CN103492329A - Method for producing glass plate - Google Patents
Method for producing glass plate Download PDFInfo
- Publication number
- CN103492329A CN103492329A CN201380000355.4A CN201380000355A CN103492329A CN 103492329 A CN103492329 A CN 103492329A CN 201380000355 A CN201380000355 A CN 201380000355A CN 103492329 A CN103492329 A CN 103492329A
- Authority
- CN
- China
- Prior art keywords
- glass
- brick
- molten tin
- low melting
- melting point
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- 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
Abstract
Provided is a method for producing a glass plate comprising a step of making molten glass (G) flow on molten tin (M) and molding the same, the molten glass (G) being continuously supplied onto the molten tin (M) in a bath (22), wherein the glass for the glass plate is an alkali free glass and the temperature of the molten glass (G) at which viscosity of the molten glass (G) becomes 104dPas is 1,200 DEG C or more. Each bottom brick (36) of the bath (22) has a total amount of a low melting element of 20 mass% or less in terms of oxides. The low melting element is an element in which the eutectic point in a binary system of oxide of the low melting element and tin oxide (SnO) is lower than the maximum temperature of an upper face (36a) of the corresponding bottom brick (36).
Description
Technical field
The present invention relates to the manufacture method of sheet glass.
Background technology
Manufacturing process as sheet glass, be widely used float glass process.Float glass process flows by making to be supplied to continuously melten glass on the molten tin in bath that to form shape be band plate-like (for example referring to Patent Document 1) on molten tin.
In order to prevent the oxidation of molten tin, the atmosphere on molten tin is set as the reducing atmosphere that contains hydrogen.
Bath for example consists of unlimited upward case shape metal casing and the end brick and the side brick that are arranged in metal casing.As end brick and side brick, generally use aluminum oxide (Al
2o
3)-silicon-dioxide (SiO
2) be brick.
The prior art document
Patent documentation
Patent documentation 1: Japanese kokai publication sho 50-3414 communique
Summary of the invention
Invent problem to be solved
Molten tin in bath is heated from top, and therefore temperature is lower downwards.Therefore, be dissolved in gaseous constituent (such as oxygen or hydrogen, water etc.) in molten tin can be in temperature the upper surface supersaturation of lower end brick separate out and form bubble.In addition, the gas seen through from end brick forms bubble at the upper surface of end brick.
During to a certain extent big or small of these air bubble growths, from the upper surface of end brick, break away from, float to the interface of molten tin and melten glass, at the lower surface formation concavity defect of melten glass.As a result, the contact surface (bottom surface) in the sheet glass as goods and molten tin forms concavity defect (FOBB (Fine Open Bottom Bubble, fine open bottom bubble)).
In the past, the position that produces FOBB disperseed, so the yield rate of sheet glass is low.The inventor this time finds, this situation is particularly remarkable when the glass of sheet glass is the forming temperature non-alkali glass higher than general soda-lime glass.
The present invention completes in view of the above problems, and its purpose is to provide the manufacture method of the sheet glass of the good non-alkali glass of yield rate.
For the means of dealing with problems
In order to address the above problem, the manufacture method of the sheet glass of a mode of the present invention is to have flow on the described molten tin manufacture method of sheet glass of the operation that forms shape of melten glass on the molten tin that makes to be supplied to continuously in bath, wherein,
The glass of described sheet glass is non-alkali glass, and the viscosity of described melten glass reaches 10
4the temperature of described melten glass during dPas is more than 1200 ℃,
In each end brick of described bath, it is below 20 quality % that the total content of low melting point element is converted into oxide compound,
The eutectic point of the oxide compound that described low melting point element is this low melting point element and two composition systems of stannic oxide (SnO) is lower than the element of the top temperature of the upper surface of corresponding brick of the described end.
The invention effect
According to the present invention, provide the manufacture method of the sheet glass of the good non-alkali glass of yield rate.
The accompanying drawing explanation
Fig. 1 is the explanatory view of the float bath that uses in the forming process of non-alkali glass plate of an embodiment of the invention.
Fig. 2 means the figure of molten tin to the relation of the shape of the bubble that forms on the wettability of the end brick of an embodiment of the invention and end brick.
Fig. 3 means the figure of molten tin to the relation of the shape of the bubble that forms on the wettability of brick of the existing end and end brick.
Fig. 4 is the SEM photo of cut surface of the crucible of embodiment 1.
Fig. 5 is the explanatory view of test that the evaluation in embodiment 1 is investigated with the number of defects of formation on glass.
Fig. 6 is the SEM photo of cut surface of the crucible of comparative example 1.
Fig. 7 is the SEM photo that amplify the part of Fig. 6.
Fig. 8 utilizes the EDS pair of zone identical with the SEM photo of Fig. 7 to carry out ultimate analysis and the Sn element spectral that obtains.
Fig. 9 utilizes the EDS pair of zone identical with the SEM photo of Fig. 7 to carry out ultimate analysis and the Al element spectral that obtains.
