CN103168010A - Method for manufacturing glass plate - Google Patents

Method for manufacturing glass plate Download PDF

Info

Publication number
CN103168010A
CN103168010A CN2012800031085A CN201280003108A CN103168010A CN 103168010 A CN103168010 A CN 103168010A CN 2012800031085 A CN2012800031085 A CN 2012800031085A CN 201280003108 A CN201280003108 A CN 201280003108A CN 103168010 A CN103168010 A CN 103168010A
Authority
CN
China
Prior art keywords
glass
quality
melten glass
temperature
bubble
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
Application number
CN2012800031085A
Other languages
Chinese (zh)
Other versions
CN103168010B (en
Inventor
君岛哲郎
月向仁志
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Avanstrate Inc
Original Assignee
Avanstrate Inc
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Avanstrate Inc filed Critical Avanstrate Inc
Priority to CN201510086677.6A priority Critical patent/CN104724908B/en
Publication of CN103168010A publication Critical patent/CN103168010A/en
Application granted granted Critical
Publication of CN103168010B publication Critical patent/CN103168010B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
    • C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
    • C03B5/225—Refining
    • 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
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
    • C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
    • C03B5/18—Stirring devices; Homogenisation
    • C03B5/187—Stirring devices; Homogenisation with moving elements
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
    • C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
    • C03B5/235—Heating the glass
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
    • C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
    • C03B5/42—Details of construction of furnace walls, e.g. to prevent corrosion; Use of materials for furnace walls
    • C03B5/43—Use of materials for furnace walls, e.g. fire-bricks
    • 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
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Glass Compositions (AREA)

Abstract

This method for manufacturing a glass plate includes a melting step, a fining step, and a forming step. In the melting step, molten glass is produced by using at least electrical heating to melt a glass feedstock containing SnO2 as a fining agent. The fining step includes the following: a bubble-removal process, after the melting step, in which the temperature of the molten glass is raised to at least 1,630 DEG C at a rate of at least 2 DEG C/min so as to generate bubbles therein in order to perform bubble removal; and an absorption process, after the bubble-removal process, in which the temperature of the molten glass is reduced so as to make the molten glass absorb the bubbles therein. In the forming step, the post-fining-step molten glass is formed into plate glass.

Description

The manufacture method of sheet glass
Technical field
The present invention relates to a kind of glass plate manufacturing method that utilizes glass tube down-drawing.
Background technology
In the glass substrate used at the flat-panel monitors such as liquid-crystal display or plasma display (hereinafter referred to as " FPD "), used thickness is for example the thinner sheet glass of 0.5mm～0.7mm.This FPD is for example the size of 300mm * 400mm with glass substrate in 1st generation, but becomes the size of 2850mm * 3050mm in the 10th generation.
In order to manufacture the large-sized FPD glass substrate after this 8th generation, the most often use overflow downdraw.Overflow downdraw is included in forming furnace overflows by the top that makes melten glass self-forming body and is shaped to the operation of plate glass and plate glass is carried out the operation of Slow cooling in the Slow cooling stove below formed body.The Slow cooling stove is by after introducing plate glass between paired roller and being stretched as required thickness, in the mode of the internal strain that reduces plate glass or pyrocondensation, plate glass carried out to Slow cooling.Afterwards, using plate glass be cut into specific size and as sheet glass and lamination on other sheet glass, then take care of.Perhaps by glass plate conveyance to subsequent processing.
The sheet glass that to manufacture by this moulding is formed with the glass substrate of the liquid-crystal display of semiconductor element for glass surface, but for the characteristic of the semiconductor element that do not make to form at this glass surface deteriorated because the glass of glass substrate forms, even and if preferably use and do not contain the sheet glass of alkali metal component fully or contain also few sheet glass of its content.
Yet, if exist bubble can become the reason of display defect in sheet glass, therefore, exist the sheet glass of bubble as glass substrate for plane display device improper.Therefore, require bubble not remain in sheet glass.Especially for liquid crystal display glass substrate or OLED display glass substrate, the requirement of bubble is stricter.
Yet, deteriorated for the characteristic that suppresses semiconductor element, even if do not contain alkali metal component or contain its content, also there are the following problems for a small amount of sheet glass: contain in a large number alkali-metal sheet glass with soda-lime glass etc. and compare, its high temperature viscosity is high, and the melten glass that bubble is difficult in manufacturing breaks away from.
From reduce the viewpoint of carrying capacity of environment, the high As of toxicity that requires restriction to use in the past 2o 3use.Therefore, replace in recent years As 2o 3and will with As 2o 3compare the poor SnO of clarification function 2or Fe 2o 3as finings, use.SnO 2or Fe 2o 3can become the devitrification of glass or painted reason, therefore can't in order to ensure with As 2o 3equal clarification function and being added in glass in a large number.Therefore, bubble more easily remains in the sheet glass as the finished product.
To this, a kind of technology has been proposed, wherein, for example rise to 1650 ℃ and, in carrying out the manufacture method of glass substrate of deaeration, the β that melten glass is had in order to improve the deaeration effect-OH value is for more than 0.485/mm (patent documentation 1) in the non-alkali glass temperature that Vitrification is produced under 1300 ℃～1500 ℃.
The prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2005-97090 communique
Summary of the invention
The problem that invention will solve
Herein, even if be for example also, during a small amount of glass forms, can be dissolved in the SO in melten glass not containing basic metal or containing its content 2melting degree little, therefore once produce SO 2bubble, bubble easily remains in the sheet glass as the finished product as defect.
But, in the technology of putting down in writing at above-mentioned patent documentation 1, existence can't fully suppress to clarify the SO after operation 2the problem of the generation of bubble.
Therefore, the object of the present invention is to provide a kind ofly when manufacturing sheet glass, can reduce efficiently the manufacture method of the sheet glass that remains in the bubble in sheet glass.
For the means of dealing with problems
The 1st mode of the present invention is the manufacture method of sheet glass.
This manufacture method comprises:
Melt operation, wherein, at least utilize the energising heating will contain SnO 2frit as finings melts, thereby makes melten glass;
The clarification operation, it comprises: deaeration is processed, and wherein, after described melting operation, with the heat-up rate more than 2 ℃/minute, the temperature of described melten glass is warming up to more than 1630 ℃, generates thus bubble and carry out deaeration in described melten glass; And absorb processing, and wherein, after described deaeration is processed, make described melten glass cooling, thus the bubble in described melten glass is absorbed in described melten glass; And
Molding procedure, wherein, be shaped to plate glass by the described melten glass after described clarification operation.
Now, the SnO that preferably sheet glass of manufacturing contains 0.01 quality %～0.5 quality % 2.Further, preferably the combination of the sheet glass of manufacturing contains SnO 2and Fe 2o 3, in this case, be preferably the SnO that contains 0.01 quality %～0.5 quality % 2, and the Fe that contains 0.01 quality %～0.1 quality % 2o 3.
The 2nd mode of the present invention, as the manufacture method of the described sheet glass of the 1st mode of the present invention, wherein, in described molding procedure, utilizes overflow downdraw to form plate glass by described melten glass.
The 3rd mode of the present invention is as the of the present invention the 1st or the manufacture method of the described sheet glass of the 2nd mode, wherein, the intensification of the described melten glass in described clarification operation is at least used to connect and is carried out the melting groove of described melting operation and to carry out the metal tube between the clarifying tank of described clarification operation, and is undertaken by the electric current that control flows into described metal tube.
