WO2014171459A1 - Float bath roof member, float plate glass production device using same, and method for producing float plate glass - Google Patents

Float bath roof member, float plate glass production device using same, and method for producing float plate glass Download PDF

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Publication number
WO2014171459A1
WO2014171459A1 PCT/JP2014/060738 JP2014060738W WO2014171459A1 WO 2014171459 A1 WO2014171459 A1 WO 2014171459A1 JP 2014060738 W JP2014060738 W JP 2014060738W WO 2014171459 A1 WO2014171459 A1 WO 2014171459A1
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Prior art keywords
float
float bath
roof member
mass
plate glass
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PCT/JP2014/060738
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French (fr)
Japanese (ja)
Inventor
和雄 浜島
瑞樹 松岡
信之 伴
真毅 後藤
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旭硝子株式会社
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Priority to KR1020157029617A priority Critical patent/KR20160002774A/en
Priority to CN201480022193.9A priority patent/CN105339315B/en
Publication of WO2014171459A1 publication Critical patent/WO2014171459A1/en

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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
    • 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
    • C04B35/16—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 silicates other than clay
    • C04B35/18—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 silicates other than clay rich in aluminium oxide
    • C04B35/185—Mullite 3Al2O3-2SiO2
    • 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
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3232—Titanium oxides or titanates, e.g. rutile or anatase
    • 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
    • C04B2235/327—Iron group oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3272—Iron oxides or oxide forming salts thereof, e.g. hematite, magnetite
    • 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
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/54—Particle size related information
    • C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
    • C04B2235/5427—Particle size related information expressed by the size of the particles or aggregates thereof millimeter or submillimeter sized, i.e. larger than 0,1 mm
    • 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
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/54—Particle size related information
    • C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
    • C04B2235/5436—Particle size related information expressed by the size of the particles or aggregates thereof micrometer sized, i.e. from 1 to 100 micron
    • 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
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/54—Particle size related information
    • C04B2235/5463—Particle size distributions
    • 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
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/54—Particle size related information
    • C04B2235/5463—Particle size distributions
    • C04B2235/5472—Bimodal, multi-modal or multi-fraction
    • 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
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/72—Products characterised by the absence or the low content of specific components, e.g. alkali metal free alumina ceramics
    • 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
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/72—Products characterised by the absence or the low content of specific components, e.g. alkali metal free alumina ceramics
    • C04B2235/725—Metal content

Definitions

  • the present invention relates to a float bath roof member, a float plate glass manufacturing apparatus using the same, and a method for manufacturing a float plate glass.
  • a float method is known as one method for producing plate glass.
  • (1) molten glass is introduced into a bath containing molten tin called a float bath, (2) On the molten tin, the molten glass is continuously conveyed from upstream to downstream, (3) Sheet glass is manufactured by discharging from the float bath while cooling this molten glass.
  • a ceiling part called a float bath roof is installed at the top of the float bath.
  • This float bath roof is composed of refractory bricks whose lower surface (ie, the side facing the float bath) is engaged with a plurality of hangers, that is, the float bath roof has a suspended structure (Patent Documents 1 and 2). reference).
  • Refractory bricks used for float bath roofs are relatively lightweight, have heat resistance that can be used for a long time at temperatures as high as 1000 ° C, and can be a disadvantage of glass produced when used at high temperatures.
  • Alumina (Al 2 O 3 ) -silica (SiO 2 ) -based refractory bricks can be used for reasons such as a small amount, among which sillimanite-based refractory bricks can be applied to various molding methods, Can be used for any reason that can be molded into shape.
  • Creep deformation of refractory bricks progresses more as the temperature is higher, so when molding glass with higher viscosity into a plate shape, or even when glass of the same composition is molded into thin plate glass, The problem is even more pronounced when the ambient temperature in the float bath is increased when forming a thin plate glass having a thickness of preferably 0.7 mm or less, more preferably 0.5 mm or less, and even more preferably 0.3 mm or less. It is thought that it becomes. Further, since the amount of creep deformation increases with time according to the holding time in a high temperature environment, it becomes a particular problem when the float bath is used over a long period of time.
  • the present invention provides a float bath roof member in which creep deformation during use in a high temperature environment is suppressed, a float plate glass manufacturing apparatus using the same, and a float plate glass manufacturing method The purpose is to provide.
  • the present invention provides an alumina in which 90% by mass or more of the crystalline phase is a mullite phase and the total content of sodium oxide, potassium oxide, titanium oxide, and iron oxide is 2% by mass or less.
  • -It is composed of a silica-based sintered body and is composed of coarse particles having an average crystal grain size D50 of 1.0 mm or more, and fine particles having an average crystal grain size D50 of 0.1 mm or less, and the mass of the coarse grains and fine grains Float bath roof members having a ratio of 85 to 60% by mass and 15 to 40% by mass are provided.
  • the float bath roof member according to one aspect of the present invention preferably has a creep rate of 1 ⁇ 10 ⁇ 8 / sec or less in a bending creep test (1300 ° C., load 3.5 MPa) with a sample size of 25 mm ⁇ 15 mm ⁇ 100 mm. .
  • the float bath roof member according to one embodiment of the present invention preferably has a 1000 hour creep strength of 6 MPa or more in a bending creep test (1300 ° C.) with a sample size of 25 mm ⁇ 15 mm ⁇ 100 mm.
  • the coarse particles and fine particles preferably include mullite particles, and the mullite particles are preferably electrofused mullite particles.
  • the crystal phase other than the mullite phase that is, the content of corundum and cristobalite in the crystal phase is 10 with respect to the crystal phase of the alumina-silica-based sintered body. It is preferable that it is below mass%.
  • the crystal phase other than the mullite phase is preferably corundum or cristobalite, and the corundum content is preferably high in both.
  • a float sheet glass manufacturing apparatus comprising: a float bath in which molten tin is housed; and a float bath roof installed at an upper portion of the float bath.
  • the float bath roof is composed of the float bath roof member of the present invention.
  • one aspect of the present invention provides a float sheet glass manufacturing method including producing a float sheet glass using the float sheet glass manufacturing apparatus of one aspect of the present invention.
  • the float plate glass is a float glass for display, and the thickness of the float glass is 0.7 mm or less.
  • a float plate glass that is required to increase the atmospheric temperature in the float bath, such as when producing a plate glass using a highly viscous glass such as an alkali-free glass or a thin plate glass. It is suitable for manufacturing.
  • this feature makes it suitable for using a float bath for a long period of time and for a method of manufacturing a float glass sheet.
  • FIG. 1 is a graph showing the relationship between load and fracture time in a bending creep test.
  • the float bath roof member according to one aspect of the present invention is made of an alumina-silica-based sintered body, and is suspended on a float bath by a hanger like a refractory brick in Patent Documents 1 and 2. It is a roof.
  • a float bath roof is formed by arranging a plurality of float bath roof members on the top of the float bath. For this reason, the said member requires the insertion part for the suspension support by a hanger, and the combination part with another member, and a favorable moldability is calculated
  • the float bath roof member of the present invention is an alumina-silica system in which 90% by mass or more of the crystalline phase is mullite phase and the total content of sodium oxide, potassium oxide, titanium oxide and iron oxide is 2% by mass or less.
  • the sintered body is composed of coarse particles having an average crystal grain diameter D50 of 1.0 mm or more, and fine grains having an average crystal grain diameter D50 of 0.1 mm or less, and the mass ratio of the coarse grains to the fine grains is 85 to 60% by mass and 15 to 40% by mass.
  • sillimanite-based sintered bodies As described above, conventionally, as a float bath roof member, among alumina-silica-based sintered bodies, sillimanite-based sintered bodies have been mainly used.
  • the sillimanite-based sintered body is a kind of high alumina sintered brick using a relatively high purity raw material, and includes mullite, corundum, and cristobalite as a crystal phase.
  • corundum which is alumina, gradually plastically deforms when used in a high temperature environment of 1200 ° C. or higher.
  • cristobalite causes a phase transition (phase transformation) at a temperature of 1400 ° C.
  • the float bath roof member of the present invention in which 90% by mass or more of the crystal phase of the alumina-silica-based sintered body is a mullite phase, does not undergo plastic deformation or phase transition ( Cracks due to volume changes due to phase transformations are less likely to occur. For this reason, there is little creep deformation.
  • the float bath roof member of the present invention is composed of two types of alumina-silica-based sintered bodies (coarse grains and fine grains) having different average crystal grain sizes. 90% by mass or more of the crystal phase of each of these two types of alumina-silica-based sintered bodies is the mullite phase.