Figure 10 utilizes the EDS pair of zone identical with the SEM photo of Fig. 7 to carry out ultimate analysis and the Si element spectral that obtains.
Figure 11 is the SEM photo of cut surface of the crucible of reference example 1.
Embodiment
Below, with reference to accompanying drawing to describing for implementing mode of the present invention.In addition, in following accompanying drawing, also description thereof is omitted for the symbol same or corresponding to same or corresponding formation mark.
The manufacture method of the sheet glass of present embodiment has for example melting process, forming process, annealing operation and cut-out operation.
In melting process, plurality of raw materials is mixed with to the frit fusing formed, obtains melten glass.After dropping in smelting furnace by frit, utilize the flame radiation heat of spraying from burner to make its fusing, make melten glass.
In forming process, the melten glass obtained in melting process is supplied on the molten tin in bath continuously, makes melten glass flow and form shape on molten tin, obtain plate glass (so-called glass ribbon).Plate glass carries out cooling in mobile along pre-determined direction, and mentions from molten tin.
In annealing operation, by the plate glass that obtains in forming process in the annealing furnace annealing.Plate glass is annealed in the outlet horizontal feed from the entrance of annealing furnace in annealing furnace on roller.
Cut off in operation, use stapling machine that the plate glass after annealing in annealing operation is cut into to predetermined size.Cut off in operation, two edge parts (so-called ear) of the width of plate glass are cut.This is because two edge parts of the width of plate glass are subject to the impact of surface tension etc. and become thicker.
Like this, obtain the sheet glass as goods.The glass of sheet glass is alkali-free metal oxide (Na in fact
2o, K
2o, Li
2o etc.) non-alkali glass.In non-alkali glass, for example the total content of alkalimetal oxide can, for below 0.1 quality %, can be used as the substrate that for example liquid-crystal display is used and use.
Non-alkali glass is for example with mean to contain 50%～73% SiO of (preferably 50～66%) of the quality % based on oxide compound
2, 10.5%～24% Al
2o
3, 0%～12% B
2o
3, 0%～8% MgO, 0%～14.5% CaO, 0%～24% SrO, 0%～13.5% BaO, 0%～5% ZrO
2, and MgO+CaO+SrO+BaO is 8%～29.5% (preferably 9%～29.5%).
In the situation that take into account high strain-point and high melting, preferably non-alkali glass means to contain 58%～66% SiO with the quality % based on oxide compound
2, 15%～22% Al
2o
3, 5%～12% B
2o
3, 0%～8% MgO, 0%～9% CaO, 3%～12.5% SrO, 0%～2% BaO, and MgO+CaO+SrO+BaO is 9%～18%.
In the situation that want to obtain extra high strain point, preferably non-alkali glass means to contain 54%～73% SiO with the quality % based on oxide compound
2, 10.5%～22.5% Al
2o
3, 0%～5.5% B
2o
3, 0%～8% MgO, 0%～9% CaO, 0%～16% SrO, 0%～2.5% BaO, and MgO+CaO+SrO+BaO is 8%～26%.
In the situation of non-alkali glass, the viscosity of melten glass reaches 10
4the temperature of melten glass during dPas (pool) is more than 1200 ℃.The viscosity of melten glass reaches approximately 10
4the position of dPas is set near the entrance 12 of the float bath 10 (with reference to figure 1) used in forming process usually.The melten glass be supplied on molten tin M at entrance 12 places of float bath 10 forms in mobile along pre-determined direction.
Fig. 1 is the explanatory view of the float bath that uses in the forming process of sheet glass of an embodiment of the invention.
In float bath 10 (being designated hereinafter simply as " groove 10 "), the melten glass G that makes to be supplied to continuously on the molten tin M in bath 22 flows and forms shape on molten tin M.After being supplied on molten tin M by melten glass G near the entrance 12 of groove 10, carry out coolingly in mobile along pre-determined direction, mention from molten tin M near the outlet 14 of groove 10.
Groove 10 is by the bath 22 of accommodating molten tin M, along the sidewall 24 of the periphery upper limb setting of bath 22 with link with sidewall 24 and the ceiling 26 etc. that covers the top of bath 22 forms.Be provided with on ceiling 26 to the gas that is formed on the space 28 supply reducing gas between bath 22 and ceiling 26 and supply with road 30.In addition, gas is supplied with in road 30 and is inserted and be connected with the well heater 32 as heating source.
In order to prevent the oxidation of molten tin M, gas is supplied with road 30 and is supplied with reducing gas to the space 28 in groove 10.The hydrogen that reducing gas contains 1～15 volume % for example, the nitrogen of 85～99 volume %.In order to prevent that atmosphere from sneaking into from the gap between the brick that forms sidewall 24 etc., the spaces 28 in groove 10 are set as higher than atmospheric air pressure.
For the temperature distribution in regulating tank 10, at for example flow direction of melten glass G (directions X) and the upper compartment of terrain of width (Y-direction), be provided with a plurality of well heaters 32.The output rating of control heater 32 so that the temperature of melten glass G from the entrance 12 of groove 10, towards outlet 14, reduce gradually.In addition, the output rating of control heater 32 is so that the thickness of melten glass G reaches even on width (Y-direction).