The 4th mode of the present invention is as the manufacture method of the described sheet glass of any one in the 1st～3rd mode of the present invention, and wherein, the viscosity of the described melten glass in the temperature of 1630 ℃ is 130 pools～350 pools.
The 5th mode of the present invention is as the manufacture method of the described sheet glass of any one in the 1st～4th mode of the present invention, wherein, and the R ' of described sheet glass 2the content of O be 0 quality %～2.0 quality % (R ' 2o is Li 2o, Na 2o and K 2the total of contained composition among O).
The 6th mode of the present invention is as the manufacture method of the described sheet glass of any one in the 1st～5th mode of the present invention, and wherein, described sheet glass contains: SiO 2: 50 quality %～70 quality %, B 2o 3: 5 quality %～18 quality %, Al 2o 3: 10 quality %～25 quality %, MgO:0 quality %～10 quality %, CaO:0 quality %～20 quality %, SrO:0 quality %～20 quality %, BaO:0 quality %～10 quality %, RO:5 quality %～20 quality % are (wherein, R is at least a kind that is selected from Mg, Ca, Sr and Ba, and the RO total that is composition contained among MgO, CaO, SrO and BaO).
The 7th mode of the present invention, as the manufacture method of the described sheet glass of any one in the 1st～6th mode of the present invention, wherein, in described absorption is processed, makes described melten glass be cooled to the scope of 1600 ℃ to 1500 ℃ with the cooling rate more than 2.5 ℃/minute.
The 8th mode of the present invention, as the manufacture method of the described sheet glass of any one in the 1st～7th mode of the present invention, wherein, between described clarification operation and described molding procedure, comprises the agitating procedure that the composition of melten glass is stirred in heterogeneity,
In described melting operation, the temperature that the temperature while starting with the melting than described melten glass is higher is supplied to described clarification operation by described melten glass,
In described clarification operation, with the lower temperature of temperature after processing than described absorption, described melten glass is supplied to described agitating procedure,
In described molding procedure, the viscosities il (pool) of described melten glass of take is supplied with described melten glass as the temperature of log η=4.3～5.7, then is shaped to plate glass.
The invention effect
The manufacture method of the sheet glass of aforesaid way can reduce the bubble remained in sheet glass efficiently.
The accompanying drawing explanation
Fig. 1 is the process picture sheet of manufacture method of the sheet glass of present embodiment.
Fig. 2 schematically shows the figure that is melted the device of operation～cutting action in the manufacture method of sheet glass of present embodiment.
Fig. 3 is the figure that mainly means the device formation of being clarified operation of present embodiment.
Fig. 4 is the figure that mainly means the device formation of carrying out molding procedure and cutting action of present embodiment.
Fig. 5 is the figure from the melting operation to an example of the temperature history of molding procedure of explanation present embodiment.
When meaning carrying out deaeration and processing of present embodiment, Fig. 6 is included in the O in melten glass 2output and the figure of the relation of heat-up rate.
Fig. 7 means contained SO in the hole in the glass after reproduction remains in the bubble in sheet glass 2the figure of measurement result of content.
Fig. 8 means in the experimental furnace of the temperature history of the melten glass shown in mimic diagram 5 figure of the relation of bubble rank while making sheet glass and cooling rate.
Fig. 9 means the figure of the relation that is present in the interior bubble rank of sheet glass and cooling rate when the device of the manufacture sheet glass utilized shown in Fig. 2 is manufactured sheet glass.
Figure 10 means the figure of the relation that is present in the interior bubble rank of sheet glass and heat-up rate when the device of the manufacture sheet glass utilized shown in Fig. 2 is manufactured sheet glass.
Embodiment
Below, the manufacture method of the sheet glass of present embodiment is described.
(the whole summary of the manufacture method of sheet glass)
Fig. 1 is the process picture sheet of manufacture method of the sheet glass of present embodiment.
The manufacture method of sheet glass mainly has melting operation (ST1), clarification operation (ST2), the operation that homogenizes (ST3), supplies with operation (ST4), molding procedure (ST5), Slow cooling operation (ST6) and cutting action (ST7).In addition, also have to grind and cut operation, grinding step, matting, inspection operation, bale packing operation etc., and will be in the bale packing operation a plurality of glass plate conveyances of institute's lamination to the operating personnel of order party.
Fig. 2 is the figure that schematically shows the glass substrate manufacturing installation that is melted operation (ST1)～cutting action (ST7).As shown in Figure 2, this device mainly has fusing device 200, shaped device 300, reaches cutting unit 400.Fusing device 200 mainly has the groove 201 of melting, clarifying tank 202, steel basin 203, reaches glass supply-pipe 204,205,206.It should be noted that, glass supply-pipe 204,205 is as described below be flow melten glass MG metal tube and there is the clarification function, be therefore in fact also clarifying tank.Below, glass supply-pipe 204 is called to the 1st clarifying tank 204, clarifying tank 202 is called to the 2nd clarifying tank 202, glass supply-pipe 205 is called to the 3rd clarifying tank 205.It should be noted that, the body part to the 1st clarifying tank the 204, the 3rd clarifying tank 205, glass supply-pipe 206 and the 2nd clarifying tank 202 and steel basin 203 between each groove of shaped device 300 after connection melting groove 201 consists of platinum or platinum alloy pipe.The 1st clarifying tank 204 and the 3rd clarifying tank 205 are cylindric or groove shape.
In melting operation (ST1), at least by the energising heating that has utilized electrode, will be added with SnO 2as finings and be supplied to the frit that melts in groove 201, contain SnO 2frit as finings melts, and obtains thus melten glass.Further, except utilizing the energising heating of electrode, thereby also can utilize not shown flame to melt frit, obtain melten glass.In the situation that utilize the melting of the frit of energising heating and flame, particularly, the liquid level that utilizes not shown raw material throwing device to make frit be dispersed in melten glass MG is supplied with.Frit is heated by the gas phase that becomes high temperature in flame and is slowly melted, thereby is dissolved in melten glass MG.Utilize the energising heating that melten glass MG is heated up.It should be noted that, melting operation or melting operation and clarify between operation, also can in melten glass, be utilized the foaming of oxygen.It should be noted that, preferably do not bubbled at the initial stage that melts operation.Its reason is, for example, at the initial stage (temperature that melten glass is less than 1540 ℃) that melts operation, while in melting groove 201, melten glass MG being switched on to heating, with the resistance that forms the parts such as brick that melt groove 201, compare, the resistance of glass is larger, therefore electric current easily flows in the parts such as brick, and is difficult to utilize the electrode pair melten glass MG heating of switching on.
