WO2014013913A1 - Procédé de fabrication de plaque de verre et plaque de verre - Google Patents
Procédé de fabrication de plaque de verre et plaque de verre Download PDFInfo
- Publication number
- WO2014013913A1 WO2014013913A1 PCT/JP2013/068777 JP2013068777W WO2014013913A1 WO 2014013913 A1 WO2014013913 A1 WO 2014013913A1 JP 2013068777 W JP2013068777 W JP 2013068777W WO 2014013913 A1 WO2014013913 A1 WO 2014013913A1
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- glass
- glass plate
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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
-
- 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
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
- C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
- C03C3/093—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium containing zinc or zirconium
Definitions
- the present invention relates to a method for producing a glass plate and a glass plate.
- the float method is widely used as a glass plate forming method.
- molten glass continuously supplied onto molten tin in a float bath (hereinafter also simply referred to as “bath”) is flowed over molten tin and formed into a strip shape (for example, Patent Document 1). reference).
- the atmosphere in the bath is a reducing atmosphere containing hydrogen gas in order to prevent oxidation of molten tin.
- Hydrogen gas reacts with oxygen gas mixed from the outside to prevent oxidation of molten tin.
- the present invention has been made in view of the above-described problems, and an object of the present invention is to provide a method for producing a glass plate with good quality on the main surface in contact with the reducing atmosphere in the bus, and a glass plate.
- a method for producing a glass plate according to the aspect (1) of the present invention comprises: In the method for producing a glass plate, including a step of forming molten glass that is continuously supplied onto molten tin in a float bath and flowing on the molten tin, The molten glass immediately before being supplied into the float bath is characterized in that the total content of impurities Au, Cu, and Ag is 0.5 mass ppm or less.
- the manufacturing method of the glass plate by aspect (2) of this invention is the following.
- the method for producing a glass plate including a step of forming molten glass that is continuously supplied onto molten tin in a float bath and flowing on the molten tin,
- the molten glass immediately before being supplied into the float bath is characterized in that the total content of impurities F, Cl, Br and I is 200 ppm by mass or less.
- the glass plate by aspect (3) of this invention is In a glass plate formed by flowing molten glass continuously supplied on molten tin in a float bath on the molten tin,
- the total content of impurities Au, Cu, and Ag is 0.5 mass ppm or less.
- the glass plate by aspect (4) of this invention is In a glass plate formed by flowing molten glass continuously supplied on molten tin in a float bath on the molten tin,
- the total content of impurities F, Cl, Br and I is 200 mass ppm or less.
- a glass plate manufacturing method and a glass plate with good quality of the main surface in contact with the reducing atmosphere in the bus are provided.
- FIG. 1 is an explanatory view (1) of a glass plate manufacturing apparatus according to an embodiment of the present invention.
- FIG. 2 is an explanatory view (2) of the glass plate manufacturing apparatus according to the embodiment of the present invention.
- the method for producing a glass plate according to the present embodiment includes, for example, a melting step, a forming step, a slow cooling step, and a cutting step, and further includes a polishing step as necessary.
- polishing process is performed according to the use of a glass plate.
- glass raw materials prepared by mixing a plurality of types of raw materials are melted to obtain molten glass.
- the glass raw material is put into the melting furnace, it is melted by the radiant heat of the flame injected from the burner to become molten glass.
- the molten glass obtained in the melting step is continuously supplied onto the molten tin in the bath, and the molten glass is flowed on the molten tin and molded to obtain a plate-like glass (so-called glass ribbon).
- This forming method is called a float method.
- the atmosphere in the bath is a reducing atmosphere containing hydrogen gas in order to prevent oxidation of molten tin.
- the glass sheet is cooled while flowing in a predetermined direction, and is pulled up from the molten tin in the vicinity of the exit of the bath.
- the sheet glass obtained in the forming step is slowly cooled in a slow cooling furnace.
- the plate glass is gradually cooled while being transported horizontally on the roll from the inlet to the outlet of the slow cooling furnace.
- Sulfurous acid (SO 2 ) gas or the like is sprayed on the surface of the sheet glass near the inside of the inlet of the slow cooling furnace, and a scratch-proof film is formed on the surface layer of the sheet glass. Since the outlet of the slow cooling furnace is open to the atmosphere, the atmosphere in the slow cooling furnace is an air atmosphere.
- the sheet glass slowly cooled in the slow cooling step is cut into a predetermined size by a cutting machine.
- both edges (so-called ears) in the width direction of the sheet glass are cut off. This is because both edges in the width direction of the plate-like glass become thick due to the influence of surface tension and the like.