Bath 22 consists of unlimited upward case shape metal casing 34 and the end brick 36 and the side bricks 38 that are arranged in metal casing 34.Metal casing 34 prevent atmosphere from the side or below sneak in bath 22.At the bottom of polylith, brick 36 is two-dimensional arrangements with the slight gap of the degree that can not be in contact with one another because of thermal expansion.At the bottom of polylith, brick 36 is surrounded by the polylith side brick 38 that is arranged in ring-type.
Molten tin M in bath 22 is heated from top by well heater 32, and therefore, temperature is lower downwards.Therefore, the upper surface 36a supersaturation that is dissolved in the end brick 36 that gaseous constituent (such as oxygen or hydrogen, water etc.) in molten tin M is lower in temperature is separated out and forms bubble B.The gas seen through from end brick 36 in addition, (such as hydrogen etc.) form bubble B at the upper surface 36a of end brick 36.
When these bubbles B grows into to a certain degree big or small, from the upper surface 36a of end brick 36, break away from, float to the interface of molten tin M and melten glass G, at the lower surface formation concavity defect of melten glass G.As a result, the contact surface (bottom surface) at the sheet glass as goods and molten tin M forms concavity defect (FOBB).
The inventor is conceived to: in the situation that the total mass of the bubble B of unit time generation is identical, the size of bubble B is larger one by one, and the quantity of bubble B is fewer.In order to make bubble B grow greatlyr, importantly reduce the wettability of molten tin M to end brick 36 on end brick 36.
Fig. 2 means the figure of molten tin to the relation of the shape of the bubble that forms on the wettability of the end brick of an embodiment of the invention and end brick.Fig. 3 means the figure of molten tin to the relation of the shape of the bubble that forms on the wettability of brick of the existing end and end brick.The molten tin of Fig. 2 to the wettability of the end brick of present embodiment lower than the molten tin of Fig. 3 the wettability to brick of the existing end." wettability is low " refers to that molten tin is difficult for brick of the wetting end, and " wettability is high " refers to easily brick of the wetting end of molten tin.For ease of explanation, the shape of bubble when first high to wettability describes.
As shown in Figure 3, in the past, because wettability is high, therefore, molten tin M was little to the contact angle θ 100 of end brick 6, and end brick 6 is little with the contact area of bubble B100.Therefore, molten tin M wants to enter between end brick 6 and bubble B100, so bubble B100 is growing to such an extent that easily from end brick 6, break away from and form a plurality of small bubbles B100 before large.
Generally speaking, molten metal is low to the wettability of oxide compound, and therefore, when the production of sheet glass starts, molten tin M is low to the wettability of end brick 6.But think, follow the process of time, the stannic oxide contained on a small quantity in molten tin M as impurity reacts with end brick 6 and forms responding layer (metamorphic layer) on the surface of end brick 6, and therefore, wettability uprises.
On the other hand, in present embodiment, in order to suppress reacting of molten tin M and end brick 36, using the total content of low melting point element to be converted into oxide compound is that the following brick of 20 quality % is as each end brick 36.The eutectic point of the oxide compound that " low melting point element " is this low melting point element and two composition systems of stannic oxide (SnO) is lower than the element of the top temperature of the upper surface 36a of corresponding end brick 36.Temperature can produce liquid phase during higher than eutectic point, and therefore, the oxide compound of low melting point element carries out with reacting acutely of stannic oxide.Stannic oxide contains in molten tin M as the impurity trace, the stannic oxide in molten tin M optionally with end brick 36 in the high part of the concentration of low melting point element react.The stannic oxide contained in molten tin M is because molten tin M is exposed to when reason based on producing makes sidewall 24 to atmosphere opening the air that enters in groove 10, gap between the brick that forms sidewall 24 is sneaked into the air in groove 10 and formed.
At this, for " the total content of low melting point element ", when the low melting point element number is a kind, be the content of a kind of low melting point element, at the low melting point element number, while being multiple, be the total content of multiple low melting point element.
The top temperature of the upper surface 36a of end brick 36 is because of each end brick 36 different (more downstream is lower), and therefore, the kind of low melting point element also can be different because of each end brick 36.Near the outlet 14 of groove 10, the top temperature of the upper surface 36a of end brick 36a is low, therefore, in end brick 36, can not have low melting point element.
As low melting point element, can enumerate such as silicon (Si) etc.Oxide compound (the SiO of silicon
2) with the eutectic point of stannic oxide be approximately 850 ℃, lower than the top temperature of the upper surface 36a of brick of most of end 36.