Clarification operation (ST2) is at least carried out in the 1st clarifying tank the 204, the 2nd clarifying tank 202 and the 3rd clarifying tank 205.In the clarification operation, by making the melten glass MG in the 1st clarifying tank 204, heat up, be included in the O that contains in melten glass MG 2, CO 2or SO 2bubble etc. gaseous constituent can absorb because of the SnO as finings 2reduction reaction and the O that produces 2and growing, and the liquid level of emersion melten glass MG and discharging.In addition, in the clarification operation, the internal drop of the gaseous constituent in the bubble caused due to the reduction of the temperature of melten glass MG is low and pass through SnO 2reduction reaction and the SnO that obtains can produce oxidizing reaction because of the reduction of the temperature of melten glass MG, will remain in the O in the bubble in melten glass MG thus 2again absorb to melten glass MG bubble collapse etc. gaseous constituent.Oxidizing reaction based on finings and reduction reaction are that the temperature by adjusting melten glass MG is carried out.The adjustment of the temperature of melten glass MG be by adjust the 1st clarifying tank the 204, the 2nd clarifying tank 202, and the temperature of the 3rd clarifying tank 205 carry out.The adjustment of the temperature of each clarifying tank is to be undertaken by the combination of following any heating, method of cooling or these methods: to the direct-electrifying heating of pipe energising itself; Or utilize be configured in the 1st clarifying tank the 204, the 2nd clarifying tank the 202, the 3rd clarifying tank 205 around well heater indirect heating that each groove is heated; And cooler indirectly cooling that utilizes air cooling, water-cooled; To the 1st clarifying tank the 204, the 2nd clarifying tank the 202, the 3rd clarifying tank 205 air blowings or water spray etc.In addition, in Fig. 2, the groove of being clarified is divided into the 1st clarifying tank the 204, the 2nd clarifying tank the 202, the 3rd clarifying tank 205 these 3 parts, also further refinements certainly.
In the adjustment of the temperature of the melten glass MG of present embodiment, be used as the direct-electrifying heating of one of aforesaid method.Particularly, not shown metal-made flange in being arranged at the 1st clarifying tank 204 from melten glass MG to the 2nd clarifying tank 202 that supply with, and be arranged on the 2nd clarifying tank 202 in not shown metal-made flange between streaming current (arrow in Fig. 3), further, not shown metal-made flange in being arranged at the 2nd clarifying tank 202, and be arranged on streaming current (arrow in Fig. 3) between the not shown metal-made flange in the 2nd clarifying tank 202 in downstream side of melten glass MG with respect to this metal rim, thus, adjust the temperature of melten glass MG.In the present embodiment, first zone between the metal-made flange, and the metal-made flange between flow respectively certain electric current and to the heating of switching on of the 1st clarifying tank 204 and the 2nd clarifying tank 202 of the 2nd zone, adjust thus the temperature of melten glass MG, but this energising heating is not limited to utilize the logical electrically heated temperature adjustment in 2 zones, also can carry out the energising heating in 1 zone or the heating of switching in the zone more than 3, thereby carry out the temperature adjustment of melten glass MG.
In the operation that homogenizes (ST3), utilize agitator 203a to be stirred the melten glass MG in the steel basin 203 of supplying with by the 3rd clarifying tank 205, carry out thus homogenizing of glass ingredient.Steel basin 203 more than 2 also can be set.
In supplying with operation (ST4), by glass supply-pipe 206, melten glass is supplied to shaped device 300.
In shaped device 300, carry out molding procedure (ST5) and Slow cooling operation (ST6).
In molding procedure (ST5), melten glass is shaped to plate glass G, and makes the fluid of plate glass G.In the present embodiment, use the overflow downdraw of having utilized following formed body 310.In Slow cooling operation (ST6), will be through moulding and mobile plate glass G is cooling in the mode that does not produce internal strain.
In cutting action (ST7), in cutting unit 400, the plate glass G that will be supplied with by shaped device 300 is cut into specific length, obtains thus sheet glass.To further be cut into specific size through the sheet glass of cutting, thereby make the sheet glass of target size.Afterwards, carry out glass end face grind cut, the cleaning of grinding and sheet glass, further, after checking and having or not the defects such as bubble or brush line, using the sheet glass of passed examination product as the finished product, carry out bale packing.
(clarification operation)
Fig. 3 is the figure that the device formation of operation is clarified in main expression.The clarification operation comprises the deaeration operation and absorbs operation.In the deaeration operation, melten glass MG is warming up to more than 1630 ℃, and makes the SnO as finings 2emit oxygen, this oxygen is entered in the bubble B both deposited of melten glass MG, the bubble diameter of the bubble B that both deposited is enlarged.Thus, by result from bubble B composition of gases within that the temperature of melten glass MG rises in press the expansion that rises the bubble diameter caused, with result from the synergy of reduction of the melten glass MG viscosity that the temperature of melten glass MG rises, the speed of floating of bubble B improves, thereby has promoted deaeration.
In absorbing processing, by with deaeration, processing the temperature that makes on the contrary melten glass MG, reduce, oxygen in bubble B in melten glass MG is absorbed again and the temperature by melten glass MG reduces and makes the internal drop of the gaseous constituent in bubble B low to melten glass MG, synergy based on them, bubble diameter is dwindled, and bubble B is disappeared in melten glass MG.
It should be noted that, in the deaeration operation, with the heat-up rate more than 2 ℃/minute, the temperature of melten glass MG is warming up to more than 1630 ℃.So-called heat-up rate more than 2 ℃/minute refers to, the average heating speed of for example, for example, melten glass MG in the scope of temperature (be 1580 ℃, and be the scope of 1560 ℃～1620 ℃) the arrival clarifying temp (1630 ℃～1700 ℃) of the melten glass MG of the temperature of melten glass MG after melting operation is more than 2 ℃/minute.For example, in the 1st clarifying tank 204, the temperature of melten glass MG is in the situation more than 1630 ℃, and heat-up rate means from the melten glass MG melted in the 1st clarifying tank 204 that being exported to of groove 200 is connected and certainly flows into the average heating speed of outflow.
The 1st clarifying tank the 204, the 2nd clarifying tank 202 and the 3rd clarifying tank 205 are to give the device of the absorption of deaeration that melten glass MG carries out melten glass MG and bubble B by the temperature history by above-mentioned.Therefore, have and can or be cooled to the temp regulating function of target temperature by the 1st clarifying tank the 204, the 2nd clarifying tank 202 and the heating of the 3rd clarifying tank 205.
The temperature adjustment separately of the 1st clarifying tank the 204, the 2nd clarifying tank 202 and the 3rd clarifying tank 205 utilizes the combination of following any method or these methods to carry out: the direct-electrifying heating that each clarifying tank itself is switched on; Or utilization is configured in the indirect heating of the clarifying tank of each groove not shown well heater on every side; And water cooler indirectly cooling that utilizes air cooling, water-cooled; To each clarifying tank blown, water spray; Etc..
According to Fig. 3, illustrate in greater detail clarification.
During the liquid state melting glass MG that will melt and contain in a large number the bubble B that the decomposition reaction because of frit generates in melting groove 201 is directed into the 1st clarifying tank 204.
In the 1st clarifying tank 204, the platinum by the body as the 1st clarifying tank 204 or the heating of platinum alloy pipe and melten glass MG is heated to more than 1630 ℃, by promoting the reduction reaction of finings, and by a large amount of oxygen evolution to melten glass MG.For the bubble B both deposited in melten glass MG, the expansion of the bubble diameter of the upper ascending effect of the pressure of the gaseous constituent in the bubble B that the temperature of melten glass MG of resulting from rises, the oxygen discharged with reduction reaction because of finings spread and enter in bubble B superimposedly, and the bubble diameter of the bubble B both deposited enlarges because of this synergy.Now, till with the heat-up rate more than 2 ℃/minute, melten glass MG being heated to reach the temperature more than 1630 ℃.It should be noted that, the 1st clarifying tank 204 to the 2 clarifying tank 202 pipe sections are less, and different from the 2nd clarifying tank 202, the top open space does not have the atmosphere space of gas phase, therefore, in other words, in the 1st clarifying tank 204, melten glass MG is flowed in the mode of the inboard section integral body of filling the 1st clarifying tank 204, therefore with the 2nd clarifying tank 202, compares the temperature that can make efficiently melten glass MG and rises.That is, and be warming up to more than 1630 ℃ and compare in the interior temperature by melten glass MG of the 2nd clarifying tank 202,
In the situation that the interior temperature by melten glass MG of the 1st clarifying tank 204 is warming up to more than 1630 ℃, can reduce the Heating temperature of the 2nd clarifying tank 202, therefore from the volatilization of the platinum alloy that suppresses to form the 2nd clarifying tank 202 or the viewpoint of melting loss, be preferred.
