WO2013145922A1 - Procédé de fabrication d'une plaque de verre - Google Patents

Procédé de fabrication d'une plaque de verre Download PDF

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Publication number
WO2013145922A1
WO2013145922A1 PCT/JP2013/053756 JP2013053756W WO2013145922A1 WO 2013145922 A1 WO2013145922 A1 WO 2013145922A1 JP 2013053756 W JP2013053756 W JP 2013053756W WO 2013145922 A1 WO2013145922 A1 WO 2013145922A1
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WIPO (PCT)
Prior art keywords
glass
molten
brick
oxide
glass plate
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PCT/JP2013/053756
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English (en)
Japanese (ja)
Inventor
丈宜 三浦
史朗 谷井
泰夫 林
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旭硝子株式会社
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Priority to CN201380000355.4A priority Critical patent/CN103492329B/zh
Priority to KR1020137012611A priority patent/KR101384375B1/ko
Publication of WO2013145922A1 publication Critical patent/WO2013145922A1/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
    • C03B18/16—Construction of the float tank; Use of material for the float tank; Coating or protection of the tank wall
    • 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
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/10—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminium oxide
    • C04B35/101—Refractories from grain sized mixtures
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/10—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminium oxide
    • C04B35/101—Refractories from grain sized mixtures
    • C04B35/106—Refractories from grain sized mixtures containing zirconium oxide or zircon (ZrSiO4)
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3201—Alkali metal oxides or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3206—Magnesium oxides or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3208—Calcium oxide or oxide-forming salts thereof, e.g. lime
    • 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 glass plate.
  • the float method is widely used as a glass plate forming method.
  • molten glass continuously supplied onto molten tin in a bathtub is caused to flow on molten tin to be formed into a strip shape (for example, see Patent Document 1).
  • the atmosphere on the molten tin is a reducing atmosphere containing hydrogen gas in order to prevent oxidation of the molten tin.
  • the bathtub is composed of, for example, a box-shaped metal case opened upward, and a bottom brick and a side brick installed in the metal case.
  • alumina (Al 2 O 3 ) -silica (SiO 2 ) brick is generally used as the bottom brick and the side brick.
  • the molten tin in the bathtub is heated from above, the temperature becomes lower as it goes downward. Therefore, gas components (for example, oxygen, hydrogen, water, etc.) dissolved in the molten tin are supersaturated on the upper surface of the relatively low temperature bottom brick to form bubbles. Moreover, the gas which permeate
  • gas components for example, oxygen, hydrogen, water, etc.
  • the yield of glass plates was low because the locations where FOBBs occurred were dispersed.
  • the present inventors have found that the glass of the glass plate is conspicuous in the case of alkali-free glass having a high molding temperature as compared with general soda lime glass.
  • This invention was made in view of the said subject, Comprising: It aims at provision of the manufacturing method of the glass plate of an alkali free glass with a favorable yield.
  • a method for producing a glass plate includes: In the method for producing a glass plate, the method includes a step of forming molten glass that is continuously supplied onto molten tin in a bath and flowing on the molten tin.
  • the glass of the glass plate is alkali-free glass, and the temperature of the molten glass at which the viscosity of the molten glass is 10 4 dPa ⁇ s is 1200 ° C.
  • Each bottom brick of the bathtub has a total content of low melting point elements of 20% by mass or less in terms of oxide,
  • the low melting point element is an element having a lower eutectic point in the binary system of the oxide of the low melting point element and tin oxide (SnO) than the maximum temperature of the upper surface of the corresponding bottom brick.
  • FIG. 3 is a SEM photograph of a cut surface of a crucible according to Comparative Example 1. It is the SEM photograph which expanded a part of FIG. It is the map of Sn element which carried out the element analysis of the same area
  • the glass plate manufacturing method according to the present embodiment includes, for example, a melting step, a forming step, a slow cooling step, and a cutting step.