In present embodiment, in each end brick 36, to be converted into oxide compound be 20 quality % following (preferably 15 quality % are following, more preferably 10 quality % are following) to the total content of low melting point element, and therefore, each end brick 36 reacts hardly with molten tin M.This be because, it is 20 quality % when following that the total content of low melting point element is converted into oxide compound, other elements formation oxide compounds in most of low melting point element and end brick 36, the fusing point of this oxide compound is higher than the top temperature of the upper surface 36a of end brick 36.Because each end brick 36 reacts hardly with molten tin M, therefore, the production from sheet glass start after after a while, molten tin M is also low to the wettability of each end brick 36.
In addition, in present embodiment, in each end brick 36, to be converted into oxide compound be below 20 quality % to the total content of low melting point element, but also can not make the total content of low melting point element in brick 36 of whole ends be converted into oxide compound, is below 20 quality %.As long as the viscosity that the top temperature of the upper surface of end brick is melten glass G reaches 10
4it is to get final product below 20 quality % that the total content of the low melting point element at the bottom of at least one of the temperature of the following and oxide compound that surpasses low melting point element of the temperature of melten glass G during dPas and the eutectic point of two composition systems of stannic oxide in brick is converted into oxide compound, can surpass 0 quality %.
Molten tin M is low to the wettability of each end brick 36, and therefore, as shown in Figure 2, molten tin M is large to the contact angle θ of end brick 36, and end brick 36 is large with the contact area of bubble B.Therefore, molten tin M is difficult for entering between end brick 6 and bubble B, at bubble B, grows to such an extent that can not break away from from end brick 36 before large.
Like this, according to present embodiment, the size of bubble B becomes large one by one, and therefore, in the situation that the total mass of the bubble B of unit time generation is identical, the quantity of the bubble B that the unit time produces reduces.As a result, the quantity that is formed on the FOBB on the bottom surface of sheet glass reduces, and FOBB improves the yield rate of sheet glass.Reason based on following (1)～(2), obtain this effect significantly in the situation that the glass of sheet glass is non-alkali glass.
(1) with general soda-lime glass, compare, the forming temperature of the melten glass G of non-alkali glass is high, and the temperature of the upper surface 36a of end brick 36 is high.Therefore, in the situation that the chemical constitution of end brick 36 is identical, end brick 36 carries out with reacting easily of molten tin M.
(2) different from soda-lime glass, non-alkali glass is alkali-free metallic element (for example Na, K) in fact, therefore, can cause hardly nepheline ((Na, K) AlSiO of end brick 36
4) change.In nephelinization, form fine and close glass coating on end brick 36, suppress gas and see through to upper surface 36a from the inside of end brick 36.Cause hardly nephelinization in non-alkali glass, therefore, the total mass of the bubble B that the unit time produces increases.
In addition, in present embodiment, as mentioned above, each end brick 36 reacts hardly with molten tin M, and therefore, the rotten of upper surface 36a of end brick 36 is suppressed, and the disengaging of rotten particle is suppressed.The particle broken away from floats to the interface of molten tin M and melten glass G, becomes thus the defect of melten glass G, therefore, by suppressing the disengaging of particle, can improve the quality of sheet glass.
As end brick 36, use for example aluminum oxide (Al
2o
3)-calcium oxide (CaO) is brick or aluminum oxide (Al
2o
3)-zirconium white (ZrO
2) be the clayey burnt bricks such as brick.Use SiO in the clayey burnt brick
2deng as sintering aid, there is SiO
2the part that concentration is high.
Aluminum oxide-calcium oxide is that brick for example means to contain 40%～85% Al with the quality % based on oxide compound
2o
3, 10%～40% CaO, 0.5%～20% SiO
2.SiO
2content is preferably below 15 quality %, more preferably, below 10 quality %, more preferably, below 7 quality %, is particularly preferably below 3 quality %, further is particularly preferably below 1 quality %.
Aluminium oxide-zirconium oxide is that brick for example means to contain 40%～55% Al with the quality % based on oxide compound
2o
3, 30%～45% ZrO
2, 0.5%～20% SiO
2.SiO
2content is preferably below 15 quality %, more preferably, below 10 quality %, more preferably, below 7 quality %, is particularly preferably below 3 quality %, further is particularly preferably below 1 quality %.
It is below 20 quality % that side brick 38 can similarly make the total content of low melting point element be converted into oxide compound with end brick 36, also can surpass 20 quality %.During shaping, melten glass G is positioned at the inboard of side brick 38, and therefore, the bubble formed on the inner-wall surface of side brick 38 can not become the reason of FOBB.
In addition, the sheet glass of above-mentioned embodiment is used as the substrate of liquid-crystal display, but purposes also can be varied.For example, sheet glass can be used as the substrate of OLED display, the protective glass of touch panel is used.
Embodiment
Below, by embodiment etc., the present invention is specifically described.
[embodiment 1]
At first, brick is processed to prepare crucible, the metallic tin of packing in ready crucible, be arranged in electric furnace, after the atmosphere in electric furnace is replaced, under the condition of 1000 ℃, 60 minutes, makes the metallic tin melting, investigates the reactivity of molten tin and crucible.