Then, this melten glass MG is directed in the 2nd clarifying tank 202.
The 2nd clarifying tank 202 is different from the 1st clarifying tank 204, the atmosphere space that the top open space of the 2nd clarifying tank 202 inside is gas phase, but the liquid level of the bubble B emersion melten glass MG in melten glass MG and being released into outside melten glass MG.
In the 2nd clarifying tank 202, platinum by the body as the 2nd clarifying tank 202 or the heating of platinum alloy pipe and melten glass MG is continued to maintain the high temperature more than 1630 ℃, bubble B in melten glass MG floats to the top of the 2nd clarifying tank 202, in the liquid skin breakage of melten glass MG, carry out thus the deaeration of melten glass MG.Especially, for example, if melten glass MG is heated to (being 1630 ℃～1700 ℃), SnO more than 1630 ℃ 2accelerate to produce reduction reaction.Now, such as in the situation that manufacture the glass for flat panel display plate such as liquid-crystal display, the viscosity of glass is applicable to the viscosity (200 pool～800 pools) of the floating of bubble B, deaeration because the rising of the temperature of melten glass MG becomes.
Herein, the top open space above the 2nd clarifying tank 202 breaks and the gaseous constituent that discharges is released into outside the 2nd clarifying tank 202 from not shown gas discharge outlet.In the 2nd clarifying tank 202, will remove the melten glass MG that floats the bubble B that speed is fast and bubble diameter is large and be directed in the 3rd clarifying tank 205 by the floating of bubble B, deaeration.
In the present embodiment, for example as shown in Figure 3, at the 2nd clarifying tank 202 to the 3rd clarifying tank 205, in 2 different zones of extending on also can the length direction by the platinum to forming body or platinum alloy pipe respectively mobile electric current controlled the intensification of carrying out melten glass MG.In the different zones more than 3 of extending on platinum that in addition, also can be by the body to forming clarifying tank or the length direction of platinum alloy pipe respectively mobile electric current controlled the intensification of carrying out melten glass MG.
So, the intensification of melten glass MG by least 2 the different zones that are controlled at clarifying tank respectively mobile electric current carry out, from the viewpoint that deaeration highly-efficient treatment ground is carried out, be preferred.
In the 3rd clarifying tank 205, the degree of the platinum by the body as the 3rd clarifying tank 205 or platinum alloy pipe cooling or the heating by suppressing the 3rd clarifying tank 205, and carry out the cooling of melten glass MG.The temperature of melten glass MG reduces because this is cooling, therefore, does not carry out the floating of bubble B, deaeration, the pressure decreased of the gaseous constituent in residual less bubble B, and bubble diameter slowly diminishes.Further, if the temperature of melten glass MG becomes below 1600 ℃, in processing, deaeration passes through SnO 2reduction reaction and the part of the SnO that obtains absorbs oxygen, and become SnO again 2.Therefore, as the oxygen of the gaseous constituent in bubble B, again absorbed to melten glass MG, B is more and more less for bubble, is absorbed in melten glass MG and final the disappearance.Now, with average more than 2 ℃/minute, more preferably average speed more than 3 ℃/minute is cooled to melten glass MG the temperature range of 1600 ℃ to 1500 ℃.It should be noted that, the section of the 3rd clarifying tank 205 is less than the 2nd clarifying tank 202, therefore, with the 2nd clarifying tank 202, compares and can make more efficiently melten glass MG cooling.That is, and carrying out cooling comparing in the interior temperature to melten glass MG of the 2nd clarifying tank 202, in the situation that the interior temperature to melten glass MG of the 3rd clarifying tank 205 is carried out is cooling, can accelerate cooling rate, is preferred from this viewpoint.
In the example depicted in fig. 3, the clarifying tank of being clarified operation is divided into the 1st clarifying tank the 204, the 2nd clarifying tank 202, reaches the 3rd clarifying tank 205 these 3 parts, certain also further refinement of clarifying tank.The refinement clarifying tank can carry out the temperature adjustment of melten glass MG more meticulously.Especially from the situation that change kind or the meltage of melten glass MG, more easily carrying out the viewpoint of temperature adjustment, the refinement clarifying tank is favourable.
In addition, in described explanation, for the purpose of simplifying the description, according to making melten glass MG be warming up to 1630 ℃ in the 1st clarifying tank 204, carry out the floating of bubble B, the deaeration of melten glass MG in the 2nd clarifying tank 202, the mode that melten glass MG carries out the absorption of bubble B by the cooling of melten glass MG in the 3rd clarifying tank 205 describes the functional separation of each clarifying tank, but also can function not separated fully for each clarifying tank.The part midway of length direction that can near the 2nd clarifying tank 202, as the formation that melten glass MG is heated up, also can be configured to the part of the cooling that starts melten glass MG midway between to the of the length direction of the 2nd clarifying tank 202 3 clarifying tanks 205.
In the present embodiment, surface temperature by measuring the 1st clarifying tank the 204, the 2nd clarifying tank 202, the 3rd clarifying tank 205, do not have the surface temperature in the outside of the mobile clarifying tank of melten glass MG to carry out temperature control, can heat-up rate, the cooling rate that dissolve glass MG be managed thus.Can be by computer simulation, utilization is supplied to the flow velocity of melten glass MG of clarifying tank and the condition of temperature, precomputes the relation of the medial temperature (mean value of temperature that has the melten glass MG of temperature distribution in clarifying tank) of the surface temperature of the 1st clarifying tank the 204, the 2nd clarifying tank 202 and the 3rd clarifying tank 205 and mobile melten glass MG in the 1st clarifying tank the 204, the 2nd clarifying tank 202 and the 3rd clarifying tank 205.Therefore, the surface temperature that can measure according to the outside of clarifying tank, thus utilize above-mentioned relation to calculate heat-up rate, cooling rate manages heat-up rate, cooling rate.It should be noted that, the flow velocity of melten glass MG can calculate according to the volume of each device and the amount of melten glass MG that flows into the time per unit of shaped device 300.In addition, the temperature of melten glass MG can calculate according to viscosity and the thermal conductivity of glass.
So, after deaeration is processed, the greenhouse cooling to 1600 ℃ that makes melten glass MG with for example cooling rate more than 2 ℃/minute to the reason of the temperature range of 1500 ℃ is, as described below, and the number of bubbles remained in as the per unit mass in the sheet glass of the finished product is reduced.So-called bubble refers to the bubble had with the equal above volume of the volume of the bubble of the volume of predefined bubble, for example diameter 20 μ m herein.
It should be noted that, above-mentioned cooling rate more can reduce the number of bubbles remained in sheet glass more soon, but this reduction effect diminishes along with the rising of above-mentioned cooling rate.Above-mentioned cooling rate is preferably more than 3 ℃/minute.It should be noted that, for the upper limit of above-mentioned cooling rate, there is no special setting, but in the situation that industrial manufacture sheet glass, because of following reason, 50 ℃/minute is the upper limit.