  • the proportion of mullite phase in the crystal phase of alumina-silica-based sintered body is lower than 90% by mass, cracking occurs due to volume change due to plastic deformation or phase transition (phase transformation) of crystal phase other than mullite phase (corundum or cristobalite). Occurs and creep deformation increases.
  • the float bath roof member of the present invention can contain a crystal phase other than the mullite phase, that is, corundum and cristobalite, up to 10% by mass of the crystal phase of the alumina-silica-based sintered body.
  • the crystal phase other than the mullite phase may be either corundum or cristobalite.
  • the corundum content is preferably high.
  • the proportion of the mullite phase in the crystal phase of the alumina-silica-based sintered body is more preferably 95% by mass or more, and further preferably 97% by mass or more.
  • the alumina-silica-based sintered body contains sodium oxide, potassium oxide, titanium oxide, and iron oxide
  • silica (SiO 2 ) in the sintered body when used in a high temperature environment of 900 ° C. or higher, silica (SiO 2 ) in the sintered body and Reacts to form a glass phase.
  • the sintered body is softened, so that creep deformation increases. Therefore, the alumina-silica-based sintered body used for the float bath roof member preferably has a low content of these components.
  • the total content of sodium oxide, potassium oxide, titanium oxide, and iron oxide in the alumina-silica-based sintered body is 2% by mass or less.
  • the float bath roof member of the present invention is composed of two types of alumina-silica-based sintered bodies (coarse grains and fine grains) having different average crystal grain sizes.
  • the total content of sodium oxide, potassium oxide, titanium oxide and iron oxide in each of these two types of alumina-silica-based sintered bodies is 2% by mass or less.
  • the total content of sodium oxide, potassium oxide, titanium oxide, and iron oxide in the alumina-silica-based sintered body is more preferably 1.5% by mass or less. More preferably, it is at most mass%.
  • the float bath roof member of the present invention is made of an alumina-silica-based sintered body, each having a coarse grain having an average crystal grain size D50 of 1.0 mm or more, a fine grain having an average crystal grain size D50 of 0.1 mm or less, Consists of.
  • a block-like alumina-silica-based sintered body such as a float bath roof member
  • Those having a small particle size distribution that is, particles having a uniform particle size are usually used.
  • the particle size distribution of the crystal particles constituting the manufactured block-like alumina-silica-based sintered body is small, that is, the crystal particle size is uniform to some extent.
  • the particle size distribution of the crystal particles constituting the block-like alumina-silica-based sintered body is small, that is, if the crystal particle sizes are uniform to some extent.
  • the creep strength of the alumina-silica-based sintered body is lowered.
  • all of the crystal particles constituting the block-like alumina-silica-based sintered body have a small crystal grain size, no gap is formed between the crystal particles, but deformation and shrinkage during sintering increase. As a result, a potential crack is generated inside the sintered body and may be damaged during use.
  • the crystal grains constituting the alumina-silica-based sintered body are coarse grains having an average crystal grain diameter D50 of 1.0 mm or more and fine grains having an average crystal grain diameter D50 of 0.1 mm or less. Therefore, the above-mentioned problem in the conventional alumina-silica-based sintered body is solved. That is, by including coarse grains, deformation and shrinkage during sintering do not increase, and potential cracks do not occur inside the sintered body. This eliminates the possibility of damage during use. On the other hand, since the fine grains are filled in the gaps between the coarse grains, the crystal grains are strongly bonded to each other. This reduces the creep deformation of the sintered body. Further, the creep strength of the sintered body is improved. However, in order to obtain the above effect, the ratio of coarse particles to fine particles in the alumina-silica-based sintered body needs to satisfy a specific range described below.
  • the mass ratio of coarse particles and fine particles in the alumina-silica-based sintered body is 85 to 60% by mass and 15 to 40% by mass, respectively. If the mass ratio of fine particles in the alumina-silica-based sintered body exceeds 40% by mass (the mass ratio of coarse particles is less than 60% by mass), deformation and shrinkage during sintering increase, resulting in a decrease in production yield. To do. In addition, a potential crack may occur inside the sintered body, which may be damaged during use.
  • the mass ratio of fine grains in the alumina-silica-based sintered body is less than 15 mass% (the mass ratio of coarse grains exceeds 85 mass%), the bonding between crystal grains is not sufficient, and the alumina-silica-based sintered body is not sufficient. Creep deformation of the body increases. In addition, the creep strength of the alumina-silica-based sintered body is lowered.
  • the mass ratio of coarse particles and fine particles in the alumina-silica-based sintered body is preferably 75 to 70% by mass and 25 to 30% by mass, respectively.
  • An alumina-silica-based sintered body in which the mass ratio of coarse particles and fine particles satisfies the above-described range can be produced by the following procedure.
  • a mullite particle A having an average particle diameter D50 of 1.0 mm or more and a mullite particle B having an average particle diameter D50 of 0.1 mm or less are prepared.
  • the mullite particles A and B have a total content of sodium oxide, potassium oxide, titanium oxide and iron oxide of 2% by mass or less.
  • Mullite particles A and mullite particles B are blended so that the mass ratio thereof is 85 to 60 mass% and 15 to 40 mass%.
  • the obtained blend is filled in a mold having a predetermined shape corresponding to the shape of the float bath roof member, and heated to a predetermined temperature, for example, 1500 ° C. or higher, and sintered.
  • a predetermined temperature for example, 1500 ° C. or higher
  • the use of electrofused mullite particles is preferable because the content of impurities such as sodium oxide, potassium oxide, titanium oxide, and iron oxide becomes low.
  • the electrofused mullite particles are obtained by crushing electrofused mullite to have a predetermined size.
  • the float bath roof member according to one aspect of the present invention has suppressed creep deformation when used in a high temperature environment.
  • a creep rate in a bending creep test is used as an index of creep deformation.
  • the creep rate in the bending creep test (1300 ° C., load 3.5 MPa) described in Examples described later is preferably 1 ⁇ 10 ⁇ 8 / sec or less, more preferably 0.5 ⁇ 10 10. It is ⁇ 8 / sec or less, more preferably 0.1 ⁇ 10 ⁇ 8 / sec or less.
  • the float bath roof member according to one embodiment of the present invention has high creep strength when used in a high temperature environment.
  • the 1000-hour creep strength in a bending creep test (1300 ° C.) described in Examples described later is preferably 6 MPa or more, more preferably 8 MPa or more, and further preferably 10 MPa or more.
  • the maximum stress applied to the float bath roof member during use varies depending on the use conditions and the design of the peripheral members, but is about 0.1 to 1.0 MPa. Therefore, the float bath roof member according to one aspect of the present invention has sufficient creep strength against the stress applied during use.
  • the dimensions and shape of the float bath roof member in one aspect of the present invention are appropriately determined according to the arrangement of each member in the float bath roof.
  • it is a rectangular parallelepiped having a length of about 30 cm, a width of 5 to 8 cm, and a height of 6 to 10 cm.
  • Grooves for engaging with hangers are provided at both ends of the float bath roof member.
  • the float plate glass manufacturing apparatus in one aspect of the present invention includes a float bath in which molten tin is accommodated, and a float bath roof installed on the top of the float bath.
  • This float bath roof is composed of the float bath roof member of the present invention.
  • the float bath roof member of the present invention has suppressed creep deformation when used in a high temperature environment, and has high creep strength when used in a high temperature environment. For this reason, there is no possibility that the float bath roof member is detached from the hanger and falls, and can be used for a long period of time.
  • the float plate glass manufacturing apparatus is more suitable when manufacturing plate glass using glass with higher viscosity, or when manufacturing plate glass with a thin thickness even if the glass has the same composition.
  • a plate glass is manufactured using a glass having high viscosity such as a high-precision display glass used in a production process including a process exposed to a high temperature.
  • the method for producing a float glass sheet according to one aspect of the present invention introduces molten glass into a bath containing molten tin called a float bath, and continuously conveys the molten glass from upstream to downstream on the molten tin.
  • the glass sheet is produced by discharging the molten glass from the float bath while cooling the molten glass.
  • the above-described float bath roof member of the present invention since the above-described float bath roof member of the present invention is used, it can be stably produced for a long period of time.
  • Example 1 Comparative Examples 1 and 2
  • Example 2 As a sample for the bending creep test, an alumina-silica-based sintered body having the composition shown in the following table was prepared. The dimensions of the test sample were 25 mm ⁇ 15 mm ⁇ 100 mm.