  • 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 bathtub, and the molten glass is flowed on the molten tin to be molded to obtain a plate-like glass (so-called glass ribbon).
  • the plate glass is cooled while flowing in a predetermined direction, and pulled up from the molten tin.
  • the glass sheet obtained in the molding 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 in the slow cooling furnace.
  • 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 glass of the glass plate is an alkali-free glass that does not substantially contain an alkali metal oxide (Na 2 O, K 2 O, Li 2 O, etc.).
  • the alkali-free glass may have a total content of alkali metal oxides of 0.1% by mass or less, and is used, for example, as a substrate for a liquid crystal display.
  • the alkali-free glass is, for example, SiO 2 : 50% to 73% (preferably 50 to 66%), Al 2 O 3 : 10.5% to 24%, B 2 O 3 in terms of mass% based on oxide. : 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% MgO + CaO + SrO + BaO: 8% to 29.5% (preferably 9% to 29.5%).
  • SiO 2 58% to 66%
  • Al 2 O 3 15% to 22%, expressed by mass% based on oxide.
  • B 2 O 3 5% ⁇ 12%
  • CaO 0% ⁇ 9%
  • SrO 3% ⁇ 12.5%
  • BaO 0% ⁇ containing 2%
  • MgO + CaO + SrO + BaO 9% to 18%.
  • the alkali-free glass is preferably expressed in terms of mass% based on oxide, SiO 2 : 54% to 73%, Al 2 O 3 : 10.5% to 22.5%, B 2 O 3 : 0% to 5.5%, MgO: 0% to 8%, CaO: 0% to 9%, SrO: 0% to 16%, BaO: 0% to 2.5%, MgO + CaO + SrO + BaO: 8 % To 26%.
  • the temperature of the molten glass at which the viscosity of the molten glass is 10 4 dPa ⁇ s (poise) is 1200 ° C. or higher.
  • the place where the viscosity of the molten glass is about 10 4 dPa ⁇ s is usually set near the inlet 12 of the float bath 10 (see FIG. 1) used in the molding process.
  • the molten glass supplied onto the molten tin M at the inlet 12 of the float bath 10 is molded while flowing in a predetermined direction.
  • FIG. 1 is an explanatory diagram of a float bath used in a glass plate forming process according to an embodiment of the present invention.
  • Float bath 10 (hereinafter simply referred to as “bath 10”) is formed by causing molten glass G continuously supplied onto molten tin M in bathtub 22 to flow on molten tin M.
  • the molten glass G is supplied onto the molten tin M near the inlet 12 of the bath 10, cooled while flowing in a predetermined direction, and pulled up from the molten tin M near the outlet 14 of the bath 10.
  • the bath 10 includes a bathtub 22 that accommodates molten tin M, a side wall 24 that is installed along the outer peripheral upper edge of the bathtub 22, a ceiling 26 that is connected to the side wall 24 and covers the top of the bathtub 22.
  • the ceiling 26 is provided with a gas supply path 30 for supplying a reducing gas to a space 28 formed between the bathtub 22 and the ceiling 26.
  • a heater 32 as a heating source is inserted into the gas supply path 30.
  • the gas supply path 30 supplies a reducing gas to the space 28 in the bus 10 in order to prevent the molten tin M from being oxidized.
  • the reducing gas contains, for example, 1 to 15% by volume of hydrogen gas and 85 to 99% by volume of nitrogen gas.
  • the space 28 in the bus 10 is set to a pressure higher than the atmospheric pressure in order to prevent air from being mixed in through a gap between bricks constituting the side wall 24.
  • a plurality of heaters 32 are provided, for example, at intervals in the flow direction (X direction) and the width direction (Y direction) of the molten glass G.
  • the output of the heater 32 is controlled so that the temperature of the molten glass G decreases as it goes from the inlet 12 to the outlet 14 of the bus 10.
  • the output of the heater 32 is controlled so that the thickness of the molten glass G is uniform in the width direction (Y direction).