As brick, prepare as aluminum oxide (Al
2o
3)-calcium oxide (CaO) is the brick A of brick.Brick A means to contain 5.7% SiO with the quality % based on oxide compound
2, 66.0% Al
2o
3, 26.0% CaO, 1.5% MgO, 0.3% Na
2o, 0.1% Fe
2o
3, other compositions are separately lower than 0.1%.The chemical constitution of brick A is utilized fluorescent x-ray analyzer, and (electrical industry of science Co., Ltd. manufactures, and ZSX100e) is measured.
Crucible is processed into to round-ended cylinder shape (the thickness 3mm of internal diameter 6mm, internal height 6mm, diapire, the thickness 2mm of sidewall).
Metallic tin is used the metallic tin that purity is 99.95 quality % (Northeast chemical company manufactures, superfine).So that the mode weighing metallic tin that the thickness of molten tin is 5mm is put into crucible.
For the atmosphere in electric furnace, use vacuum pump by after being evacuated to 1kPa in electric furnace, by gas supply pipe, to supply gas in electric furnace, replaced.As gas, use the nitrogen that oxygen concentration is 1000 volume ppm.Use nitrogen to be because the reactivity of nitrogen and oxygen is low, bring impact can to oxygen concentration.
The reactivity of molten tin and crucible by the crucible that makes to be cooled to room temperature with resin, solidify after by its cut-out, (scanning electronic microscope ， キ ー エ Application ス company manufactures, and VE-9800) observes cut surface and is investigated to use SEM.
Fig. 4 shows the SEM photo of cut surface of the crucible of embodiment 1.Shown by Fig. 4, at the inner bottom surface of crucible 41, do not observe the responding layer with molten tin 44.In addition, between crucible 41 and molten tin 44, formed partly gap 45, the wettability of 44 pairs of crucibles 41 of known molten tin is low.
Fig. 5 shows the test of the evaluation of investigation embodiment 1 with the number of defects of formation on glass.In this test, prepare brick A is processed and the crucible 51 that obtains, the metallic tin of packing in ready crucible 51, will estimate with glass 53 and load on carbon jig 52.Then, crucible 51 is arranged in the electric furnace of glove box, after the atmosphere in electric furnace is replaced, the temperature in the rising electric furnace, make to estimate with glass 53 thermal distortion and loading on molten tin 54 under conducting oneself with dignity.Then, the temperature in electric furnace is kept 10 minutes under 1100 ℃, then, the temperature in electric furnace is reduced to 800 ℃, manually the evaluation of solidifying is mentioned from molten tin 54 with glass 53.Then, in electric furnace, to estimating, with glass 53, annealed, investigated the quantity of estimating the FOBB formed on the part contacted with molten tin 54 with glass 53.
Metallic tin is used the metallic tin that purity is 99.95 quality % (Northeast chemical company manufactures, superfine).So that the mode weighing metallic tin that the thickness of molten tin is 20mm is put into crucible.
As estimating with glass 53, prepare non-alkali glass plate (vertical 40mm, horizontal 40mm, thickness 0.7mm).This non-alkali glass plate means to contain 60.0% SiO with the quality % based on oxide compound
2, 17.0% Al
2o
3, 8.0% B
2o
3, 3.0% MgO, 4.5% CaO, 7.5% SrO.The chemical constitution of sheet glass is utilized fluorescent x-ray analyzer, and (electrical industry of science Co., Ltd. manufactures, and ZSX100e) is measured.
For the atmosphere in electric furnace, use vacuum pump by after being evacuated to 1kPa in electric furnace, by gas supply pipe, to supply gas in electric furnace, replaced.As gas, use the nitrogen that density of hydrogen is 10 volume %.
Estimate with defect (FOBB) number formed on glass 53 by will estimate be cooled to room temperature with glass 53 after, the part (5mm * 5mm) that contacts with molten tin 54 with glass 53 of use observation by light microscope evaluation investigated.Large defect (diameter is greater than 300 μ m) number is 0, and little defect (diameter 10～300 μ m) number is 2.In addition, little number of defects is in a ratio of below 10% with the sum of large number of defects and the situation of comparative example described later 1.
Infer that the few reason of number of defects is, few as the content of low melting point element Si in the brick A of the material of crucible 51.Because the content of Si is few, therefore as shown in Figure 4, crucible 41 reacts hardly with molten tin 44, and the wettability of 44 pairs of crucibles 41 of molten tin is low.Because wettability is low, therefore as shown in Figure 3, the bubble formed on the inner bottom surface of crucible is difficult for floating, under the state that keeps bubble, grows greatlyr, result, and little number of defects is few.
[embodiment 2]
In embodiment 2, prepare as aluminum oxide (Al
2o
3)-calcium oxide (CaO) is the brick B of brick, investigates similarly to Example 1 the number of defects of estimating with formation on glass.Brick B means to contain 5.8% SiO with the quality % based on oxide compound
2, 82.4% Al
2o
3, 10.2% CaO, 1.2% MgO, 0.2% Na
2o, 0.2% Fe
2o
3, other compositions are separately lower than 0.1%.