  • the alumina-silica-based sintered body is a mixture of mullite particles A having an average particle diameter D50 of 1.0 mm or more and mullite particles B having an average particle diameter D50 of 0.1 mm or less in a predetermined mixing ratio. was obtained by heating to 1500 ° C. or higher and sintering.
  • Mullite particles A and B are obtained by crushing electrofused mullite and dividing it into mullite A and B according to the particle size. For this reason, coarse grains (average crystal grain size D50 is 1.0 mm or more) and fine grains (average crystal grain size D50 is 0.1 mm or less) constituting the alumina-silica-based sintered body are mullite in the crystal phase.
  • the ratio of the phase and the content of impurities are the same numerical value.
  • the impurity content in the table is the total content of sodium oxide, potassium oxide, titanium oxide, and iron oxide.
  • the alumina-silica sintered body of Example 1 in which the proportion of the mullite phase in the crystal phase is 90% by mass or more is that of Comparative Examples 1 and 2 in which the proportion of the mullite phase in the crystal phase is less than 90% by mass.
  • the creep rate was low and the creep deformation was small.
  • the alumina-silica sintered body of Example 1 was creeped compared to the alumina-silica sintered bodies of Comparative Examples 1 and 2 in which the proportion of the mullite phase in the crystal phase was less than 90% by mass.
  • Example 2 Comparative Example 3
  • a float bath roof member was produced using an alumina-silica sintered body having the same composition as in Example 1. This was installed on the existing float bath roof.
  • Comparative Example 3 a conventional sillimanite refractory brick was installed as a float bath roof member. The dimensions and shape of the float bath roof member are as described above. Further, the maximum stress applied to the float bath roof member during use is as described above. After 4 weeks with the atmospheric temperature in the float bath set to 1300 ° C., the center portion of the refractory brick of Comparative Example 3 was bent downward, and it was confirmed by visual observation that the creep deformation occurred. In addition, many cracks occurred on the bottom surface of the refractory brick. On the other hand, in the float bath roof member of Example 2, creep deformation and generation of cracks were not recognized.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
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  • Organic Chemistry (AREA)
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  • Compositions Of Oxide Ceramics (AREA)

Abstract

Provided are: a float bath roof member in which creep deformation during use is suppressed; a float plate glass production device using said float bath roof member; and a method for producing float plate glass. This float bath roof member is made of an alumina-silica-based sintered compact in which: greater than or equal to 90 mass% of each crystal phase is a mullite phase; the total content of sodium oxide, potassium oxide, titanium oxide, and iron oxide is less than or equal to 2 mass%; the sintered compact is constituted by coarse grains with an average crystal grain size D50 of 1.0 mm or greater, and fine grains with an average crystal grain size D50 of 0.1 mm or less; and the respective mass ratios of said coarse grains and said fine grains are 85-60 mass% and 15-40 mass%.

Description

フロートバスルーフ部材、それを用いたフロート板ガラス製造装置、およびフロート板ガラス製造方法Float bath roof member, float plate glass manufacturing apparatus using the same, and float plate glass manufacturing method
　本発明は、フロートバスルーフ部材、それを用いたフロート板ガラス製造装置、およびフロート板ガラスの製造方法に関する。 The present invention relates to a float bath roof member, a float plate glass manufacturing apparatus using the same, and a method for manufacturing a float plate glass.
　板ガラスを製造する一方法として、フロート法が知られている。このフロート法では、（１）フロートバスと呼ばれる溶融スズを収容する浴槽内に、溶融ガラスを導入し、
（２）溶融スズ上で、溶融ガラスを上流から下流に沿って連続的に搬送し、
（３）この溶融ガラスを冷却しながら、フロートバスから排出させることにより、板ガラスが製造される。 A float method is known as one method for producing plate glass. In this float process, (1) molten glass is introduced into a bath containing molten tin called a float bath,
(2) On the molten tin, the molten glass is continuously conveyed from upstream to downstream,
(3) Sheet glass is manufactured by discharging from the float bath while cooling this molten glass.
　通常、フロートバスの上部には、フロートバスルーフと呼ばれる天井部分が設置される。このフロートバスルーフは、下面（すなわちフロートバスと対面する側）が複数のハンガーに係合された耐火物レンガで構成され、すなわちフロートバスルーフは、吊り構造となっている（特許文献１～２参照）。 Usually, a ceiling part called a float bath roof is installed at the top of the float bath. This float bath roof is composed of refractory bricks whose lower surface (ie, the side facing the float bath) is engaged with a plurality of hangers, that is, the float bath roof has a suspended structure (Patent Documents 1 and 2). reference).
日本国特開平６－２３９６３１号公報Japanese Patent Laid-Open No. 6-239631 日本国特開２００１－１３９３３６号公報Japanese Unexamined Patent Publication No. 2001-139336
　フロートバスルーフに使用する耐火物レンガには、比較的軽量で、１０００℃程度までの高温で長期使用が可能な耐熱性を有し、高温での使用時に製造するガラスの欠点となり得る蒸発物の量が少ないなどの理由から、アルミナ（Ａｌ２Ｏ３）－シリカ（ＳｉＯ２）系の耐火物レンガが使用でき、中でも、シリマナイト系の耐火物レンガが、種々の成形方法が適用でき、種々の形状に成形可能などの理由から、使用できる。 Refractory bricks used for float bath roofs are relatively lightweight, have heat resistance that can be used for a long time at temperatures as high as 1000 ° C, and can be a disadvantage of glass produced when used at high temperatures. Alumina (Al 2 O 3 ) -silica (SiO 2 ) -based refractory bricks can be used for reasons such as a small amount, among which sillimanite-based refractory bricks can be applied to various molding methods, Can be used for any reason that can be molded into shape.
　フロートバスの冷間修理などにおいて、フロートバスルーフを構成する耐火物レンガにクリープ変形が認められる場合がある。フロートバスルーフを構成する耐火物レンガは、ハンガーに係合された吊り構造となっているため、耐火物レンガのクリープ変形が進行すると、ハンガーから脱離して落下するおそれがある。また、クリープ変形が過度に進行した場合、耐火物レンガにクラックが発生するおそれもある。
　耐火物レンガのクリープ変形は、温度が高いほどより進行するため、より粘性が高いガラスを板状に成形する場合や、同じ組成のガラスであっても、厚さが薄い板ガラスに成形する場合、好ましくは０．７ｍｍ以下、より好ましくは０．５ｍｍ以下、さらに好ましくは０．３ｍｍ以下の厚さが薄い板ガラスに成形する場合に、フロートバス内の雰囲気温度を高めた際に、問題がさらに顕著になると考えられる。
　また、クリープ変形量は、高温環境中での保持時間に応じて経時的に増加するため、フロートバスを長期間にわたって使用するうえで特に問題となる。 In cold repair of a float bath, creep deformation may be observed in the refractory bricks that constitute the float bath roof. Since the refractory brick constituting the float bath roof has a suspended structure engaged with the hanger, when the creep deformation of the refractory brick progresses, it may be detached from the hanger and fall. Further, when creep deformation proceeds excessively, cracks may occur in the refractory bricks.
Creep deformation of refractory bricks progresses more as the temperature is higher, so when molding glass with higher viscosity into a plate shape, or even when glass of the same composition is molded into thin plate glass, The problem is even more pronounced when the ambient temperature in the float bath is increased when forming a thin plate glass having a thickness of preferably 0.7 mm or less, more preferably 0.5 mm or less, and even more preferably 0.3 mm or less. It is thought that it becomes.
Further, since the amount of creep deformation increases with time according to the holding time in a high temperature environment, it becomes a particular problem when the float bath is used over a long period of time.
　本発明は、上記した従来技術の問題点を解決するため、高温環境下での使用時におけるクリープ変形が抑制されたフロートバスルーフ用部材、それを用いたフロート板ガラス製造装置、およびフロート板ガラス製造方法を提供することを目的とする。 In order to solve the above-described problems of the prior art, the present invention provides a float bath roof member in which creep deformation during use in a high temperature environment is suppressed, a float plate glass manufacturing apparatus using the same, and a float plate glass manufacturing method The purpose is to provide.