  • the bathtub 22 includes a box-shaped metal case 34 opened upward, and a bottom brick 36 and a side brick 38 installed in the metal case 34.
  • the metal case 34 prevents air from entering the bathtub 22 from the side or from below.
  • the plurality of bottom bricks 36 are two-dimensionally arranged at a slight interval so as not to contact each other due to thermal expansion.
  • the plurality of bottom bricks 36 are surrounded by a plurality of side bricks 38 arranged in a ring shape.
  • the molten tin M in the bathtub 22 is heated from above by the heater 32, the temperature becomes lower as it goes downward. Therefore, gas components (for example, oxygen, hydrogen, water, etc.) dissolved in the molten tin M are supersaturated on the upper surface 36a of the relatively low temperature bottom brick 36 to form bubbles B. Further, gas (for example, hydrogen) that has permeated through the bottom brick 36 forms bubbles B on the upper surface 36 a of the bottom brick 36.
  • gas components for example, oxygen, hydrogen, water, etc.
  • the inventors of the present invention focused on the fact that the number of bubbles B decreases as the size of each bubble B increases, when the total mass of bubbles B generated per unit time is the same. In order for the bubbles B to grow greatly on the bottom brick 36, it is important to reduce the wettability of the molten tin M with respect to the bottom brick 36.
  • FIG. 2 is a diagram showing the relationship between the wettability of molten tin with respect to the bottom brick and the shape of the bubbles formed on the bottom brick according to an embodiment of the present invention.
  • FIG. 3 is a diagram showing the relationship between the wettability of molten tin with respect to a conventional bottom brick and the shape of bubbles formed on the bottom brick.
  • the wettability of molten tin with respect to the bottom brick of the present embodiment of FIG. 2 is lower than the wettability of molten tin with respect to the conventional bottom brick of FIG.
  • Low wettability means that molten tin is difficult to wet with respect to the bottom brick
  • high wettability means that molten tin is easily wetted with respect to the bottom brick.
  • the wettability of the molten metal to the oxide is low, the wettability of the molten tin M to the bottom brick 6 is low at the start of production of the glass plate.
  • tin oxide slightly contained as an impurity in the molten tin M reacts with the bottom brick 6, and a reaction layer (modified layer) is formed on the surface of the bottom brick 6. Will be higher.
  • each bottom brick 36 is a brick whose total content of low melting point elements is 20% by mass or less in terms of oxide.
  • the “low melting point element” is an element whose eutectic point in the binary system of the low melting point element oxide and tin oxide (SnO) is lower than the maximum temperature of the upper surface 36a of the corresponding bottom brick 36. is there. When the temperature becomes higher than the eutectic point, a liquid phase is formed, and the reaction between the oxide of the low melting point element and tin oxide proceeds rapidly.
  • Tin oxide is contained in the molten tin M in a small amount as an impurity, and the tin oxide in the molten tin M selectively reacts with the portion of the bottom brick 36 where the concentration of the low melting point element is high.
  • the tin oxide contained in the molten tin M is air that has entered the bus 10 when the side wall 24 is opened to the atmosphere for production reasons, or air that has entered the bus 10 from the gaps between the bricks constituting the side wall 24. It is formed by exposing molten tin M.
  • “the total content of low melting point elements” is the content of one low melting point element when the number of low melting point elements is one, and when there are a plurality of low melting point elements, The total content of elements.
  • the kind of the low melting point element may be different for each bottom brick 36.
  • the low melting point element may not be present in the bottom brick 36.
  • low melting point element examples include silicon (Si).
  • the eutectic point of silicon oxide (SiO 2 ) and tin oxide is about 850 ° C., which is lower than the maximum temperature of the upper surface 36 a of most bottom bricks 36.
  • the total content of the low melting point elements is 20% by mass or less (preferably 15% by mass or less, more preferably 10% by mass or less) in terms of oxide.