- the main surface of the glass plate obtained in the cutting step is polished.
- the main surface (hereinafter referred to as “bottom surface”) in contact with the molten tin in the bath is polished according to the use of the glass plate.
- the main surface opposite to the bottom surface and in contact with the reducing atmosphere in the bus (hereinafter referred to as “top surface”) is not polished.
- a glass plate is used as a window glass for vehicles, a window glass for buildings, a substrate for display, a cover glass for display, or a substrate for photomask, for example.
- the “display” includes a flat panel display (FPD) such as a liquid crystal display (LCD), a plasma display (PDP), and an organic EL display.
- FPD flat panel display
- LCD liquid crystal display
- PDP plasma display
- organic EL display organic EL display.
- the thickness of the substrate for display is exemplified by 1 mm or less.
- the thickness of the glass plate used for flexible liquid crystal panels, such as a tablet terminal is 0.3 mm or less.
- the glass type of the glass plate is selected according to the use of the glass plate.
- a glass substrate for LCD alkali-free glass is used.
- soda lime glass is used in the case of a window glass for a vehicle, a window glass for a building, and a glass substrate for a PDP.
- soda lime glass is used in the case of a cover glass for display.
- soda lime glass that can be chemically strengthened is mainly used in the case of a substrate for a photomask.
- quartz glass having a low thermal expansion coefficient is mainly used.
- the alkali-free glass is, for example, expressed by mass% based on oxide, SiO 2 : 50 to 66%, Al 2 O 3 : 10.5 to 24%, B 2 O 3 : 0 to 12%, MgO: 0 to 8%, CaO: 0 to 14.5%, SrO: 0 to 24%, BaO: 0 to 13.5%, ZrO 2 : 0 to 5%, SnO: 0 to 3%, MgO + CaO + SrO + BaO: 9 to 29.5%, and the total content of alkali metal oxides may be 0.1% or less.
- the alkali-free glass is preferably expressed in terms of mass% based on oxide, SiO 2 : 58 to 66%, Al 2 O 3 : 15 to 22%, B 2 O 3 : 5 to 12%, MgO: 0 to 8 %, CaO: 0 to 9%, SrO: 3 to 12.5%, BaO: 0 to 2%, SnO: 0 to 1%, MgO + CaO + SrO + BaO: 9 to 18%, The total content is 0.1% or less.
- Soda lime glass is, for example, expressed in terms of mass% based on oxide, SiO 2 : 65 to 75%, Al 2 O 3 : 0 to 3%, CaO: 5 to 15%, MgO: 0 to 15%, Na 2 O: 10 to 20%, K 2 O: 0 to 3%, Li 2 O: 0 to 5%, Fe 2 O 3 : 0 to 3%, TiO 2 : 0 to 5%, CeO 2 : 0 to 3% BaO: 0 to 5%, SrO: 0 to 5%, B 2 O 3 : 0 to 5%, ZnO: 0 to 5%, ZrO 2 : 0 to 5%, SnO 2 : 0 to 3%, SO 3 : Contains 0 to 0.5%.
- FIG. 1 and 2 are explanatory diagrams of a glass plate manufacturing apparatus according to an embodiment of the present invention.
- FIG. 1 is a plan sectional view of the bus
- FIG. 2 is a side sectional view of the bus.
- the molten glass 30 is cooled while flowing on the molten tin 20 in the bath 10 and formed into a strip shape.
- the upper space in the bath 10 is filled with a reducing atmosphere 40 containing hydrogen gas.
- the upper space in the bus 10 is maintained at a positive pressure higher than the atmospheric pressure.
- the bus 10 is provided with a spout trip 50, a heater 60, an air supply path 70, an exhaust path 80, and the like.
- the spout trip 50 is a supply path for supplying the molten glass 30 into the bath 10, and is installed at the entrance 12 of the bus 10.
- the spout trip 50 is connected to a melting furnace for producing the molten glass 30.
- the heater 60 heats the inside of the bus 10, and is suspended from the ceiling of the bus 10, for example, as shown in FIG.
- a plurality of heaters 60 are provided at intervals in the flow direction (X direction) and the width direction (Y direction) of the molten glass 30 and are arranged in a matrix.
- the X direction and the Y direction are horizontal directions orthogonal to each other.
- the output of the heater 60 is controlled so that the temperature of the molten glass 30 decreases as it goes from the inlet 12 to the outlet 14 of the bus 10.
- the output of the heater 60 is controlled so that the thickness of the molten glass 30 is uniform in the width direction (Y direction).