　上記した目的を達成するため、本発明は、各々結晶相の９０質量％以上がムライト相であり、かつ、酸化ナトリウム、酸化カリウム、酸化チタン、酸化鉄の合計含有量が２質量％以下のアルミナ－シリカ系焼結体からなり、平均結晶粒径Ｄ５０が１．０ｍｍ以上の粗粒、および、平均結晶粒径Ｄ５０が０．１ｍｍ以下の細粒で構成され、該粗粒および細粒の質量比が、８５～６０質量％、および、１５～４０質量％であるフロートバスルーフ部材を提供する。 In order to achieve the above object, the present invention provides an alumina in which 90% by mass or more of the crystalline phase is a mullite phase and the total content of sodium oxide, potassium oxide, titanium oxide, and iron oxide is 2% by mass or less. -It is composed of a silica-based sintered body and is composed of coarse particles having an average crystal grain size D50 of 1.0 mm or more, and fine particles having an average crystal grain size D50 of 0.1 mm or less, and the mass of the coarse grains and fine grains Float bath roof members having a ratio of 85 to 60% by mass and 15 to 40% by mass are provided.
　本発明の一態様におけるフロートバスルーフ部材は、サンプルサイズ２５ｍｍ×１５ｍｍ×１００ｍｍでの曲げクリープ試験（１３００℃、負荷３．５ＭＰａ）におけるクリープ速度が１×１０-８／ｓｅｃ以下であることが好ましい。 The float bath roof member according to one aspect of the present invention preferably has a creep rate of 1 × 10 −8 / sec or less in a bending creep test (1300 ° C., load 3.5 MPa) with a sample size of 25 mm × 15 mm × 100 mm. .
　また、本発明の一態様におけるフロートバスルーフ部材は、サンプルサイズ２５ｍｍ×１５ｍｍ×１００ｍｍでの曲げクリープ試験（１３００℃）における１０００時間クリープ強度が６ＭＰａ以上であることが好ましい。 Further, the float bath roof member according to one embodiment of the present invention preferably has a 1000 hour creep strength of 6 MPa or more in a bending creep test (1300 ° C.) with a sample size of 25 mm × 15 mm × 100 mm.
また、本発明の一態様におけるフロートバスルーフ部材は、前記粗粒及び細粒がムライト粒子を含み、該ムライト粒子が電融ムライト粒子であることが好ましい。 In the float bath roof member according to an aspect of the present invention, the coarse particles and fine particles preferably include mullite particles, and the mullite particles are preferably electrofused mullite particles.
また、本発明の一態様におけるフロートバスルーフ部材は、前記結晶相において、ムライト相以外の結晶相、すなわち、コランダムおよびクリストバライトの含有率が、アルミナ－シリカ系焼結体の結晶相に対して１０質量％以下であることが好ましい。 In the float bath roof member according to one aspect of the present invention, the crystal phase other than the mullite phase, that is, the content of corundum and cristobalite in the crystal phase is 10 with respect to the crystal phase of the alumina-silica-based sintered body. It is preferable that it is below mass%.
また、本発明の一態様におけるフロートバスルーフ部材は、前記ムライト相以外の結晶相が、コランダムおよびクリストバライトのいずれであって、両者のうち、コランダムの含有割合が高いことが好ましい。 In the float bath roof member according to an aspect of the present invention, the crystal phase other than the mullite phase is preferably corundum or cristobalite, and the corundum content is preferably high in both.
　また、本発明の一態様のフロート板ガラス製造装置においては、内部に溶融スズが収容されるフロートバスと、前記フロートバスの上部に設置されるフロートバスルーフと、を備えるフロート板ガラス製造装置であって、
　前記フロートバスルーフが、本発明のフロートバスルーフ部材で構成されていることを特徴とするフロート板ガラス製造装置を提供する。 Further, in the float sheet glass manufacturing apparatus of one aspect of the present invention, a float sheet glass manufacturing apparatus comprising: a float bath in which molten tin is housed; and a float bath roof installed at an upper portion of the float bath. ,
The float bath roof is composed of the float bath roof member of the present invention.
　さらに、本発明の一態様は、本発明の一態様のフロート板ガラス製造装置を使用してフロート板ガラスを作製することを含むフロート板ガラス製造方法を提供する。 Furthermore, one aspect of the present invention provides a float sheet glass manufacturing method including producing a float sheet glass using the float sheet glass manufacturing apparatus of one aspect of the present invention.
　また、本発明の一態様のフロート板ガラス製造方法において、前記フロート板ガラスが、ディスプレイ用のフロートガラスであり、該フロートガラスの厚さが０．７ｍｍ以下であることが好ましい。 Moreover, in the float plate glass manufacturing method of one embodiment of the present invention, it is preferable that the float plate glass is a float glass for display, and the thickness of the float glass is 0.7 mm or less.
　本発明のフロートバスルーフ部材は、高温環境下での使用時におけるクリープ変形が抑制されている。
　このため、板ガラスの製造時において、フロートバスルーフ部材がハンガーから脱離して落下するおそれや、フロートバスルーフ部材にクラックが発生するおそれが低減されている。
　また、この特徴により、無アルカリガラスなど、粘性が高いガラスを用いて板ガラスを製造する際や、薄板ガラスを製造する際のように、フロートバス内の雰囲気温度を高くすることが求められるフロート板ガラスの製造に好適である。
　また、この特徴により、フロートバスを長期間にわたって使用し、フロート板ガラスの製造方法に使用するのに好適である。 In the float bath roof member of the present invention, creep deformation during use in a high temperature environment is suppressed.
For this reason, at the time of manufacture of plate glass, the possibility that the float bath roof member may be detached from the hanger and dropped, and the possibility that cracks may occur in the float bath roof member are reduced.
In addition, due to this feature, a float plate glass that is required to increase the atmospheric temperature in the float bath, such as when producing a plate glass using a highly viscous glass such as an alkali-free glass or a thin plate glass. It is suitable for manufacturing.
In addition, this feature makes it suitable for using a float bath for a long period of time and for a method of manufacturing a float glass sheet.
図１は、曲げクリープ試験における負荷と破断時間との関係を示したグラフである。FIG. 1 is a graph showing the relationship between load and fracture time in a bending creep test.
　以下、本発明の一態様におけるフロートバスルーフ部材およびそれを用いたフロート板ガラス製造装置について説明する。 Hereinafter, a float bath roof member and a float sheet glass manufacturing apparatus using the float bath roof member according to an aspect of the present invention will be described.
　本発明の一態様におけるフロートバスルーフ部材は、アルミナ－シリカ系の焼結体からなり、特許文献１、２における耐火物レンガのように、フロートバスの上部に、ハンガーによって吊支してフロートバスルーフをなすものである。通常は、フロートバスの上部に、複数のフロートバスルーフ部材を配設して、フロートバスルーフをなす。このため、当該部材にはハンガーによる吊支のための挿入部や他部材との組み合わせ部が必要であり、良好な成形性が求められる。 The float bath roof member according to one aspect of the present invention is made of an alumina-silica-based sintered body, and is suspended on a float bath by a hanger like a refractory brick in Patent Documents 1 and 2. It is a roof. Usually, a float bath roof is formed by arranging a plurality of float bath roof members on the top of the float bath. For this reason, the said member requires the insertion part for the suspension support by a hanger, and the combination part with another member, and a favorable moldability is calculated | required.
　本発明のフロートバスルーフ部材は、各々結晶相の９０質量％以上がムライト相であり、かつ、酸化ナトリウム、酸化カリウム、酸化チタン、酸化鉄の合計含有量が２質量％以下のアルミナ－シリカ系焼結体からなり、平均結晶粒径Ｄ５０が１．０ｍｍ以上の粗粒、および、平均結晶粒径Ｄ５０が０．１ｍｍ以下の細粒で構成され、該粗粒および細粒の質量比が、８５～６０質量％、および、１５～４０質量％である。 The float bath roof member of the present invention is an alumina-silica system in which 90% by mass or more of the crystalline phase is mullite phase and the total content of sodium oxide, potassium oxide, titanium oxide and iron oxide is 2% by mass or less. The sintered body is composed of coarse particles having an average crystal grain diameter D50 of 1.0 mm or more, and fine grains having an average crystal grain diameter D50 of 0.1 mm or less, and the mass ratio of the coarse grains to the fine grains is 85 to 60% by mass and 15 to 40% by mass.