  • the brick 36 and the molten tin M hardly react. If the total content of the low melting point elements is 20% by mass or less in terms of oxide, most of the low melting point elements constitute oxides with other elements in the bottom brick 36, and the melting point of the oxides. This is because the temperature is higher than the maximum temperature of the upper surface 36 a of the bottom brick 36. Since each bottom brick 36 and molten tin M hardly react, the wettability of molten tin M with respect to each bottom brick 36 is low even when time elapses from the start of glass plate production.
  • the total content of low melting point elements in each bottom brick 36 is 20% by mass or less in terms of oxides, but the total content of low melting point elements in all bottom bricks 36 is in terms of oxides. It may not be 20 mass% or less.
  • the maximum temperature of the upper surface of the bottom brick is equal to or lower than the temperature of the molten glass G at which the viscosity of the molten glass G is 10 4 dPa ⁇ s, and the eutectic point in the binary system of the low melting point element oxide and tin oxide
  • the total content of the low melting point elements may be 20% by mass or less in terms of oxide, and may exceed 0% by mass, at least one bottom brick having a temperature exceeding.
  • the size of each bubble B increases, if the total mass of bubbles B generated per unit time is the same, the number of bubbles B generated per unit time decreases.
  • the number of FOBBs formed on the bottom surface of the glass plate is reduced, and the yield of FOBB is increased.
  • the alkali-free glass has a higher molding temperature of the molten glass G and a higher temperature of the upper surface 36a of the bottom brick 36 than a general soda lime glass. Therefore, when the chemical composition of the bottom brick 36 is the same, the reaction between the bottom brick 36 and the molten tin M is likely to proceed.
  • alkali-free glass does not substantially contain alkali metal elements (for example, Na, K), so that the bottom brick 36 is hardly converted to nepheline ((Na, K) AlSiO 4 ).
  • alkali metal elements for example, Na, K
  • nepheline (Na, K) AlSiO 4
  • Nephelinization forms a dense glass layer on the bottom brick 36 and suppresses gas permeation from the inside of the bottom brick 36 to the upper surface 36a.
  • nephelinization hardly occurs, so that the total mass of bubbles B generated per unit time increases.
  • the bottom bricks 36 and the molten tin M hardly react with each other, so that the alteration of the upper surface 36a of the bottom brick 36 is suppressed, and the detachment of the altered particles is suppressed. Since the desorbed particles float up to the interface between the molten tin M and the molten glass G and become a defect of the molten glass G, the quality of the glass plate can be improved by suppressing the desorption of the particles.
  • a viscous fired brick such as alumina (Al 2 O 3 ) -calcia (CaO) brick or alumina (Al 2 O 3 ) -zirconia (ZrO 2 ) brick is used.
  • SiO 2 or the like is used as a sintering aid, and there is a portion having a high SiO 2 concentration.
  • the alumina-calcia brick contains, for example, Al 2 O 3 : 40% to 85%, CaO: 10% to 40%, and SiO 2 : 0.5% to 20% in terms of mass% based on oxide.
  • the SiO 2 content is preferably 15% by mass or less, more preferably 10% by mass or less, further preferably 7% by mass or less, particularly preferably 3% by mass or less, and even more preferably 1% by mass or less.
  • Alumina-zirconia bricks contain, for example, Al 2 O 3 : 40% to 55%, ZrO 2 : 30% to 45%, SiO 2 : 0.5% to 20% in terms of mass% based on oxide. .
  • the SiO 2 content is preferably 15% by mass or less, more preferably 10% by mass or less, further preferably 7% by mass or less, particularly preferably 3% by mass or less, and even more preferably 1% by mass or less.
  • the side brick 38 may have a total content of low melting point elements of 20% by mass or less in terms of oxide, or may exceed 20% by mass, as with the bottom brick 36. Since the molten glass G is inside the side brick 38 at the time of molding, the bubbles formed on the inner wall surface of the side brick 38 do not cause FOBB.