- the air supply path 70 is a passage for supplying reducing gas into the bus 10 and is installed on the ceiling of the bus 10 as shown in FIG.
- a plurality of air supply paths 70 are provided at intervals in a predetermined direction (X direction).
- the reducing gas may be a mixed gas of hydrogen gas and nitrogen gas.
- the proportion of hydrogen gas in the reducing gas is, for example, 0.1 to 15% by volume.
- the exhaust path 80 is a passage for exhausting the reducing atmosphere 40, and is installed on the side wall of the bus 10 as shown in FIG.
- a plurality of exhaust passages 80 are provided at intervals in a predetermined direction (X direction).
- a plate glass obtained by forming the molten glass 30 into a strip shape is pulled up from the molten tin 20 near the outlet 14 of the bath 10. Thereafter, the plate-like glass becomes a product glass plate through a slow cooling step, a cutting step, and the like.
- the reducing atmosphere 40 in the bus 10 contains components volatilized from the molten tin 20 and the molten glass 30 in addition to the reducing gas supplied from the air supply passage 70.
- components including simple substances and compounds
- components having a low vapor pressure are inherently difficult to volatilize and are not a problem.
- the component with high vapor pressure is discharged out of the bath 10 as gas, there is usually no problem.
- a component having a low vapor pressure has a higher vapor pressure and can be volatilized if it becomes a specific compound (for example, a halide), but once volatilized, it is immediately reduced by hydrogen gas in the reducing atmosphere 40, As a result, it may return to the original low vapor pressure component in the atmosphere. Then, since a component having a low vapor pressure is unlikely to exist as a gas, it becomes an agglomerate in the reducing atmosphere 40 and falls on the molten glass 30, which may be a defect.
- the element having a low vapor pressure as a simple substance and easily becoming a halide include Group 11 elements such as Au, Cu, and Ag.
- the Group 11 element has the same valence electron structure as the alkali metal element, and easily becomes a monovalent ion and easily becomes a halide. Therefore, as a halide, the group 11 element is changed from the molten tin 20 or the molten glass 30 to the reducing atmosphere 40. Easy to strip. Further, when Au, Cu, and Ag become monovalent ions, they easily diffuse in the molten tin 20 and the molten glass 30 and easily move to the interface with the reducing atmosphere 40, so that they easily volatilize in the reducing atmosphere 40. . When the gold halide, copper halide, and silver halide in the reducing atmosphere 40 are reduced by hydrogen gas, Au, Cu, and Ag with low original vapor pressure are generated. Since Au, Cu, and Ag hardly exist as a gas as a simple substance, they become aggregates in the reducing atmosphere 40.
- the aggregate includes at least one element of Au, Cu, and Ag, and may further include an element other than Au, Cu, and Ag.
- the molten glass 30 immediately before being supplied into the bath 10 has a total content of impurities Au, Cu, and Ag (hereinafter collectively referred to as “Au etc.”) of 0.5 mass ppm. It is as follows. When the total content of Au or the like is 0.5 mass ppm or less, there are few components in the molten glass 30 that volatilize from the molten glass 30 to the reducing atmosphere 40 and become aggregates. Therefore, the aggregate is difficult to grow in the reducing atmosphere 40 and the aggregate is difficult to fall on the upper surface of the molten glass 30. Therefore, the quality of the top surface of the glass plate is improved. A more preferable range is 0.3 mass ppm or less, and a still more preferable range is 0.1 mass ppm or less.
- the total content of Au and the like in the molten glass 30 immediately before being supplied into the bath 10 is slightly smaller than the total content of Au and the like in the glass raw material charged into the melting furnace. This is because Au and the like gradually evaporate from the glass to the outside in the melting step.
- the total content of Au and the like in the glass raw material is 1.0 mass so that the total content of Au and the like in the molten glass 30 immediately before being supplied into the bath 10 is 0.5 mass ppm or less. It is preferably at most ppm. A more preferable range is 0.5 mass ppm or less, and a further preferable range is 0.3 mass ppm or less.
- the molten glass 30 immediately before being supplied into the bath 10 has a total content of impurities F, Cl, Br, and I (hereinafter collectively referred to as “F etc.”) of 200 mass. ppm or less.
- F or the like as a simple substance has a boiling point lower than the glass forming temperature, and promotes volatilization of Au or the like.
- the total content of F and the like in the molten glass 30 immediately before being supplied into the bath 10 is slightly smaller than the total content of F and the like in the glass raw material charged into the melting furnace. This is because F and the like gradually evaporate from the glass to the outside in the melting step.