　上述したように、従来、フロートバスルーフ部材としては、アルミナ－シリカ系の焼結体の中でも、シリマナイト系の焼結体が主として用いられていた。シリマナイト系の焼結体とは、比較的高純度な原料を用いた高アルミナ質焼結レンガの１種であり、結晶相として、ムライト、コランダム、クリストバライトが混在するものである。
　アルミナ－シリカ系焼結体の結晶相のうち、アルミナであるコランダムは１２００℃以上の高温環境下で使用すると、徐々に塑性変形する。一方、クリストバライトは１４００℃以下の温度では相転移（相変態）を起こしトリディマイトに変態し、体積変化による割れを誘発する。そのため、これらの結晶相を多く含む焼結体は、塑性変形や割れの発生に起因してクリープ変形する。
　これに対し、ムライトは、１２００℃以上の高温環境下で使用しても、塑性変形や相転移（相変態）を起こさない。そのため、アルミナ－シリカ系焼結体の結晶相の９０質量％以上がムライト相である本発明のフロートバスルーフ部材は、１２００℃以上の高温環境下で使用しても、塑性変形や相転移（相変態）による体積変化による割れが発生しにくい。このため、クリープ変形が少ない。
　なお、詳しくは後述するが、本発明のフロートバスルーフ部材は、平均結晶粒径が異なる２種類のアルミナ－シリカ系焼結体（粗粒、細粒）で構成される。これら２種類のアルミナ－シリカ系焼結体各々の結晶相の９０質量％以上がムライト相である。
　アルミナ－シリカ系焼結体の結晶相に占めるムライト相の割合が９０質量％より低いと、ムライト相以外の結晶相（コランダムやクリストバライト）の塑性変形や相転移（相変態）による体積変化により割れが発生し、クリープ変形が大きくなる。 As described above, conventionally, as a float bath roof member, among alumina-silica-based sintered bodies, sillimanite-based sintered bodies have been mainly used. The sillimanite-based sintered body is a kind of high alumina sintered brick using a relatively high purity raw material, and includes mullite, corundum, and cristobalite as a crystal phase.
Among the crystalline phases of the alumina-silica-based sintered body, corundum, which is alumina, gradually plastically deforms when used in a high temperature environment of 1200 ° C. or higher. On the other hand, cristobalite causes a phase transition (phase transformation) at a temperature of 1400 ° C. or lower, transforms to tridymite, and induces cracking due to volume change. Therefore, a sintered body containing a large amount of these crystal phases undergoes creep deformation due to the occurrence of plastic deformation and cracks.
In contrast, mullite does not cause plastic deformation or phase transition (phase transformation) even when used in a high temperature environment of 1200 ° C. or higher. Therefore, the float bath roof member of the present invention, in which 90% by mass or more of the crystal phase of the alumina-silica-based sintered body is a mullite phase, does not undergo plastic deformation or phase transition ( Cracks due to volume changes due to phase transformations are less likely to occur. For this reason, there is little creep deformation.
As will be described in detail later, the float bath roof member of the present invention is composed of two types of alumina-silica-based sintered bodies (coarse grains and fine grains) having different average crystal grain sizes. 90% by mass or more of the crystal phase of each of these two types of alumina-silica-based sintered bodies is the mullite phase.
When the proportion of mullite phase in the crystal phase of alumina-silica-based sintered body is lower than 90% by mass, cracking occurs due to volume change due to plastic deformation or phase transition (phase transformation) of crystal phase other than mullite phase (corundum or cristobalite). Occurs and creep deformation increases.
　本発明のフロートバスルーフ部材は、ムライト相以外の結晶相、すなわち、コランダムおよびクリストバライトを、アルミナ－シリカ系焼結体の結晶相１０質量％まで含有することができる。この場合、ムライト相以外の結晶相は、コランダムおよびクリストバライトのいずれであってもよい。但し、両者のうち、コランダムのほうが１２００℃以上の温度域で使用した際に、クリープ変形を生じさせることがないため、両者のうち、コランダムの含有割合が高いことが好ましい。
　本発明の一態様におけるフロートバスルーフ部材において、アルミナ－シリカ系焼結体の結晶相に占めるムライト相の割合が９５質量％以上であることがより好ましく、９７質量％以上であることがさらに好ましい。 The float bath roof member of the present invention can contain a crystal phase other than the mullite phase, that is, corundum and cristobalite, up to 10% by mass of the crystal phase of the alumina-silica-based sintered body. In this case, the crystal phase other than the mullite phase may be either corundum or cristobalite. However, when both corundums are used in a temperature range of 1200 ° C. or higher, creep deformation does not occur. Therefore, the corundum content is preferably high.
In the float bath roof member according to one aspect of the present invention, the proportion of the mullite phase in the crystal phase of the alumina-silica-based sintered body is more preferably 95% by mass or more, and further preferably 97% by mass or more. .
　また、アルミナ－シリカ系焼結体が、酸化ナトリウム、酸化カリウム、酸化チタン、酸化鉄を含有すると、９００℃以上の高温環境下で使用した際に、焼結体中のシリカ（ＳｉＯ２）と反応してガラス相を形成する。このようなガラス相が形成されると、焼結体が軟化するため、クリープ変形が大きくなる。そのため、フロートバスルーフ部材に用いるアルミナ－シリカ系焼結体は、これらの成分の含有量が低いことが好ましい。
　本発明の一態様におけるフロートバスルーフ部材は、アルミナ－シリカ系焼結体における酸化ナトリウム、酸化カリウム、酸化チタン、酸化鉄の合計含有量が２質量％以下であるため、１２００℃以上の高温環境下で使用した場合でも、焼結体が軟化することがなく、クリープ変形が少ない。
　上述したように、本発明のフロートバスルーフ部材は、平均結晶粒径が異なる２種類のアルミナ－シリカ系焼結体（粗粒、細粒）で構成される。これら２種類のアルミナ－シリカ系焼結体各々における酸化ナトリウム、酸化カリウム、酸化チタン、酸化鉄の合計含有量が２質量％以下である。
　本発明の一態様におけるフロートバスルーフ部材は、アルミナ－シリカ系焼結体における酸化ナトリウム、酸化カリウム、酸化チタン、酸化鉄の合計含有量が１．５質量％以下であることがより好ましく、１質量％以下であることがさらに好ましい。 In addition, when the alumina-silica-based sintered body contains sodium oxide, potassium oxide, titanium oxide, and iron oxide, when used in a high temperature environment of 900 ° C. or higher, silica (SiO 2 ) in the sintered body and Reacts to form a glass phase. When such a glass phase is formed, the sintered body is softened, so that creep deformation increases. Therefore, the alumina-silica-based sintered body used for the float bath roof member preferably has a low content of these components.
In the float bath roof member according to one aspect of the present invention, the total content of sodium oxide, potassium oxide, titanium oxide, and iron oxide in the alumina-silica-based sintered body is 2% by mass or less. Even when used below, the sintered body does not soften and creep deformation is small.
As described above, the float bath roof member of the present invention is composed of two types of alumina-silica-based sintered bodies (coarse grains and fine grains) having different average crystal grain sizes. The total content of sodium oxide, potassium oxide, titanium oxide and iron oxide in each of these two types of alumina-silica-based sintered bodies is 2% by mass or less.
In the float bath roof member according to one aspect of the present invention, the total content of sodium oxide, potassium oxide, titanium oxide, and iron oxide in the alumina-silica-based sintered body is more preferably 1.5% by mass or less. More preferably, it is at most mass%.
　本発明のフロートバスルーフ部材は、各々アルミナ－シリカ系焼結体からなる、平均結晶粒径Ｄ５０が１．０ｍｍ以上の粗粒と、平均結晶粒径Ｄ５０が０．１ｍｍ以下の細粒と、で構成される。
　フロートバスルーフ部材のような、ブロック状のアルミナ－シリカ系焼結体を製造する場合、焼結時の寸法変化率に異方性が生じにくいなどの理由から、焼結体の原料には、粒度分布が少ないもの、つまり、粒径がある程度そろったものが通常は用いられる。その結果、製造されたブロック状のアルミナ－シリカ系焼結体を構成する結晶粒子の粒度分布が少ないもの、つまり、結晶粒径がある程度そろったものとなる。
　しかしながら、ブロック状のアルミナ－シリカ系焼結体を構成する結晶粒子の粒度分布が少ない、つまり、結晶粒径がある程度そろっていると、以下の点で問題となる。
　ブロック状のアルミナ－シリカ系焼結体を構成する結晶粒子が、全て結晶粒径が大きい場合、結晶粒子間に隙間が生じる。その結果、結晶粒子同士の結合が十分ではなくなり、アルミナ－シリカ系焼結体のクリープ変形が大きくなる。また、アルミナ－シリカ系焼結体のクリープ強度が低下する。
　一方、ブロック状のアルミナ－シリカ系焼結体を構成する結晶粒子が、全て結晶粒径が小さい場合、結晶粒子間に隙間が生じることはないが、焼結時の変形や収縮が大きくなる。その結果、焼結体内部に潜在的な割れが発生して、使用時に破損するおそれがある。 The float bath roof member of the present invention is made of an alumina-silica-based sintered body, each having a coarse grain having an average crystal grain size D50 of 1.0 mm or more, a fine grain having an average crystal grain size D50 of 0.1 mm or less, Consists of.