  • the glass plate of the said embodiment is used as a board
  • a use may be various.
  • the glass plate may be used as a substrate for an organic EL display or a cover glass for a touch panel.
  • Example 1 First, a brick is processed to prepare a crucible, and metal tin is put into the prepared crucible, installed in an electric furnace, the atmosphere in the electric furnace is replaced, and then the metal tin is melted at 1000 ° C. for 60 minutes. The reactivity between molten tin and crucible was investigated.
  • brick A which is an alumina (Al 2 O 3 ) -calcia (CaO) brick
  • Brick A is expressed in terms of mass% on an oxide basis, SiO 2 : 5.7%, Al 2 O 3 : 66.0%, CaO: 26.0%, MgO: 1.5%, Na 2 O: 0. .3%, Fe 2 O 3 : 0.1%, and other components are each less than 0.1%.
  • the chemical composition of the brick A was measured with a fluorescent X-ray analyzer (manufactured by Rigaku Denki Kogyo Co., Ltd., ZSX100e).
  • the crucible was processed into a bottomed cylindrical shape (inner diameter 6 mm, inner dimension height 6 mm, bottom wall thickness 3 mm, side wall thickness 2 mm).
  • Metal tin with a purity of 99.95% by mass (manufactured by Kanto Chemical Co., Ltd., special grade) was used. Metal tin was weighed so that the thickness of molten tin was 5 mm and placed in a crucible.
  • the atmosphere in the electric furnace was replaced by evacuating the electric furnace to 1 kPa with a vacuum pump and then supplying gas into the electric furnace through a gas supply pipe.
  • gas nitrogen gas with an oxygen concentration of 1000 ppm by volume was used. Nitrogen gas was used because nitrogen gas has low reactivity with oxygen gas and does not affect the oxygen concentration.
  • the reactivity between the molten tin and the crucible was examined by solidifying the crucible cooled to room temperature with a resin and then cutting it, and observing the cut surface with an SEM (Scanning Electron Microscope, manufactured by Keyence Corporation, VE-9800).
  • FIG. 4 shows an SEM photograph of the cut surface of the crucible according to Example 1. As apparent from FIG. 4, no reaction layer with molten tin 44 was observed on the inner bottom surface of the crucible 41. Further, a gap 45 is partially formed between the crucible 41 and the molten tin 44, and it can be seen that the wettability of the molten tin 44 with respect to the crucible 41 is low.
  • FIG. 5 shows a test for examining the number of defects formed in the glass for evaluation in Example 1.
  • a crucible 51 in which brick A was processed was prepared, metal tin was put into the prepared crucible 51, and an evaluation glass 53 was placed on a carbon jig 52.
  • the crucible 51 is installed in the electric furnace of the glove box, the atmosphere in the electric furnace is replaced, the temperature in the electric furnace is increased, and the evaluation glass 53 is thermally deformed by its own weight to be formed on the molten tin 54. I put it.
  • the temperature in the electric furnace at 1100 ° C.
  • the temperature in the electric furnace was lowered to 800 ° C., and the solidified evaluation glass 53 was manually pulled up from the molten tin 54. Subsequently, the glass for evaluation 53 was gradually cooled in an electric furnace, and the number of FOBBs formed in the portion of the glass for evaluation 53 in contact with the molten tin 54 was examined.
  • the crucible 51 was processed into a bottomed cylindrical shape (inner diameter 60 mm, inner dimension height 40 mm, bottom wall thickness 10 mm, side wall thickness 10 mm).
  • Metal tin with a purity of 99.95% by mass (manufactured by Kanto Chemical Co., Ltd., special grade) was used. Metal tin was weighed so that the thickness of molten tin was 20 mm and placed in a crucible.
  • the alkali free glass plate (length 40mm, width 40mm, thickness 0.7mm) was prepared.