- the total content of F and the like in the glass raw material is 500 mass ppm or less so that the total content of F and the like in the molten glass 30 immediately before being supplied into the bath 10 is 200 mass ppm or less. It is preferable. A more preferable range is 300 mass ppm or less, and a further preferable range is 200 mass ppm or less.
- the molten tin 20 in the bus 10 has a total content of impurities such as Au of 10 mass ppm or less and a total content of F or the like of 100 mass ppm or less in order to improve the quality of the top surface. It may be.
- tin is used as a raw material of the molten tin 20 in the bath 10.
- the glass plate has a total content of Au and the like of 0.5 mass ppm or less.
- Au or the like is volatilized from the glass to the outside in the molding step and the slow cooling step, but the volatilization amount is small compared to the total amount.
- the glass composition of a glass plate and the glass composition of the molten glass 30 in a formation process are substantially the same.
- the total content of Au and the like in the glass plate is 0.5 mass ppm or less
- the total content of Au and the like in the molten glass 30 in the molding process is small, and the molten glass 30 has the There are few components which volatilize in the reducing atmosphere 40 and become the core of the aggregate. Therefore, the aggregate is difficult to grow and the aggregate is difficult to fall on the upper surface of the molten glass 30. Therefore, the quality of the top surface of the glass plate is improved.
- the glass plate has a total content of F or the like of 200 mass ppm or less. F and the like are volatilized from the glass to the outside in the molding step and the slow cooling step, but the volatilization amount is slight compared to the total amount.
- the glass composition of a glass plate and the glass composition of the molten glass 30 in a formation process are substantially the same.
- the content of F or the like in the glass plate is 200 mass ppm or less
- the content of F or the like in the molten glass 30 in the molding process is small, and Au or the like in the molten glass 30 is difficult to volatilize in the reducing atmosphere 40. In the reducing atmosphere 40, the aggregates are difficult to grow and the aggregates are difficult to fall. Therefore, the quality of the top surface of the glass plate is improved.
- the molten glass 30 of the above embodiment has a total content of (1) Au or the like of 0.5 mass ppm or less and (2) a total content of F or the like immediately before being supplied into the bath 10. However, it may satisfy only (1) or (2). This is because the deposit on the top surface occurs when there are too many impurities such as Au and impurities such as F. The same applies to the impurities of the molten tin 20 in the bath 10.
- the glass plate of the above embodiment has (1) the total content of Au and the like is 0.5 mass ppm or less, and (2) the total content of F and the like is 200 mass ppm or less. Only 1) or (2) may be satisfied.
- Example 1 a glass plate made of alkali-free glass was produced by the method shown in FIGS. Tin was used as a raw material for molten tin in the bath.
- the alkali-free glass is expressed in terms of mass% based on oxide, SiO 2 : 59.5%, Al 2 O 3 : 17%, B 2 O 3 : 8%, MgO: 3.3%, CaO: 4%, SrO: 7.6%, BaO: 0.1%, ZrO 2 : 0.1%, MgO + CaO + SrO + BaO: 15%, the balance being inevitable impurities, the total content of alkali metal oxides The amount was 0.1% or less.
- the content (mass%) of each element (including Au, F, etc.) contained in the glass raw material, the molten glass immediately before being supplied into the bath, and the glass plate was measured by wet analysis.
- analysis was performed by dissolving a sample such as a glass raw material in an acid.
- the molten glass sample immediately before being supplied into the bath was prepared by pumping the molten glass near the entrance of the bath with a sufficiently cooled iron handle and then rapidly cooling it.
- the average density (pieces / m 2 ) of deposits on the top surface of the glass plate was measured by visually observing 40 glass plates having a top surface of 1.0 m ⁇ 1.0 m.
- Table 1 shows the measurement results of the total content of Au and the like, the total content of F and the like, and the average density of the deposits.
- Example 2 to 6 glass plates were produced in the same manner as in Example 1 except that equimolar amounts of trace amounts of CuO and Ag 2 S were added to the glass raw material.
- Examples 1 to 4 are examples, and examples 5 to 6 are comparative examples.
- Example 7 the glass plate which consists of an alkali free glass was manufactured like Example 1 except having changed the glass raw material.
- the alkali-free glass is expressed in terms of mass% based on oxide, SiO 2 : 59.5%, Al 2 O 3 : 17%, B 2 O 3 : 8%, MgO: 3.3%, CaO: 4%, SrO: 7.6%, BaO: 0.1%, ZrO 2 : 0.1%, MgO + CaO + SrO + BaO: 15%, the balance being inevitable impurities, the total content of alkali metal oxides The amount was 0.1% or less.