Large defect (diameter is greater than 300 μ m) number is 0, and little defect (diameter 10～300 μ m) number is below 10.
[embodiment 3]
In embodiment 3, prepare as aluminum oxide (Al
2o
3)-zirconium white (ZrO
2) be the brick C of brick, in addition, investigate similarly to Example 1 the number of defects of estimating with formation on glass.Brick C means to contain 13.5% SiO with the quality % based on oxide compound
2, 33.0% ZrO
2, 52.0% Al
2o
3, 1.3% Na
2o, other compositions are separately lower than 0.1%.
Large defect (diameter is greater than 300 μ m) number is 0, and little defect (diameter 10～300 μ m) number is 15.
[comparative example 1]
In comparative example 1, prepare as aluminum oxide (Al
2o
3)-silicon-dioxide (SiO
2) be the brick D of brick, in addition, investigate similarly to Example 1 the reactivity of brick and molten tin.Brick D means to contain 58.0% SiO with the quality % based on oxide compound
2, 37.0% Al
2o
3, 0.4% CaO, 0.1% MgO, 0.4% P
2o
5, 0.1% Na
2o, 0.9% K
2o, 1.2% Fe
2o
3, 0.9% TiO
2, 0.1% ZrO
2, other compositions are separately lower than 0.1%.
Fig. 6 shows the SEM photo of cut surface of the crucible of comparative example 1.Fig. 7 shows the SEM photo of the part amplification of Fig. 6.Shown by Fig. 6 and Fig. 7, at the inner bottom part of crucible 61, observe the responding layer 66 with molten tin 64.In addition, crucible 61 is closely sealed with molten tin 64, and the wettability of 64 pairs of crucibles 61 of known molten tin is high.
Fig. 8 shows and utilizes the EDS pair of zone identical with the SEM photo of Fig. 7 to carry out ultimate analysis and the Sn element spectral that obtains, Fig. 9 shows and utilizes the EDS pair of zone identical with the SEM photo of Fig. 7 to carry out ultimate analysis and the Al element spectral that obtains, and Figure 10 shows and utilizes the EDS pair of zone identical with the SEM photo of Fig. 7 to carry out ultimate analysis and the Si element spectral that obtains.In Fig. 8～Figure 10, the part that brightness is higher, mean that concentration of element is higher.As EDS (Energy Dispersive X-ray Spectrometry, X-ray energy spectrometer), use the subsidiary EDS of above-mentioned SEM.
From Fig. 8～Figure 10, part 67 Sn of place that Al is few and Si is many in the inner bottom part of crucible 61 increase.This part that shows that molten tin 64 is high with Si concentration in crucible 61 has optionally occurred to react.
In addition, in comparative example 1, except using above-mentioned brick D as brick, investigate similarly to Example 1 the number of defects of estimating with formation on glass.As a result, large defect (diameter is greater than 300 μ m) number is 0, and little defect (diameter 10～300 μ m) number is 60.
Infer that the reason that number of defects is many is as the content of low melting point element Si in the brick D of crucible material many.Because the content of Si is many, therefore as shown in Figure 6 and Figure 7, the responding layer 66 of formation and molten tin 64 in crucible 61, the wettability of 64 pairs of crucibles 61 of molten tin is high.Because wettability is high, therefore as shown in Figure 2, the bubble formed on the inner bottom surface of crucible is at less state float downward, result, and little number of defects is many.
[comparative example 2]
In comparative example 2, prepare as aluminum oxide (Al
2o
3)-silicon-dioxide (SiO
2) be the brick E of brick, similarly investigate with comparative example 1 number of defects of estimating with formation on glass.Brick E means to contain 58.0% SiO with the quality % based on oxide compound
2, 37.0% Al
2o
3, 0.2% CaO, 0.3% MgO, 0.8% Na
2o, 0.9% K
2o, 1.1% Fe
2o
3, 1.6% TiO
2, other compositions are separately lower than 0.1%.
As a result, large defect (diameter is greater than 300 μ m) number is 0, and little defect (diameter 10～300 μ m) number is 70.
[reference example 1]
In reference example 1, as the gas in the electric furnace be supplied to after vacuumizing, the reducing gas that uses the nitrogen by the hydrogen of 10 volume % and 90 volume % to form, in addition, similarly investigate the reactivity of brick D and molten tin with comparative example 1.
The SEM photo of cut surface of the crucible of reference example 1 has been shown in Figure 11.Shown by Figure 11, do not observe the responding layer with molten tin 74 on crucible 71.In addition, between crucible 71 and molten tin 74, formed partly gap 75, the wettability of 74 pairs of crucibles 71 of known molten tin is low.
From the result of reference example 1 and the result of comparative example 1, the oxygen of the trace contained in the atmosphere on molten tin 74 brings impact to the wettability of brick and molten tin.Oxygen dissolves in molten tin, the SnO composition in molten tin and the SiO of crucible 71
2when the composition reaction forms responding layer, wettability improves.
By the results are shown in table 1 of the evaluation of embodiment 1～3, comparative example 1,2.In table 1, the composition of brick only illustrates SiO
2, Al
2o
3, CaO, MgO and ZrO
2.