  • This non-alkali glass plate is expressed in terms of mass% based on oxide, SiO 2 : 60.0%, Al 2 O 3 : 17.0%, B 2 O 3 : 8.0%, MgO: 3.0% CaO: 4.5% and SrO: 7.5%.
  • the chemical composition of the glass plate was measured with a fluorescent X-ray analyzer (manufactured by Rigaku Denki Kogyo Co., Ltd., ZSX100e).
  • the atmosphere in the electric furnace was replaced by evacuating the electric furnace to 1 kPa with a vacuum pump and then supplying gas into the electric furnace through a gas supply pipe.
  • gas nitrogen gas having a hydrogen concentration of 10% by volume was used.
  • the number of defects (FOBB) formed in the glass for evaluation 53 was measured by cooling the glass for evaluation 53 to room temperature, and then observing the portion (5 mm ⁇ 5 mm) in contact with the molten tin 54 of the glass for evaluation 53 with an optical microscope. I investigated. The number of large defects (diameter over 300 ⁇ m) was 0, and the number of small defects (diameter 10 to 300 ⁇ m) was 2. The total number of small defects and large defects was 10% or less as compared with the case of Comparative Example 1 described later.
  • the reason for the small number of defects is that the brick A, which is the material of the crucible 51, has a low content of Si, which is a low melting point element. Since the Si content is small, the crucible 41 and the molten tin 44 hardly react as shown in FIG. 4, and the wettability of the molten tin 44 with respect to the crucible 41 is low. Since the wettability is low, as shown in FIG. 3, the bubbles formed on the inner bottom surface of the crucible do not easily float and grow large while retaining the bubbles, and as a result, the number of small defects is small.
  • Example 2 In Example 2, brick B, which is an alumina (Al 2 O 3 ) -calcia (CaO) brick, was prepared, and the number of defects formed in the evaluation glass was examined in the same manner as in Example 1. Brick B is expressed in terms of mass% based on oxide, SiO 2 : 5.8%, Al 2 O 3 : 82.4%, CaO: 10.2%, MgO: 1.2%, Na 2 O: 0 0.2%, Fe 2 O 3 : 0.2%, and other components are each less than 0.1%.
  • Brick B is expressed in terms of mass% based on oxide, SiO 2 : 5.8%, Al 2 O 3 : 82.4%, CaO: 10.2%, MgO: 1.2%, Na 2 O: 0 0.2%, Fe 2 O 3 : 0.2%, and other components are each less than 0.1%.
  • the number of large defects is 0, and the number of small defects (diameter 10 to 300 ⁇ m) is 10 or less.
  • Example 3 In Example 3, the number of defects formed in the glass for evaluation was examined in the same manner as in Example 1 except that brick C, which is an alumina (Al 2 O 3 ) -zirconia (ZrO 2 ) -based brick, was prepared. It was. Brick C contains SiO 2 : 13.5%, ZrO 2 : 33.0%, Al 2 O 3 : 52.0%, Na 2 O: 1.3% in terms of mass% based on oxide. The other components are each less than 0.1%.
  • brick C which is an alumina (Al 2 O 3 ) -zirconia (ZrO 2 ) -based brick, was prepared. It was. Brick C contains SiO 2 : 13.5%, ZrO 2 : 33.0%, Al 2 O 3 : 52.0%, Na 2 O: 1.3% in terms of mass% based on oxide. The other components are each less than 0.1%.
  • the number of large defects is 0, and the number of small defects (diameter 10 to 300 ⁇ m) is 15.
  • Comparative Example 1 In Comparative Example 1, the reactivity between brick and molten tin was examined in the same manner as in Example 1 except that brick D, which is an alumina (Al 2 O 3 ) -silica (SiO 2 ) brick, was prepared.
  • Brick D is expressed in terms of mass% based on oxide, SiO 2 : 58.0%, Al 2 O 3 : 37.0%, CaO: 0.4%, MgO: 0.1%, P 2 O 5 : Contains 0.4%, Na 2 O: 0.1%, K 2 O: 0.9%, Fe 2 O 3 : 1.2%, TiO 2 : 0.9%, ZrO 2 : 0.1%
  • the other components are each less than 0.1%.