When manufacturing a block-like alumina-silica-based sintered body such as a float bath roof member, for the reason that anisotropy does not easily occur in the dimensional change rate during sintering, Those having a small particle size distribution, that is, particles having a uniform particle size are usually used. As a result, the particle size distribution of the crystal particles constituting the manufactured block-like alumina-silica-based sintered body is small, that is, the crystal particle size is uniform to some extent.
However, if the particle size distribution of the crystal particles constituting the block-like alumina-silica-based sintered body is small, that is, if the crystal particle sizes are uniform to some extent, the following problems arise.
When all the crystal particles constituting the block-like alumina-silica-based sintered body have a large crystal grain size, a gap is generated between the crystal particles. As a result, the bonds between the crystal grains are not sufficient, and the creep deformation of the alumina-silica-based sintered body increases. In addition, the creep strength of the alumina-silica-based sintered body is lowered.
On the other hand, when all of the crystal particles constituting the block-like alumina-silica-based sintered body have a small crystal grain size, no gap is formed between the crystal particles, but deformation and shrinkage during sintering increase. As a result, a potential crack is generated inside the sintered body and may be damaged during use.
　本発明のフロートバスルーフ部材は、アルミナ－シリカ系焼結体を構成する結晶粒子が、平均結晶粒径Ｄ５０が１．０ｍｍ以上の粗粒と、平均結晶粒径Ｄ５０が０．１ｍｍ以下の細粒と、で構成されているため、従来のアルミナ－シリカ系焼結体における上述した問題が解消される。すなわち、粗粒を含むことで、焼結時の変形や収縮が大きくならず、焼結体内部に潜在的な割れが発生することがない。これにより、使用時に破損するおそれが解消される。
　一方、粗粒間の隙間に細粒が充填されるため、結晶粒子同士が強く結合する。これにより、焼結体のクリープ変形が小さくなる。また、焼結体のクリープ強度が向上する。
　但し、上記の効果を得るためには、アルミナ－シリカ系焼結体における粗粒と細粒の比率が、以下に述べる特定の範囲を満たす必要がある。 In the float bath roof member of the present invention, the crystal grains constituting the alumina-silica-based sintered body are coarse grains having an average crystal grain diameter D50 of 1.0 mm or more and fine grains having an average crystal grain diameter D50 of 0.1 mm or less. Therefore, the above-mentioned problem in the conventional alumina-silica-based sintered body is solved. That is, by including coarse grains, deformation and shrinkage during sintering do not increase, and potential cracks do not occur inside the sintered body. This eliminates the possibility of damage during use.
On the other hand, since the fine grains are filled in the gaps between the coarse grains, the crystal grains are strongly bonded to each other. This reduces the creep deformation of the sintered body. Further, the creep strength of the sintered body is improved.
However, in order to obtain the above effect, the ratio of coarse particles to fine particles in the alumina-silica-based sintered body needs to satisfy a specific range described below.
　本発明のフロートバスルーフ部材は、アルミナ－シリカ系焼結体における粗粒および細粒の質量比が、それぞれ８５～６０質量％、および、１５～４０質量％である。
　アルミナ－シリカ系焼結体における細粒の質量比が４０質量％超（粗粒の質量比が６０質量％未満）だと、焼結時の変形や収縮が大きくなり、製造時の歩留まりが低下する。また、焼結体内部に潜在的な割れが発生して、使用時に破損するおそれがある。
　一方、アルミナ－シリカ系焼結体における細粒の質量比が１５質量％未満（粗粒の質量比が８５質量％超）だと、結晶粒子同士の結合が十分ではなく、アルミナ－シリカ系焼結体のクリープ変形が大きくなる。また、アルミナ－シリカ系焼結体のクリープ強度が低下する。
　本発明の一態様におけるフロートバスルーフ部材は、アルミナ－シリカ系焼結体における粗粒および細粒の質量比が、それぞれ７５～７０質量％、および、２５～３０質量％であることが好ましい。 In the float bath roof member of the present invention, the mass ratio of coarse particles and fine particles in the alumina-silica-based sintered body is 85 to 60% by mass and 15 to 40% by mass, respectively.
If the mass ratio of fine particles in the alumina-silica-based sintered body exceeds 40% by mass (the mass ratio of coarse particles is less than 60% by mass), deformation and shrinkage during sintering increase, resulting in a decrease in production yield. To do. In addition, a potential crack may occur inside the sintered body, which may be damaged during use.
On the other hand, if the mass ratio of fine grains in the alumina-silica-based sintered body is less than 15 mass% (the mass ratio of coarse grains exceeds 85 mass%), the bonding between crystal grains is not sufficient, and the alumina-silica-based sintered body is not sufficient. Creep deformation of the body increases. In addition, the creep strength of the alumina-silica-based sintered body is lowered.
In the float bath roof member according to one aspect of the present invention, the mass ratio of coarse particles and fine particles in the alumina-silica-based sintered body is preferably 75 to 70% by mass and 25 to 30% by mass, respectively.
　粗粒および細粒の質量比が上述した範囲を満たすアルミナ－シリカ系焼結体は、以下の手順で製造することができる。
　平均粒径Ｄ５０が１．０ｍｍ以上のムライト粒子Ａと、平均粒径Ｄ５０が０．１ｍｍ以下のムライト粒子Ｂを準備する。ムライト粒子Ａ、Ｂは、酸化ナトリウム、酸化カリウム、酸化チタン、酸化鉄の合計含有量が２質量％以下である。
　ムライト粒子Ａ、および、ムライト粒子Ｂを、それらの質量比が、８５～６０質量％、および、１５～４０質量％となるように配合する。得られた配合物を、フロートバスルーフ部材の形状に応じた、所定の形状の型に充填して、所定の温度、たとえば、１５００℃以上、に加熱して焼結させる。
　ムライト粒子Ａ、Ｂとしては、電融ムライト粒子の使用が、酸化ナトリウム、酸化カリウム、酸化チタン、酸化鉄といった不純物の含有量が低くなるので好ましい。電融ムライト粒子とは、電融ムライトを所定の寸法になるよう破砕したものである。 An alumina-silica-based sintered body in which the mass ratio of coarse particles and fine particles satisfies the above-described range can be produced by the following procedure.
A mullite particle A having an average particle diameter D50 of 1.0 mm or more and a mullite particle B having an average particle diameter D50 of 0.1 mm or less are prepared. The mullite particles A and B have a total content of sodium oxide, potassium oxide, titanium oxide and iron oxide of 2% by mass or less.
Mullite particles A and mullite particles B are blended so that the mass ratio thereof is 85 to 60 mass% and 15 to 40 mass%. The obtained blend is filled in a mold having a predetermined shape corresponding to the shape of the float bath roof member, and heated to a predetermined temperature, for example, 1500 ° C. or higher, and sintered.
As the mullite particles A and B, the use of electrofused mullite particles is preferable because the content of impurities such as sodium oxide, potassium oxide, titanium oxide, and iron oxide becomes low. The electrofused mullite particles are obtained by crushing electrofused mullite to have a predetermined size.
　本発明の一態様におけるフロートバスルーフ部材は、高温環境下で使用した際のクリープ変形が抑制されている。本明細書において、クリープ変形の指標としては、曲げクリープ試験におけるクリープ速度を用いる。具体的には、後述する実施例に記載の曲げクリープ試験（１３００℃、負荷３．５ＭＰａ）におけるクリープ速度が１×１０-８／ｓｅｃ以下であることが好ましく、より好ましくは０．５×１０-８／ｓｅｃ以下であり、さらに好ましくは０．１×１０-８／ｓｅｃ以下である。 The float bath roof member according to one aspect of the present invention has suppressed creep deformation when used in a high temperature environment. In this specification, a creep rate in a bending creep test is used as an index of creep deformation. Specifically, the creep rate in the bending creep test (1300 ° C., load 3.5 MPa) described in Examples described later is preferably 1 × 10 −8 / sec or less, more preferably 0.5 × 10 10. It is −8 / sec or less, more preferably 0.1 × 10 −8 / sec or less.