That is, if the cooling rate of melten glass MG becomes too fast, the interior oxygen of bubble B that can hinder melten glass MG is absorbed again to the phenomenon of melten glass MG, result, and the bubble B in melten glass MG itself may not can reduce.In addition, even if the thermal conductivity of glass is also at high temperature less 20～50W/ (mK) left and right, therefore, sharply cooling of melten glass MG otherwise further take special means, can only carry out from the outside of the 3rd clarifying tank 205 cooling, therefore, in the situation that accelerate above-mentioned cooling rate, only near the melten glass MG outside surface of the 3rd clarifying tank 205 is cooling, and the melten glass MG of the central part of the 3rd clarifying tank 205 maintains the state of high temperature.That is,, in the 3rd clarifying tank 205, between the outer surface part of melten glass MG and central part, temperature head becomes large.In this case, produce the problem of crystallization among the melten glass MG of outer surface part.In addition, in the 3rd clarifying tank 205, if under the temperature head of melten glass MG between the outer surface part of melten glass MG and central part becomes large state, melten glass MG is stirred, the glass that temperature head is large mixes, therefore except producing bubble B, also easily hindering uniformity aspect the composition of glass.In addition, in order to accelerate the cooling rate of melten glass MG, need to increase the heat radiation from the 3rd clarifying tank 205, therefore must make to support the thickness attenuation of the holding components such as supporting brick of the body of the platinum of the 3rd clarifying tank 205 or platinum alloy pipe.Yet, only make the thickness attenuation of holding components, the strength decreased of equipment.Therefore, in the situation that industrial manufacture sheet glass, the cooling rate of accelerating simply melten glass MG only can cause the problems referred to above, can't say appropriate.
From above content, the upper limit from the cooling rate of 1600 ℃ to 1500 ℃ of melten glass MG is preferably 50 ℃/minute, more preferably 35 ℃/minute.That is, in the present embodiment, above-mentioned cooling rate is preferably 2 ℃/minute～50 ℃/minute, and more preferably 2.5 ℃/minute～50 ℃/minute, more preferably 3 ℃/minute～35 ℃/minute.
(molding procedure)
Fig. 4 is the figure that the device formation of molding procedure and cutting action is carried out in main expression.Shaped device 300 comprises forming furnace 340 and Slow cooling stove 350.
Forming furnace 340 and Slow cooling stove 350 are that the not shown furnace wall that consists of refractory bodies such as refractory brick is around forming.Forming furnace 340 is arranged on vertical direction with respect to Slow cooling stove 350., be provided with formed body 310, atmosphere distance member 320, cooling roller 330, cooling unit 335, reach carrying roller 350a～350d in the furnace interior space formed in the furnace wall by forming furnace 340 and Slow cooling stove 350.
Formed body 310 is shaped to plate glass G for the melten glass MG that will flow into from fusing device 200 by the glass supply-pipe 206 shown in Fig. 2.About viscosities il (pool), the temperature that the melten glass while being supplied to formed body 310 is log η=4.3～5.7.The temperature of this melten glass MG is different because of the kind of glass, if glass for liquid crystal display for example is 1200 ℃～1300 ℃.Thus, in shaped device 300, make the fluid of the plate glass G of vertical lower.In formed body 310, be the elongated structure formed by refractory brick etc., as shown in Figure 4, section is wedge shape.On the top of formed body 310, be provided with the supply groove 312 as the stream of guiding melten glass.Supply with the supplying opening place of groove 312 in being arranged at shaped device 300 and be connected with the 3rd clarifying tank 205, the melten glass MG flowed into by the 3rd clarifying tank 205 flows along supplying with groove 312.Form and supply with groove 312 from supplying with mode that groove 312 overflows with melten glass MG.
The melten glass MG overflowed from supply groove 312 flows down along vertical walls and the inclined wall of the sidewall of the both sides of formed body 310.Flow through lower end 313 interflow of the melten glass of sidewall at the formed body 310 shown in Fig. 4, and be shaped to 1 plate glass G.
(glass composition)
Utilize present embodiment sheet glass manufacture method and the sheet glass manufactured can be suitably for glass substrate for plane display device.For example, have and do not contain in fact Li 2o, Na 2o, and K 2any of O, even if or contain Li 2o, Na 2o, and K 2o at least any, Li 2o, Na 2o, and K 2among O, the total amount of contained composition is also the effect that situation that the following glass of 2 quality % forms can be brought into play present embodiment efficiently, is preferred from the side.Form about glass, can preferably enumerate example shown below.
(a) SiO 2: 50 quality %～70 quality %,
(b) B 2o 3: 5 quality %～18 quality %,
(c) Al 2o 3: 10 quality %～25 quality %,
(d) MgO:0 quality %～10 quality %,
(e) CaO:0 quality %～20 quality %,
(f) SrO:0 quality %～20 quality %,
(g) BaO:0 quality %～10 quality %,
(h) RO:5 quality %～20 quality % (wherein, R is at least a kind that is selected from Mg, Ca, Sr and Ba, and RO is the total of composition contained among MgO, CaO, SrO and BaO),
(i) R ' 2o: below surpassing 0.1 quality % and 2.0 quality %, (wherein R ' is at least a kind that is selected from Li, Na and K, and R ' 2o is Li 2o, Na 2o and K 2the total of contained composition among O),
(j) be selected from SnO 2, Fe 2o 3and the metal oxide of at least a kind in cerium oxide etc.: add up to 0.05 quality %～1.5 quality %.
It should be noted that, above-mentioned (i), (j) though composition nonessential, can contain the composition of (i), (j).Do not contain in fact As in above-mentioned glass 2o 3and PbO, and contain SnO 2.It should be noted that, from the viewpoint of environmental problem, preferably do not contain in fact Sb 2o 3.
In addition, R ' (i) 2the content of O also can be 0 quality %.
Except mentioned component, for the various physical property of regulating glass, melting, clarification, and the characteristic of moulding, the sheet glass of present embodiment also can contain various other oxide compounds.As this other the example of oxide compound, though be not limited to following example, can list TiO 2, MnO, ZnO, Nb 2o 5, MoO 3, Ta 2o 5, WO 3, Y 2o 3, and La 2o 3.
In addition, in the present embodiment, SnO 2the composition that easily makes glass devitrification, therefore, in order to improve clarification property and not cause that devitrification, its containing ratio are preferably 0.01 quality %～0.5 quality %, more preferably 0.05 quality %～0.3 quality %, more preferably 0.1 quality %～0.3 quality %.
Fe 2o 3the composition that improves the infrared ray absorption of glass, and by containing Fe 2o 3can promote deaeration.Yet, Fe 2o 3it is the composition that reduces the transmitance of glass.Therefore, if Fe 2o 3content too much, for glass substrate for display, be unaccommodated.From above content, in above-mentioned metal oxide, contain Fe 2o 3situation under, from improving the clarification property and suppressing the viewpoint of reduction of the transmitance of glass, described Fe 2o 3content be preferably 0.01 quality %～0.1 quality %, 0.01 quality %～0.08 quality % more preferably.In addition, but complete deaeration operation and the also SO the decrease uptake operation from improving the clarification property with the short period of time 2the viewpoint of the generation of bubble is abundant, the SnO of preferably combination 0.01 quality %～0.5 quality % 2and the Fe of 0.01 quality %～0.1 quality % 2o 3used.