  • FIG. 6 shows a SEM photograph of the cut surface of the crucible according to Comparative Example 1.
  • FIG. 7 shows an SEM photograph in which a part of FIG. 6 is enlarged.
  • a reaction layer 66 with molten tin 64 was found on the inner bottom of the crucible 61. Further, it is understood that the crucible 61 and the molten tin 64 are in close contact with each other, and the wettability of the molten tin 64 with respect to the crucible 61 is high.
  • FIG. 8 is a map of Sn element obtained by elemental analysis of the same region as the SEM photograph of FIG. 7 by EDS
  • FIG. 9 is a map of Al element obtained by elemental analysis of the same region as the SEM photograph of FIG. 7 by EDS
  • EDS Energy Dispersive X-ray Spectrometry
  • Comparative Example 1 the number of defects formed in the glass for evaluation was examined in the same manner as in Example 1 except that the brick D was used as a brick. As a result, the number of large defects (diameter exceeding 300 ⁇ m) was 0, and the number of small defects (diameter 10 to 300 ⁇ m) was 60.
  • the brick D which is a material for the crucible, has a high content of Si, which is a low melting point element. Since the Si content is large, a reaction layer 66 with molten tin 64 is formed on the crucible 61 as shown in FIGS. 6 and 7, and the wettability of the molten tin 64 with respect to the crucible 61 is high. Since the wettability is high, the bubbles formed on the inner bottom surface of the crucible float in a small state as shown in FIG. 2, and as a result, the number of small defects is large.
  • brick E which is an alumina (Al 2 O 3 ) -silica (SiO 2 ) brick, was prepared, and the number of defects formed in the evaluation glass was examined in the same manner as in Comparative Example 1.
  • Brick E is expressed in terms of mass% based on oxide, SiO 2 : 58.0%, Al 2 O 3 : 37.0%, CaO: 0.2%, MgO: 0.3%, Na 2 O: 0 0.8%, K 2 O: 0.9%, Fe 2 O 3 : 1.1%, TiO 2 : 1.6%, and other components are each less than 0.1%.
  • the number of large defects (diameter exceeding 300 ⁇ m) was 0, and the number of small defects (diameter 10 to 300 ⁇ m) was 70.
  • Reference Example 1 was the same as Comparative Example 1 except that a reducing gas composed of 10% by volume hydrogen gas and 90% by volume nitrogen gas was used as the gas supplied into the electric furnace after evacuation. The reactivity between brick D and molten tin was investigated.
  • FIG. 11 shows an SEM photograph of the cut surface of the crucible according to Reference Example 1. As is clear from FIG. 11, no reaction layer with molten tin 74 was observed in the crucible 71. Further, a gap 75 is partially formed between the crucible 71 and the molten tin 74, and it can be seen that the wettability of the molten tin 74 with respect to the crucible 71 is low.
  • Example 1 to 3 and Comparative Examples 1 and 2 are shown in Table 1.
  • Table 1 the composition of bricks is shown only for SiO 2 , Al 2 O 3 , CaO, MgO, and ZrO 2 .

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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
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  • General Chemical & Material Sciences (AREA)
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Abstract

L'invention concerne un procédé de fabrication d'une plaque de verre comprenant une étape de formation d'un courant de verre fondu (G) sur de l'étain fondu (M) et de moulage de celui-ci, le verre fondu (G) étant adressé de façon continue sur l'étain fondu (M) dans un bain (22), le verre pour la plaque de verre étant un verre exempt d'alcali et la température du verre fondu (G) à laquelle la viscosité du verre fondu (G) devient 104dPa·s étant de 1200°C ou plus. Chaque brique de fond (36) du bain (22) a une quantité totale d'un élément à faible point de fusion de 20 % en masse ou moins en termes d'oxydes. L'élément à faible point de fusion est un élément dans lequel le point eutectique dans un système binaire d'oxyde de l'élément à faible point fusion et d'oxyde d'étain (SnO) est inférieur à la température maximale d'une face supérieure (36a) de la brique de fond correspondante (36).
