahi Glass Co Ltd フロートガラス基板表面の異物除去方法
JP2007308331A (ja) * 2006-05-18 2007-11-29 Nippon Sheet Glass Co Ltd フロートバス

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2015029455A1 (ja) * 2013-09-02 2017-03-02 日本板硝子株式会社 ガラス板の製造方法及びガラス板
US10150696B2 (en) 2013-09-30 2018-12-11 Nippon Sheet Glass Company, Limited Method for producing glass sheet
WO2015045405A1 (fr) * 2013-09-30 2015-04-02 日本板硝子株式会社 Procédé de fabrication d'une feuille de verre
JPWO2015045405A1 (ja) * 2013-09-30 2017-03-09 日本板硝子株式会社 ガラス板の製造方法
WO2015115100A1 (fr) * 2014-01-31 2015-08-06 日本板硝子株式会社 Procédé de production de plaque de verre et plaque de verre
JPWO2015115100A1 (ja) * 2014-01-31 2017-03-23 日本板硝子株式会社 ガラス板の製造方法及びガラス板
US10358381B2 (en) 2014-01-31 2019-07-23 Nippon Sheet Glass Company, Limited Method for producing glass sheet, and glass sheet
CN106242251B (zh) * 2015-06-05 2022-01-04 Ａｇｃ株式会社 浮法玻璃制造方法和浮法玻璃制造装置
CN106242251A (zh) * 2015-06-05 2016-12-21 旭硝子株式会社 浮法玻璃制造方法和浮法玻璃制造装置
KR20180077166A (ko) * 2015-10-29 2018-07-06 아사히 가라스 가부시키가이샤 디스플레이용 유리 기판, 및 디스플레이용 유리 기판의 제조 방법
KR102594924B1 (ko) 2015-10-29 2023-10-30 에이지씨 가부시키가이샤 디스플레이용 유리 기판, 및 디스플레이용 유리 기판의 제조 방법
JP2022542479A (ja) * 2020-06-08 2022-10-03 蚌埠中光▲電▼科技有限公司 高世代ｔｆｔ－ｌｃｄガラス基板生産ライン
JP7300553B2 (ja) 2020-06-08 2023-06-29 蚌埠中光▲電▼科技有限公司 高世代ｔｆｔ－ｌｃｄガラス基板生産ライン

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JP6341199B2 (ja) 2018-06-13
CN105143132A (zh) 2015-12-09
TW201500303A (zh) 2015-01-01

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