In addition, the R ' of above-mentioned (i) 2o likely makes the deterioration in characteristics of TFT and the thermal expansivity of glass is increased and destroys the composition of substrate during in thermal treatment from the glass stripping, therefore, in the situation that, as liquid crystal display glass substrate or OLED display glass substrate, preferably do not contain in fact R ' 2o.Yet, by contain on the contrary the mentioned component of specified quantitative in glass, can be in the situation that do not cause the deterioration in characteristics of TFT, the thermal expansion of glass is suppressed within the specific limits, and improve the basicity of glass, the oxidation of the metal of valence state change is become easily, and performance clarification property.In addition, R ' 2o can reduce the ratio resistance of glass, and meltability is promoted.Therefore, R ' 2o is preferably 0 quality %～2.0 quality %, more preferably surpasses 0.1 quality % and is below 1.0 quality %, more preferably 0.2 quality %～0.5 quality %.It should be noted that, be preferably and do not contain Li 2o, Na 2o, and contain the K that is difficult to produce from the glass stripping deterioration in characteristics of TFT in mentioned component most 2o.K 2the containing ratio of O is preferably 0 quality %～2.0 quality %, more preferably 0.1 quality %～1.0 quality %, more preferably 0.2 quality %～0.5 quality %.
The sheet glass of present embodiment is in order to obtain the characteristic that suitably is used as the glass substrate used in liquid-crystal display or OLED display etc., compare change with sheet glass that contains in a large number alkali etc., viscosity in the clarifying temp of melten glass MG is high, therefore, in deaeration is processed bubble to float speed easily slack-off.Especially, the glass substrate that forms low temperature polycrystalline silicon TFT at glass surface requires strain point high, so high temperature viscosity easily uprises, and the viscosity in the clarifying temp of melten glass MG further uprises.Therefore, for example, in the situation that manufacture, strain point is more than 680 ℃, particularly strain point is the glass more than 690 ℃, in deaeration is processed bubble to float speed easily further slack-off.In the situation that the sheet glass of present embodiment is the glass substrate of formation liquid-crystal display or OLED display etc., for example the viscosity of the melten glass MG in the temperature of 1630 ℃ is preferably 130 pools～350 pools.In addition, if form the glass temperature that the glass viscosity of the glass of glass substrate is log η=2.5 o'clock, be 1550 ℃～1680 ℃, present embodiment is suitable; If the scope of 1570 ℃～1680 ℃, the effect of present embodiment is remarkable; If the scope of 1590 ℃～1680 ℃, the effect of present embodiment is more remarkable.
(temperature history of melten glass)
Fig. 5 is the figure of the melting operation of explanation in present embodiment to an example of the temperature history of molding procedure.
For the frit used in the manufacture of the sheet glass of present embodiment, in order to become the chemical constitution of target, various raw materials are carried out weighing, fully mix, obtain frit thereby make.Now, by the SnO of specified quantitative 2as finings, be added in frit.The SnO that is added with obtained will so be made 2frit drop into to melt in groove 201, then at least utilize the energising heating to be melted, make thus melten glass MG.Be fed into the frit melted in groove 201 and decompose when reaching the decomposition temperature of its composition, and become melten glass MG by Vitrification.Melten glass MG flow through melt groove 201 during improve lentamente temperature, to the 1st clarifying tank 204 (glass supply-pipe 204), advance near certainly melting the bottom of groove 201.
Therefore, in melting groove 201, certainly drop into the temperature T 1 in the moment of frit to the temperature T 3 in the moment that enters the 1st clarifying tank 204 (glass supply-pipe 204), the temperature of melten glass MG has the temperature history gently risen.It should be noted that, be T1<T2<T3 in Fig. 5, but also can be T2=T3 or T2 > T3, as long as be at least T1<T3.
By flowing certain electric current and to the heating of switching on of the platinum of the 1st clarifying tank 204 or platinum alloy pipe between the not shown metal-made flange of the not shown metal-made flange at the 1st clarifying tank 204 and the 2nd clarifying tank 202, further by flowing certain electric current and to the heating of switching on of the platinum of the 2nd clarifying tank 202 or platinum alloy between another not shown metal-made flange of the not shown metal-made flange at the 2nd clarifying tank 202 and the 2nd clarifying tank 202, with the heat-up rate more than 2 ℃/minute, the melten glass MG that enters to the 1st clarifying tank 204 is warming up to from temperature T 3 to SnO 2discharge sharp the temperature T 4 (be for example more than 1630 ℃, more preferably 1630 ℃～1700 ℃, more preferably 1650 ℃～1700 ℃) of oxygen.Making heat-up rate is that reason more than 2 ℃/minute is, as described below, in the situation that heat-up rate is more than 2 ℃/minute, and O 2it is large that the burst size of gas sharply becomes.It should be noted that, temperature T 3 is larger with the difference of temperature T 4, the SnO in melten glass MG 2the O discharged 2amount more, more can promote deaeration.Therefore, temperature T 4 is preferably than temperature T 3 height 50 ℃ of left and right for example.
Further, the melten glass MG that enters to the 2nd clarifying tank 202 is maintained to temperature T 4 to the temperature T 5 roughly the same with temperature T 4.It should be noted that, in the present embodiment, the temperature regulation in temperature T 3～temperature T 5 is to utilize each clarifying tank is led to electrically heated mode, but is not limited to this mode.For example, also can utilize the indirect heating by being configured in each clarifying tank not shown well heater on every side to carry out the said temperature adjusting.
Now, promote the SnO as finings by melten glass MG being heated to 1630 ℃ on usining 2reduction reaction.Thus, a large amount of oxygen evolution is to melten glass MG.The bubble B both deposited in melten glass MG is owing to resulting from the expansion of the bubble diameter that the upper ascending effect of pressure of the gaseous constituent in the bubble B that the temperature of melten glass MG rises causes, reduction reaction based on described finings and the oxygen that discharges spreads and enters in bubble B, enlarge by this synergy bubble diameter in addition.
Bubble B after bubble diameter enlarges follows Stokes'theorem and the speed of floating of bubble B accelerates, thereby has promoted floating, breaking of bubble B.
In the 2nd clarifying tank 202, melten glass MG also continues to maintain the high temperature more than 1630 ℃, and therefore, the bubble B in melten glass MG floats the liquid surface to melten glass MG, and, in the liquid skin breakage, carries out thus the deaeration of melten glass MG.
In Fig. 5, rise to temperature T 4 in the temperature that makes melten glass MG from temperature T 3, afterwards, maintain the temperature T 5 roughly the same with temperature T 4 during carry out the deaeration processing.In Fig. 5, T4 and T5 are roughly the same, but can be T4<T5, also can be T4 > T5.
It should be noted that, it is that example in the 1st clarifying tank 204 describes that the temperature that can enumerate melten glass MG reaches temperature T 4, but also can be in the 2nd clarifying tank 202.