Table 1
Above, by embodiment and embodiment etc., the manufacture method of sheet glass is illustrated, but the present invention is not limited to the above-described embodiment and examples etc.Carry out various distortion, improvement in the scope of the purport of the present invention that can put down in writing at claims.
The application requires the right of priority of No. 2012-072495, the Japanese Patent Application that proposes to the Japanese Patent Room based on March 27th, 2012, and the full content of No. 2012-072495, Japanese Patent Application is quoted in the international application of Dao Ben.
Label declaration
10 float baths
The entrance of 12 float baths
The outlet of 14 float baths
22 baths
24 sidewalls
26 ceilings
28 spaces
30 gases are supplied with road
32 well heaters
34 metal casings
36 end bricks
38 side bricks
The M molten tin
The G melten glass
Claims (7)
1. the manufacture method of a sheet glass, have the melten glass that makes to be supplied to continuously on the molten tin in bath and flow and form the operation of shape on described molten tin, in described manufacture method,
The glass of described sheet glass is non-alkali glass, and the viscosity of described melten glass reaches 10
4the temperature of described melten glass during dPas is more than 1200 ℃,
In each end brick of described bath, it is below 20 quality % that the total content of low melting point element is converted into oxide compound,
The eutectic point of the oxide compound that described low melting point element is this low melting point element and two composition systems of stannic oxide (SnO) is lower than the element of the top temperature of the upper surface of corresponding brick of the described end.
2. the manufacture method of a sheet glass, have the melten glass that makes to be supplied to continuously on the molten tin in bath and flow and form the operation of shape on described molten tin, in described manufacture method,
The glass of described sheet glass is non-alkali glass, and the viscosity of described melten glass reaches 10
4the temperature of described melten glass during dPas is more than 1200 ℃,
Described bath comprises end brick,
The viscosity that the top temperature of the upper surface of end brick is described melten glass reaches 10
4the temperature of described melten glass during dPas is following and surpass at the bottom of at least one of temperature of eutectic point of two composition systems of the oxide compound of low melting point element and stannic oxide (SnO) in brick, it is below 20 quality % that the total content of low melting point element is converted into oxide compound
The eutectic point of the oxide compound that described low melting point element is this low melting point element and two composition systems of stannic oxide (SnO) is lower than the element of the top temperature of the upper surface of corresponding brick of the described end.
3. the manufacture method of sheet glass as claimed in claim 1 or 2, wherein, described low melting point element is silicon (Si).
4. as the manufacture method of the described sheet glass of any one in claim 1～3, wherein, brick of the described end is aluminum oxide (Al
2o
3)-calcium oxide (CaO) is brick or aluminum oxide (Al
2o
3)-zirconium white (ZrO
2) be brick.
5. as the manufacture method of the described sheet glass of any one in claim 1～4, wherein, described non-alkali glass means to contain 50%～73% SiO with the quality % based on oxide compound
2, 10.5%～24% Al
2o
3, 0%～12% B
2o
3, 0%～8% MgO, 0%～14.5% CaO, 0%～24% SrO, 0%～13.5% BaO, 0%～5% ZrO
2, and MgO+CaO+SrO+BaO is 8%～29.5%.
6. the manufacture method of sheet glass as claimed in claim 5, wherein, described non-alkali glass means to contain 58%～66% SiO with the quality % based on oxide compound
2, 15%～22% Al
2o
3, 5%～12% B
2o
3, 0%～8% MgO, 0%～9% CaO, 3%～12.5% SrO, 0%～2% BaO, and MgO+CaO+SrO+BaO is 9%～18%.