　また、本発明の一態様におけるフロートバスルーフ部材は、高温環境下で使用した際のクリープ強度が高い。具体的には、後述する実施例に記載の曲げクリープ試験（１３００℃）における１０００時間クリープ強度が６ＭＰａ以上であることが好ましく、より好ましくは８ＭＰａ以上であり、さらに好ましくは１０ＭＰａ以上である。
　使用時のフロートバスルーフ部材に加わる最大応力は、その使用条件や周辺部材の設計により異なるが、０．１～１．０ＭＰａ程度である。したがって、本発明の一態様におけるフロートバスルーフ部材は、使用時に加わる応力に対して、十分なクリープ強度を有している。 In addition, the float bath roof member according to one embodiment of the present invention has high creep strength when used in a high temperature environment. Specifically, the 1000-hour creep strength in a bending creep test (1300 ° C.) described in Examples described later is preferably 6 MPa or more, more preferably 8 MPa or more, and further preferably 10 MPa or more.
The maximum stress applied to the float bath roof member during use varies depending on the use conditions and the design of the peripheral members, but is about 0.1 to 1.0 MPa. Therefore, the float bath roof member according to one aspect of the present invention has sufficient creep strength against the stress applied during use.
　本発明の一態様におけるフロートバスルーフ部材の寸法および形状は、フロートバスルーフにおける各部材の配置等に応じて適宜される。一例を挙げると、長さ３０ｃｍ程度で、幅５～８ｃｍ、高さ６～１０ｃｍの直方体様である。フロートバスルーフ部材の両端部には、ハンガーと係合するための溝が設けられている。 The dimensions and shape of the float bath roof member in one aspect of the present invention are appropriately determined according to the arrangement of each member in the float bath roof. For example, it is a rectangular parallelepiped having a length of about 30 cm, a width of 5 to 8 cm, and a height of 6 to 10 cm. Grooves for engaging with hangers are provided at both ends of the float bath roof member.
　次に、本発明の一態様におけるフロート板ガラス製造装置について説明する。
　本発明の一態様におけるフロート板ガラス製造装置は、内部に溶融スズが収容されるフロートバスと、該フロートバスの上部に設置されるフロートバスルーフと、を備える。このフロートバスルーフは、本発明のフロートバスルーフ部材で構成されている。
　上述したように、本発明のフロートバスルーフ部材は、高温環境下で使用した際のクリープ変形が抑制されており、かつ、高温環境下で使用した際のクリープ強度が高い。
　このため、フロートバスルーフ部材が、ハンガーから脱離して落下するおそれがなく、長期間にわたって使用することができる。
　また、本発明のフロートバスルーフ部材の上記した特性、すなわち、高温環境下で使用した際のクリープ変形が抑制されており、かつ、高温環境下で使用した際のクリープ強度が高いことは、フロートバス内の雰囲気温度を高くした場合に、より有効である。
　そのため、本発明の一態様におけるフロート板ガラス製造装置は、より粘性が高いガラスを用いて板ガラスを製造する場合や、同じ組成のガラスであっても、厚さが薄い板ガラスを製造する場合に、より好ましく用いられる。
　前者の具体例としては、高温にさらされる工程を含む製作工程に供される高精度なディスプレイ用ガラスなどの粘性の高いガラスを用いて板ガラスを製造する場合が挙げられる。
　後者の具体例としては、厚さが０．７ｍｍ以下、より好ましくは０．５ｍｍ以下、さらに好ましくは０．３ｍｍ以下の板ガラスを製造する場合が挙げられる。
　本発明の一態様におけるフロート板ガラス製造方法は、フロートバスと呼ばれる溶融スズを収容する浴槽内に、溶融ガラスを導入し、溶融スズ上で、溶融ガラスを上流から下流に沿って連続的に搬送し、この溶融ガラスを冷却しながら、フロートバスから排出させることにより、板ガラスが製造するものである。本発明の一態様におけるフルート板ガラスの製造方法では、本発明の前記したフロートバスルーフ部材を使用するので、長期的に安定して製造ができる。 Next, the float glass plate manufacturing apparatus in one embodiment of the present invention will be described.
The float plate glass manufacturing apparatus in one aspect of the present invention includes a float bath in which molten tin is accommodated, and a float bath roof installed on the top of the float bath. This float bath roof is composed of the float bath roof member of the present invention.
As described above, the float bath roof member of the present invention has suppressed creep deformation when used in a high temperature environment, and has high creep strength when used in a high temperature environment.
For this reason, there is no possibility that the float bath roof member is detached from the hanger and falls, and can be used for a long period of time.
In addition, the above-described characteristics of the float bath roof member of the present invention, that is, creep deformation when used under a high temperature environment is suppressed, and the creep strength when used under a high temperature environment is high. This is more effective when the ambient temperature in the bath is increased.
Therefore, the float plate glass manufacturing apparatus according to one aspect of the present invention is more suitable when manufacturing plate glass using glass with higher viscosity, or when manufacturing plate glass with a thin thickness even if the glass has the same composition. Preferably used.
As a specific example of the former, there is a case where a plate glass is manufactured using a glass having high viscosity such as a high-precision display glass used in a production process including a process exposed to a high temperature.
As a specific example of the latter, there is a case where a plate glass having a thickness of 0.7 mm or less, more preferably 0.5 mm or less, and further preferably 0.3 mm or less is produced.
The method for producing a float glass sheet according to one aspect of the present invention introduces molten glass into a bath containing molten tin called a float bath, and continuously conveys the molten glass from upstream to downstream on the molten tin. The glass sheet is produced by discharging the molten glass from the float bath while cooling the molten glass. In the method for producing a flute sheet glass according to one aspect of the present invention, since the above-described float bath roof member of the present invention is used, it can be stably produced for a long period of time.
　以下、実施例により本発明を詳述するが、本発明はこれらの実施例に限定されるものではない。
（実施例１、比較例１，２）
　曲げクリープ試験用のサンプルとして、下記表に示す組成のアルミナ－シリカ系焼結体を準備した。試験用のサンプルの寸法は、２５ｍｍ×１５ｍｍ×１００ｍｍであった。
　なお、アルミナ－シリカ系焼結体は、平均粒径Ｄ５０が１．０ｍｍ以上のムライト粒子Ａと、平均粒径Ｄ５０が０．１ｍｍ以下のムライト粒子Ｂと、を所定の配合割合で配合したものを１５００℃以上に加熱して焼結させて得た。ムライト粒子Ａ、Ｂは、電融ムライトを破砕して、その粒径に応じてムライトＡ、Ｂに分けたものである。このため、アルミナ－シリカ系焼結体を構成する粗粒（平均結晶粒径Ｄ５０が１．０ｍｍ以上）、および、細粒（平均結晶粒径Ｄ５０が０．１ｍｍ以下）は、結晶相におけるムライト相の割合、および、不純物の含有量が同じ数値である。なお、表中の不純物含有量とは、酸化ナトリウム、酸化カリウム、酸化チタン、酸化鉄の合計含有量である。 EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these Examples.
(Example 1, Comparative Examples 1 and 2)
As a sample for the bending creep test, an alumina-silica-based sintered body having the composition shown in the following table was prepared. The dimensions of the test sample were 25 mm × 15 mm × 100 mm.
The alumina-silica-based sintered body is a mixture of mullite particles A having an average particle diameter D50 of 1.0 mm or more and mullite particles B having an average particle diameter D50 of 0.1 mm or less in a predetermined mixing ratio. Was obtained by heating to 1500 ° C. or higher and sintering. Mullite particles A and B are obtained by crushing electrofused mullite and dividing it into mullite A and B according to the particle size. For this reason, coarse grains (average crystal grain size D50 is 1.0 mm or more) and fine grains (average crystal grain size D50 is 0.1 mm or less) constituting the alumina-silica-based sintered body are mullite in the crystal phase. The ratio of the phase and the content of impurities are the same numerical value. The impurity content in the table is the total content of sodium oxide, potassium oxide, titanium oxide, and iron oxide.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　曲げクリープ試験では、負荷を２．５ＭＰａ、３．５ＭＰａとして、温度１３００℃でクリープ速度（／ｓｅｃ）を測定した。結果を下記表に示す。 In the bending creep test, the creep rate (/ sec) was measured at a temperature of 1300 ° C. under a load of 2.5 MPa and 3.5 MPa. The results are shown in the table below.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　また、曲げクリープ試験では、負荷と破断時間との関係を評価した。結果を図１に示す。
　表２の結果から、結晶相におけるムライト相の割合が９０質量％以上の実施例１のアルミナ－シリカ焼結体は、結晶相におけるムライト相の割合が９０質量％未満の比較例１，２のアルミナ－シリカ焼結体に比べて、クリープ速度が低く、クリープ変形が少ないことが確認された。また、図１の結果から、実施例１のアルミナ－シリカ焼結体は、結晶相におけるムライト相の割合が９０質量％未満の比較例１，２のアルミナ－シリカ焼結体に比べて、クリープ速度が低く、クリープ変形が少ないことが確認された。また、図１の結果から、実施例のアルミナ－シリカ焼結体は、比較例１，２のアルミナ－シリカ焼結体に比べて、クリープ強度が高いことが確認された。 In the bending creep test, the relationship between load and rupture time was evaluated. The results are shown in FIG.