In addition, preferably, the 1st top temperature of melten glass when melten glass MG flows through the 1st clarifying tank 204 equates with the 2nd top temperature that flows through the melten glass MG of the 2nd clarifying tank 202 when interior or is higher than it.Thus, at melten glass, when the 1st clarifying tank 204 moves to the 2nd clarifying tank 202, the temperature of melten glass MG is fully high, and more than maintaining the temperature of finings generation reduction reaction, therefore, the 2nd clarifying tank 202 does not need the heating for further melten glass being heated up.Therefore, the Heating temperature of the 2nd clarifying tank 202 can be suppressed to ground lower than in the past.Therefore, can suppress the 2nd clarifying tank 202 volatilizations that the free platinum of platinum or platinum alloy form, and can manufacture impurity such as platinum crystallisate that volatilization due to platinum is attached to the inner-wall surface in the 2nd clarifying tank 202 and sneak into defect that melten glass MG produces, result from the few sheet glass of defect of above-mentioned impurity.Flow through the 1st clarifying tank 204 midway at melten glass MG, the temperature of melten glass MG is preferably and reaches the 1st top temperature.In this case, with the situation that melten glass reaches the 1st top temperature and the 2nd top temperature at the link position of the 1st clarifying tank 204 and the 2nd clarifying tank 202, compare, the Heating temperature step-down of the 2nd clarifying tank 202, therefore, can more easily suppress the 2nd clarifying tank 202 volatilizations that the free platinum of platinum or platinum alloy form.
Then, enter to the melten glass MG of the 3rd clarifying tank 205 from the 2nd clarifying tank 202 because absorbing residual bubble B, and for example, be cooled to the temperature T 7 (temperature that is applicable to agitating procedure via temperature T 6 (1600 ℃) from temperature T 5, its type because of glass types and whipping appts is different, is for example 1500 ℃).
Temperature by melten glass MG reduces, and does not produce the floating of bubble B, deaeration, and the pressure that remains in the gaseous constituent in the vesicle in melten glass MG also descends, and bubble diameter diminishes gradually.Further, if the temperature of melten glass MG becomes below 1600 ℃, SnO is (by SnO 2reduction and obtain) a part absorb oxygen, and become SnO again 2.Therefore, the interior oxygen of bubble B residual in melten glass MG is absorbed again to melten glass MG, and vesicle further diminishes.Melten glass MG absorbs this vesicle, and vesicle finally disappears.
Oxidizing reaction by this SnO absorbs the O as the gaseous constituent in bubble B 2be treated to and absorb process, it is carrying out during being reduced to temperature T 7 via temperature T 6 from temperature T 5.In Fig. 5, the cooling rate of temperature T 5～T6 is faster than the cooling rate of temperature T 6～T7, but the cooling rate of temperature T 5～T6 also the cooling rate of comparable temperature T 6～T7 is slow, also can equate.Be preferably at least during this absorption is processed, the temperature of melten glass MG is cooled to the temperature range of 1600 ℃ to 1500 ℃ with the cooling rate more than 2 ℃/minute.Yet, from increasing the cooling rate of melten glass MG when the condition of high temperature more, and suppress earlier following SO 2diffusion, make to be absorbed into the SO in bubble B 2the viewpoint reduced is set out, and the cooling rate that is preferably temperature T 5～T6 is faster than the cooling rate of temperature T 6～T7.; in absorbing processing; be preferably melten glass MG below 1500 ℃ (particularly; be the scope of the melten glass temperature when being supplied to molding procedure from 1500 ℃, for example 1500 ℃～1300 ℃) temperature range in cooling rate slower than the cooling rate in the temperature range at 1600 ℃ to 1500 ℃.
In addition, slower than the cooling rate of temperature T 5～T6 by the cooling rate that makes temperature T 6～T7, can make to be absorbed into the SO in bubble B 2reduce, and make to flow into outer surface part in the 3rd clarifying tank 205 (glass supply-pipe 205) of melten glass MG of steel basin 203 and the temperature head between central part diminishes.
It should be noted that, from the productivity that improves sheet glass and the viewpoint of cutting down equipment cost, in absorbing processing, be preferably melten glass MG below 1500 ℃ (particularly, be the scope of the melten glass temperature when being supplied to molding procedure from 1500 ℃, for example 1500 ℃～1300 ℃) temperature range in the temperature range of cooling rate than 1600 ℃ to 1500 ℃ in cooling rate fast.It should be noted that, carrying out in the temperature controlled situation of this melten glass MG, preferably be provided for adjusting the flow adjuster of the amount of the melten glass MG be supplied to molding procedure.
In addition, from reducing the SO be absorbed in bubble B 2and the viewpoint of amount that can be supplied to by the temperature treatment adjustment of the melten glass MG in glass supply-pipe 206 the melten glass MG of molding procedure is set out, in absorbing processing, the cooling rate be preferably in the temperature range of the cooling rate of melten glass MG in the temperature range below 1500 ℃ than 1600 ℃ to 1500 ℃ is slow.Thus, without glass supply-pipe 206 being processed into to special shape or except glass supply-pipe 206 and flow adjuster is set in addition, and the quantitative change that flows into the melten glass MG of molding procedure obtains easily and adjusts.In addition, can make to flow into outer surface part in the glass supply-pipe 206 of melten glass MG of molding procedure and the temperature head between central part diminishes.
Process rear or absorb processing midway in above-mentioned absorption, melten glass MG enters to steel basin 203.Steel basin 203 homogenizes melten glass MG for the composition inequality that reduces melten glass MG.It should be noted that, in steel basin 203, also can proceed above-mentioned absorption and process.After this, melten glass MG is lowered the temperature for example, until be the temperature T 8 that is applicable to the moulding in molding procedure, 1200 ℃～1300 ℃.
As mentioned above, comprise the agitating procedure that the composition to melten glass MG stirs in heterogeneity between clarification operation and molding procedure.So-called referring between clarification operation and molding procedure between the opportunity that opportunity of starting in the clarification operation on opportunity that agitating procedure starts and molding procedure start.The agitating procedure of melten glass MG can clarified starting of operation midway, also can after the clarification operation, start.It should be noted that, in Fig. 1, clarification operation (ST2) and the operation that homogenizes (ST3) mean by the order of the priority on the opportunity started.In melting operation, the temperature T 3 that the temperature T 1 while starting with the melting than melten glass MG is high is supplied to the clarification operation by melten glass MG.In the clarification operation, with the temperature lower than temperature T 7, melten glass MG is supplied to agitating procedure.In agitating procedure, take, in the temperature as log η=4.3～5.7 aspect viscosities il (pool), melten glass MG is supplied to forming process.In molding procedure, in the temperature of melten glass MG, be for example, under the state of 1200 ℃～1300 ℃, melten glass MG to be shaped to plate glass.It should be noted that, the liquid phase viscosity of sheet glass is preferably that log η=more than 4, the liquidus temperature of sheet glass is preferably 1050 ℃～1270 ℃.By being this liquid phase viscosity and liquidus temperature, applicable overflow downdraw is as forming method.
Fig. 6 is the measurement result of carrying out in experimental furnace, and it means the O in melten glass that is included in when carrying out deaeration processes 2output and the figure of the relation of heat-up rate.Heat-up rate is the V-bar in the temperature range of 1550 ℃ to 1640 ℃.Sheet glass for this mensuration has the glass composition identical with glass substrate for display with alkali-metal poor liquid crystal, and uses SnO 2as finings.Particularly, use and there is the liquid crystal glass substrate for display that glass shown below forms, obtained the measurement result shown in Fig. 6.
SiO 2: 60 quality %
Al 2o 3: 19.5 quality %
B 2o 3: 10 quality %
CaO:5.3 quality %
SrO:5 quality %
SnO 2: 0.2 quality %
Known according to Fig. 6, in order to improve O 2output, as long as make the heat-up rate of melten glass MG, be more than 2 ℃/minute.It should be noted that, in the measurement result of Fig. 6, CO 2be by lamination on being formed with the glass substrate of cavity other glass substrate and gas (CO in sealed cavity 2), heat each glass substrate and it is merged under this state, make thus its form with bubble in melten glass MG exist.