7. the manufacture method of sheet glass as claimed in claim 5, wherein, described non-alkali glass means to contain 54%～73% SiO with the quality % based on oxide compound
2, 10.5%～22.5% Al
2o
3, 0%～5.5% B
2o
3, 0%～8% MgO, 0%～9% CaO, 0%～16% SrO, 0%～2.5% BaO, and MgO+CaO+SrO+BaO is 8%～26%.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012072495 | 2012-03-27 | ||
| JP2012-072495 | 2012-03-27 | ||
| PCT/JP2013/053756 WO2013145922A1 (en) | 2012-03-27 | 2013-02-15 | Method for producing glass plate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103492329A true CN103492329A (en) | 2014-01-01 |
| CN103492329B CN103492329B (en) | 2015-12-02 |
Family
ID=49259204
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201380000355.4A Active CN103492329B (en) | 2012-03-27 | 2013-02-15 | The manufacture method of sheet glass |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JPWO2013145922A1 (en) |
| KR (1) | KR101384375B1 (en) |
| CN (1) | CN103492329B (en) |
| TW (1) | TW201339110A (en) |
| WO (1) | WO2013145922A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105621864A (en) * | 2014-11-25 | 2016-06-01 | 旭硝子株式会社 | Float glass production device and float glass production method |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015224150A (en) * | 2014-05-27 | 2015-12-14 | 旭硝子株式会社 | Method for producing alkali-free glass |
| DE102017124625A1 (en) * | 2016-12-22 | 2018-06-28 | Schott Ag | Thin glass substrate, method and apparatus for its manufacture |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5420087A (en) * | 1993-02-17 | 1995-05-30 | Didier-Werke Ag | Refractory or fireproof brick as tin bath bottom brick |
| CN1898168A (en) * | 2003-12-26 | 2007-01-17 | 旭硝子株式会社 | Alkali - free glass and its production method and liquid crystal display panel |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07109129A (en) * | 1993-10-12 | 1995-04-25 | Yootai:Kk | Fire brick for lining float bath |
| JP3988209B2 (en) * | 1996-06-03 | 2007-10-10 | 旭硝子株式会社 | Alkali-free glass and liquid crystal display panel |
| JP4612331B2 (en) * | 2004-04-30 | 2011-01-12 | オーセラ株式会社 | Refractory material for float bath and float bath |
| JP4789058B2 (en) * | 2004-06-23 | 2011-10-05 | 日本電気硝子株式会社 | Alkali-free glass substrate |
| WO2009054314A1 (en) * | 2007-10-25 | 2009-04-30 | Asahi Glass Company, Limited | Method for production of non-alkali glass |
| JP5446030B2 (en) * | 2007-12-19 | 2014-03-19 | 日本電気硝子株式会社 | Glass substrate |
-
2013
- 2013-02-15 KR KR1020137012611A patent/KR101384375B1/en active IP Right Grant
- 2013-02-15 WO PCT/JP2013/053756 patent/WO2013145922A1/en active Application Filing
- 2013-02-15 JP JP2013513436A patent/JPWO2013145922A1/en active Pending
- 2013-02-15 CN CN201380000355.4A patent/CN103492329B/en active Active
- 2013-02-21 TW TW102106086A patent/TW201339110A/en unknown
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5420087A (en) * | 1993-02-17 | 1995-05-30 | Didier-Werke Ag | Refractory or fireproof brick as tin bath bottom brick |
| CN1898168A (en) * | 2003-12-26 | 2007-01-17 | 旭硝子株式会社 | Alkali - free glass and its production method and liquid crystal display panel |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105621864A (en) * | 2014-11-25 | 2016-06-01 | 旭硝子株式会社 | Float glass production device and float glass production method |
| CN105621864B (en) * | 2014-11-25 | 2019-05-07 | Agc 株式会社 | Float glass manufacturing device and float glass making process |
Also Published As
| Publication number | Publication date |
|---|---|
| KR101384375B1 (en) | 2014-04-10 |
| TW201339110A (en) | 2013-10-01 |
| WO2013145922A1 (en) | 2013-10-03 |
| JPWO2013145922A1 (en) | 2015-12-10 |
| KR20130119441A (en) | 2013-10-31 |
| CN103492329B (en) | 2015-12-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102066276B (en) | LAS-type float glass | |
| CN104039730B (en) | Glass base plate for chemical reinforcement, and method for producing same | |
| EP2398745A1 (en) | Spinel isopipe for fusion forming alkali containing glass sheets | |
| WO2014127108A1 (en) | High volume production of display quality glass sheets having low zirconia levels | |
| CN104876425A (en) | Float Process For Producing A Float Glass Pane And Float Glass Pane | |
| US11584680B2 (en) | Alkali-free glass substrate | |
| CN103492329B (en) | The manufacture method of sheet glass | |
| TW201345849A (en) | Glass plate | |
| CN107759055B (en) | Float glass plate and method for producing same | |
| WO2017002844A1 (en) | Glass substrate production method and glass substrate production device | |
| CN101443283A (en) | Process for producing alkali-free glass | |
| US20190084860A1 (en) | Alkali-free glass substrate | |
| KR20140118848A (en) | Method for making glass sheet | |
| KR102080003B1 (en) | Method for producing glass plate, and glass plate | |
| KR102141856B1 (en) | Alkali-free glass substrate | |
| US11718553B2 (en) | Alkali-free glass substrate | |
| JP2022112743A (en) | float glass substrate | |
| KR20220072779A (en) | Alkali-free glass substrate and method for producing alkali-free float glass substrate | |
| CN104487390B (en) | The manufacturing method and glass plate of glass plate | |
| EP3176133A1 (en) | A method of processing a glass | |
| JP2022083980A (en) | Non-alkali glass substrate, and production method of non-alkali float glass substrate | |
| JP2007302509A (en) | Method for manufacturing glass and apparatus related to manufacturing of glass | |
| Lindig | Solar Glass Melting | |
| CN104114505A (en) | Plate glass production device, and plate glass production method | |
| CN104797538A (en) | Plate glass production method and plate glass production device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CP01 | Change in the name or title of a patent holder | ||
| CP01 | Change in the name or title of a patent holder |
Address after: Tokyo, Japan Patentee after: AGC Corporation Address before: Tokyo, Japan Patentee before: Asahi Glass Co., Ltd. |