From the results of Table 2, the alumina-silica sintered body of Example 1 in which the proportion of the mullite phase in the crystal phase is 90% by mass or more is that of Comparative Examples 1 and 2 in which the proportion of the mullite phase in the crystal phase is less than 90% by mass. Compared to the alumina-silica sintered body, it was confirmed that the creep rate was low and the creep deformation was small. Further, from the results of FIG. 1, the alumina-silica sintered body of Example 1 was creeped compared to the alumina-silica sintered bodies of Comparative Examples 1 and 2 in which the proportion of the mullite phase in the crystal phase was less than 90% by mass. It was confirmed that the speed was low and the creep deformation was small. Further, from the results of FIG. 1, it was confirmed that the alumina-silica sintered bodies of the examples had higher creep strength than the alumina-silica sintered bodies of Comparative Examples 1 and 2.
（実施例２、比較例３）
　実施例２では、実施例１と同一組成のアルミナ－シリカ焼結体を用いてフロートバスルーフ部材を作製した。これを既存のフロートバスルーフに設置した。また、比較例３として、従来のシリマナイト系の耐火物レンガをフロートバスルーフ部材として設置した。フロートバスルーフ部材の寸法および形状は、前述した通りである。また、使用時のフロートバスルーフ部材に加わる最大応力は、前記前述した通りである。フロートバス内の雰囲気温度を１３００℃として４週間経過した後に、比較例３の耐火物レンガは中心部が下向けに撓んでおり、クリープ変形したことが目視により確認できた。また、耐火物レンガの底面には多くのクラックが発生していた。これに対し、実施例２のフロートバスルーフ部材では、クリープ変形、および、クラックの発生は認められなかった。 (Example 2, Comparative Example 3)
In Example 2, a float bath roof member was produced using an alumina-silica sintered body having the same composition as in Example 1. This was installed on the existing float bath roof. As Comparative Example 3, a conventional sillimanite refractory brick was installed as a float bath roof member. The dimensions and shape of the float bath roof member are as described above. Further, the maximum stress applied to the float bath roof member during use is as described above. After 4 weeks with the atmospheric temperature in the float bath set to 1300 ° C., the center portion of the refractory brick of Comparative Example 3 was bent downward, and it was confirmed by visual observation that the creep deformation occurred. In addition, many cracks occurred on the bottom surface of the refractory brick. On the other hand, in the float bath roof member of Example 2, creep deformation and generation of cracks were not recognized.
本出願は、２０１３年４月１８日出願の日本特許出願２０１３－０８７２２４に基づくものであり、その内容はここに参照として取り込まれる。 This application is based on Japanese Patent Application No. 2013-087224 filed on April 18, 2013, the contents of which are incorporated herein by reference.

Claims (9)

  1. 　各々結晶相の９０質量％以上がムライト相であり、かつ、酸化ナトリウム、酸化カリウム、酸化チタン、酸化鉄の合計含有量が２質量％以下のアルミナ－シリカ系焼結体からなり、平均結晶粒径Ｄ５０が１．０ｍｍ以上の粗粒、および、平均結晶粒径Ｄ５０が０．１ｍｍ以下の細粒で構成され、それぞれの質量比が、８５～６０質量％、および、１５～４０質量％であるフロートバスルーフ部材。 90% by mass or more of each crystal phase is a mullite phase, and is composed of an alumina-silica-based sintered body having a total content of sodium oxide, potassium oxide, titanium oxide, and iron oxide of 2% by mass or less. It is composed of coarse grains having a diameter D50 of 1.0 mm or more and fine grains having an average crystal grain diameter D50 of 0.1 mm or less, and the mass ratios thereof are 85 to 60% by mass and 15 to 40% by mass, respectively. A float bath roof member.
  2. 　サンプルサイズ２５ｍｍ×１５ｍｍ×１００ｍｍでの曲げクリープ試験（１３００℃、負荷３．５ＭＰａ）におけるクリープ速度が１×１０-８／ｓｅｃ以下である、請求項１に記載のフロートバスルーフ部材。 The float bath roof member according to claim 1, wherein a creep rate in a bending creep test (1300 ° C, load 3.5 MPa) at a sample size of 25 mm × 15 mm × 100 mm is 1 × 10 −8 / sec or less.
  3. 　サンプルサイズ２５ｍｍ×１５ｍｍ×１００ｍｍでの曲げクリープ試験（１３００℃）における１０００時間クリープ強度が６ＭＰａ以上である、請求項１または２に記載のフロートバスルーフ部材。 The float bath roof member according to claim 1 or 2, wherein a 1000 hour creep strength in a bending creep test (1300 ° C) with a sample size of 25 mm x 15 mm x 100 mm is 6 MPa or more.
  4. 　前記粗粒及び細粒がムライト粒子を含み、該ムライト粒子が電融ムライト粒子である請求項１～３のいずれか一項に記載のフロートバスルーフ部材。 The float bath roof member according to any one of claims 1 to 3, wherein the coarse particles and fine particles contain mullite particles, and the mullite particles are electrofused mullite particles.
  5. 　前記結晶相において、ムライト相以外の結晶相、すなわち、コランダムおよびクリストバライトの含有率が、アルミナ－シリカ系焼結体の結晶相に対して１０質量％以下である請求項１～４のいずれか一項に記載のフロートバスルーフ部材。 The content of crystal phases other than the mullite phase, that is, corundum and cristobalite, in the crystal phase is 10% by mass or less based on the crystal phase of the alumina-silica-based sintered body. The float bath roof member according to Item.
  6. 　前記ムライト相以外の結晶相が、コランダムおよびクリストバライトのいずれであって、両者のうち、コランダムの含有割合が高い請求項１～５のいずれか一項に記載のフロートバスルーフ部材。 The float bath roof member according to any one of claims 1 to 5, wherein the crystal phase other than the mullite phase is either corundum or cristobalite, and the corundum content is high in both.
  7. 　内部に溶融スズが収容されるフロートバスと、前記フロートバスの上部に設置されるフロートバスルーフと、を備えるフロート板ガラス製造装置であって、
    　前記フロートバスルーフが、請求項１～６のいずれか一項に記載のフロートバスルーフ部材で構成されていることを特徴とするフロート板ガラス製造装置。     A float sheet glass manufacturing apparatus comprising: a float bath in which molten tin is housed; and a float bath roof installed on top of the float bath,
    An apparatus for producing a float sheet glass, wherein the float bath roof is constituted by the float bath roof member according to any one of claims 1 to 6.
  8. 　請求項７に記載のフロート板ガラス製造装置を使用してフロート板ガラスを作製することを含むフロート板ガラス製造方法。 A float plate glass manufacturing method including producing a float plate glass using the float plate glass manufacturing apparatus according to claim 7.
  9. 　前記フロート板ガラスが、ディスプレイ用のフロートガラスであり、該フロートガラスの厚さが０．７ｍｍ以下である請求項８に記載のフロート板ガラス製造方法。 The float plate glass manufacturing method according to claim 8, wherein the float plate glass is a float glass for display, and the thickness of the float glass is 0.7 mm or less.
PCT/JP2014/060738 2013-04-18 2014-04-15 Float bath roof member, float plate glass production device using same, and method for producing float plate glass WO2014171459A1 (en)

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JP3217177B2 (en) 1993-02-12 2001-10-09 旭硝子株式会社 Float glass manufacturing equipment
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JP2011251896A (en) * 2010-06-01 2011-12-15 Lg Chem Ltd Apparatus and method for manufacturing glass plate

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019195635A1 (en) * 2018-04-06 2019-10-10 Corning Incorporated Purified aluminosilicate refractory compositions

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