- Example 8 to 12 glass plates were produced in the same manner as in Example 7, except that a trace amount of CaF 2 was added to the glass raw material.
- Examples 7 to 10 are examples, and examples 11 to 12 are comparative examples.
- the total content of Au and the like is 0.5 mass ppm or less, and the total content of F and the like is 200. It can be seen that if the mass is less than or equal to ppm, the defects of the deposits are sufficiently reduced.
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Abstract
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201380038234.9A CN104487390B (zh) | 2012-07-17 | 2013-07-09 | 玻璃板的制造方法以及玻璃板 |
KR1020157001174A KR102080003B1 (ko) | 2012-07-17 | 2013-07-09 | 유리판의 제조 방법 및 유리판 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2012159048A JP2015171957A (ja) | 2012-07-17 | 2012-07-17 | ガラス板の製造方法、及びガラス板 |
JP2012-159048 | 2012-07-17 |
Publications (1)
Publication Number | Publication Date |
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WO2014013913A1 true WO2014013913A1 (fr) | 2014-01-23 |
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ID=49948743
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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PCT/JP2013/068777 WO2014013913A1 (fr) | 2012-07-17 | 2013-07-09 | Procédé de fabrication de plaque de verre et plaque de verre |
Country Status (4)
Country | Link |
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JP (1) | JP2015171957A (fr) |
KR (1) | KR102080003B1 (fr) |
TW (1) | TW201410622A (fr) |
WO (1) | WO2014013913A1 (fr) |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2006106195A (ja) * | 2004-10-01 | 2006-04-20 | Nippon Electric Glass Co Ltd | ディスプレイ基板 |
JP2007099576A (ja) * | 2005-10-06 | 2007-04-19 | Nippon Sheet Glass Co Ltd | フロートガラス製造方法及びフロートガラス製造装置 |
WO2009054411A1 (fr) * | 2007-10-25 | 2009-04-30 | Asahi Glass Co., Ltd. | Procédé de fabrication du verre à vitre |
JP2011157249A (ja) * | 2010-02-03 | 2011-08-18 | Asahi Glass Co Ltd | 溶融ガラス調量用ツィールおよび溶融ガラスの供給方法。 |
JP2011201711A (ja) * | 2010-03-24 | 2011-10-13 | Hoya Corp | ディスプレイ用カバーガラスおよびディスプレイ |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2003048054A1 (fr) * | 2001-11-30 | 2003-06-12 | Corning Incorporated | Procede et appareil d'homogeneisation de verre liquide par agitation |
EP1705160A4 (fr) * | 2003-12-26 | 2009-05-06 | Asahi Glass Co Ltd | Verre ne comprenant pas d'alcali, procede de production associe et panneau d'affichage a cristaux liquides |
DE102009000348B4 (de) | 2008-08-28 | 2011-09-01 | Schott Ag | Verfahren zur Herstellung von Flachglas |
-
2012
- 2012-07-17 JP JP2012159048A patent/JP2015171957A/ja active Pending
-
2013
- 2013-07-09 KR KR1020157001174A patent/KR102080003B1/ko active IP Right Grant
- 2013-07-09 WO PCT/JP2013/068777 patent/WO2014013913A1/fr active Application Filing
- 2013-07-17 TW TW102125633A patent/TW201410622A/zh unknown
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2006106195A (ja) * | 2004-10-01 | 2006-04-20 | Nippon Electric Glass Co Ltd | ディスプレイ基板 |
JP2007099576A (ja) * | 2005-10-06 | 2007-04-19 | Nippon Sheet Glass Co Ltd | フロートガラス製造方法及びフロートガラス製造装置 |
WO2009054411A1 (fr) * | 2007-10-25 | 2009-04-30 | Asahi Glass Co., Ltd. | Procédé de fabrication du verre à vitre |
JP2011157249A (ja) * | 2010-02-03 | 2011-08-18 | Asahi Glass Co Ltd | 溶融ガラス調量用ツィールおよび溶融ガラスの供給方法。 |
JP2011201711A (ja) * | 2010-03-24 | 2011-10-13 | Hoya Corp | ディスプレイ用カバーガラスおよびディスプレイ |
Also Published As
Publication number | Publication date |
---|---|
KR102080003B1 (ko) | 2020-02-24 |
JP2015171957A (ja) | 2015-10-01 |
TW201410622A (zh) | 2014-03-16 |
CN104487390A (zh) | 2015-04-01 |
KR20150036095A (ko) | 2015-04-07 |
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