PCT/JP2013/053756 2012-03-27 2013-02-15 Procédé de fabrication d'une plaque de verre WO2013145922A1 (fr)

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CN105314846A (zh) * 2014-05-27 2016-02-10 旭硝子株式会社 无碱玻璃及其制造方法
US11745459B2 (en) * 2016-12-22 2023-09-05 Schott Ag Thin glass substrate, in particular a borosilicate glass thin glass substrate, method and apparatus for its production

Families Citing this family (1)

* Cited by examiner, † Cited by third party
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JP2016098160A (ja) * 2014-11-25 2016-05-30 旭硝子株式会社 フロートガラス製造装置、およびフロートガラス製造方法

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JPH072536A (ja) * 1993-02-17 1995-01-06 Didier Werke Ag スズ浴用敷きれんがとしての耐火れんが
JPH1072237A (ja) * 1996-06-03 1998-03-17 Asahi Glass Co Ltd 無アルカリガラスおよび液晶ディスプレイパネル
JP2005314186A (ja) * 2004-04-30 2005-11-10 Ohcera Co Ltd フロートバス用耐火材及びフロートバス
JP2006036625A (ja) * 2004-06-23 2006-02-09 Nippon Electric Glass Co Ltd 無アルカリガラス基板
JP2009167090A (ja) * 2007-12-19 2009-07-30 Nippon Electric Glass Co Ltd ガラス基板

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JPH07109129A (ja) * 1993-10-12 1995-04-25 Yootai:Kk フロートバス内張用耐火れんが
WO2005063642A1 (fr) * 2003-12-26 2005-07-14 Asahi Glass Company, Limited Verre ne comprenant pas d'alcali, procede de production associe et panneau d'affichage a cristaux liquides
JP5267464B2 (ja) * 2007-10-25 2013-08-21 旭硝子株式会社 無アルカリガラスの製造方法

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JPH072536A (ja) * 1993-02-17 1995-01-06 Didier Werke Ag スズ浴用敷きれんがとしての耐火れんが
JPH1072237A (ja) * 1996-06-03 1998-03-17 Asahi Glass Co Ltd 無アルカリガラスおよび液晶ディスプレイパネル
JP2005314186A (ja) * 2004-04-30 2005-11-10 Ohcera Co Ltd フロートバス用耐火材及びフロートバス
JP2006036625A (ja) * 2004-06-23 2006-02-09 Nippon Electric Glass Co Ltd 無アルカリガラス基板
JP2009167090A (ja) * 2007-12-19 2009-07-30 Nippon Electric Glass Co Ltd ガラス基板

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105314846A (zh) * 2014-05-27 2016-02-10 旭硝子株式会社 无碱玻璃及其制造方法
CN105314846B (zh) * 2014-05-27 2018-04-24 旭硝子株式会社 无碱玻璃及其制造方法
US11745459B2 (en) * 2016-12-22 2023-09-05 Schott Ag Thin glass substrate, in particular a borosilicate glass thin glass substrate, method and apparatus for its production
US11890844B2 (en) 2016-12-22 2024-02-06 Schott Ag Thin glass substrate, method and apparatus for its production
US11993062B2 (en) 2016-12-22 2024-05-28 Schott Ag Composite glass pane
US12005687B2 (en) 2016-12-22 2024-06-11 Schott Ag Thin glass substrate, method and apparatus for its production

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CN103492329B (zh) 2015-12-02
KR20130119441A (ko) 2013-10-31
CN103492329A (zh) 2014-01-01
TW201339110A (zh) 2013-10-01
KR101384375B1 (ko) 2014-04-10

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