In the present embodiment, there is no the upper limit of the essence of heat-up rate, as long as be for example below 10 ℃/minute.The thermal conductivity of glass is little, therefore, in order to make heat-up rate increase, must increase area of heat transfer.In order to increase area of heat transfer, can enumerate and reduce as the internal diameter of the 1st clarifying tank 204 of metal tube or the 2nd clarifying tank 202 etc., further to form more longways in the longitudinal direction the 1st clarifying tank 204 or the 2nd clarifying tank 202 etc.In addition, in order to increase area of heat transfer, also can enumerate the temperature that makes the 1st clarifying tank 204 or the 2nd clarifying tank 202 etc. and rise to significantly the temperature higher than the temperature of melten glass MG.Yet, if reduce the internal diameter of the 1st clarifying tank 204 or the 2nd clarifying tank 202 etc., further form more longways in the longitudinal direction the 1st clarifying tank 204 or the 2nd clarifying tank 202 etc., can cause device for producing glass sheet to maximize, not preferred.In addition, if make the temperature of the 1st clarifying tank 204 or the 2nd clarifying tank 202 etc. rise to significantly the temperature higher than the temperature of melten glass MG, likely Yin Gaowen and breakage of device for producing glass sheet.Therefore, the substantial upper limit of heat-up rate is preferably below 10 ℃/minute.From above content, heat-up rate is preferably 2 ℃/minute～10 ℃/minute, and more preferably 3 ℃/minute～8 ℃/minute, more preferably 3 ℃/minute～6.5 ℃/minute.In this scope, can carry out efficiently the deaeration processing, and reduce and remain in the bubble in sheet glass efficiently.
In addition, as mentioned above, during the absorption of the bubble carried out after deaeration is processed is processed, melten glass MG is cooled to the temperature range of 1600 ℃～1500 ℃ with the cooling rate more than 2 ℃/minute.It is to be undertaken by following illustrated reason.
Make melten glass MG from temperature T 3 be warming up to temperature T 4 then reach temperature T 5 during, melten glass MG is warming up to SnO 2the temperature that discharges oxygen and reduce, 1600 ℃～more than 1630 ℃, therefore can promote bubble absorption in melten glass MG by SnO 2the oxygen discharged, in addition, the molten O be stored in melten glass MG after can promoting to reach a high temperature 2, CO 2, SO 2diffusion, thereby make the molten O be stored in melten glass MG 2, CO 2, SO 2be absorbed in above-mentioned bubble B.It should be noted that, change to some extent according to glass ingredient to the melting degree of the gaseous constituent in melten glass MG, but be SO 2situation under, in alkali-metal content glass how, melting degree is high, even if but the melting degree can be dissolved in melten glass MG in not containing basic metal or containing the sheet glass also used for a small amount of liquid crystal display glass substrate as in this embodiment in is low.In the sheet glass used at liquid crystal display glass substrate, originally can not add artificially S (sulphur) composition as frit, but as in the impurity in raw material or the combustion gases (Sweet natural gas, city gas, propane gas etc.) that use in melting groove 201 as impurity and micro-containing.Therefore, the S composition oxidation contained as this impurity and become SO 2, spread and enter in the bubble B be included in melten glass MG.SO 2therefore be difficult to again be absorbed, as bubble B and residual.With in the past by As 2o 3during as finings, compare, this phenomenon occurs very significantly.
By SnO 2in situation about forming as the glass of finings, the hold-time of melten glass MG in high temperature is longer, more can promote SO 2to the bubble B internal diffusion of both having deposited in melten glass MG.It is believed that, this is because after reaching a high temperature, SO 2velocity of diffusion in melten glass MG is accelerated, and becomes and easily enters in bubble B.
It should be noted that, long if the temperature of melten glass MG remains on the time of the high temperature more than 1630 ℃, can cause melten glass MG by over reduction, when carrying out the cooling of melten glass MG, easily produce following SO 2bubble.On the other hand, if the time remained on more than 1630 ℃ is too short, the deaeration in deaeration operation is insufficient.Therefore, by the temperature of melten glass MG remain on time more than 1630 ℃ be preferably 15 minutes～90 minutes, more preferably 30 minutes～60 minutes.
After this, when temperature T 5 to temperature T 7 is carried out the cooling of melten glass MG, pass through SnO 2reduction and the SnO that obtains absorbs O because of oxidizing reaction 2and oxidation.Therefore, be present in the O in bubble B residual in melten glass MG 2by SnO, absorbed.Yet, the SO in melten glass MG 2or CO 2diffusion in the bubble B of Xiang Jicun still maintains.Therefore, with temperature T 3, in during temperature T 5, compare, temperature T 5 is to the SO of the gaseous constituent in the bubble B in during temperature T 7 2, CO 2concentration high.Especially, in the melten glass MG used in present embodiment, be alkali-metal poor composition, so SO 2melting degree in melten glass MG is little.Therefore, if SO 2once be absorbed by bubble B as gas, this SO 2be difficult to be absorbed in melten glass MG in absorbing processing.
Above, in temperature T 5 to during temperature T 7, the O in bubble B 2because the oxidizing reaction of SnO is absorbed into SnO, but SO 2, CO 2diffusion in the bubble B of Xiang Jicun still maintains, and by making, is therefore between short-term during this period, can reduce SO 2, CO 2diffusion in the bubble B of Xiang Jicun, and can suppress the growth of bubble B.Therefore, in during processing in temperature T 5 to the absorption of temperature T 7, make melten glass MG be cooled to the temperature range of 1600 ℃ to 1500 ℃ with the cooling rate more than 2 ℃/minute, can suppress as described as follows the number of bubbles in sheet glass thus.
Fig. 7 means contained SO in the hole after the bubble B reproduced in glass 2the figure of measurement result of content, it means SO 2the content interdependence of holding time with respect to temperature condition and the temperature of glass.The size of the size Expressing bubble B of the bullet in Fig. 7, and mean SO 2content.
Sheet glass has the glass identical with glass substrate for display with alkali-metal poor above-mentioned liquid crystal and forms, and contains SnO 2as finings.The liquid crystal display glass substrate that the glass that while particularly, using the measurement result that has and obtain Fig. 6, the sheet glass of made is identical forms.
Thereby the melten glass that this glass is formed is shaped to the tabular sheet glass that obtains, and on this sheet glass, perforate is carried out in artificially, and the sheet glass that the congener glass of the sandwich of the sheet glass after perforate forms in oxygen atmosphere, make thus to be filled with O 2hole as bubble, reproduce.For the sheet glass with this hole, heat-treat under the temperature to more than 1200 ℃ and temperature are held time the condition of carrying out various variations, and measure the SO in hole by gasometry 2content.Sheet glass is heated to more than 1200 ℃, so sheet glass is molten state, can reproduces the bubble B remained in melten glass.
Known according to Fig. 7, in the temperature more than 1500 ℃ roughly, be filled with O 2hole in contain SO 2.Especially, be more high temperature, further temperature is held time longer, SO 2content more increase.This means molten being stored in as the SO in the glass of molten state 2diffusion Yin Gaowen and promoted, and be absorbed in hole.
Therefore, during the absorption of melten glass MG after deaeration is processed processed, be preferably to be cooled to rapidly and be less than 1500 ℃, in the present embodiment, be preferably melten glass MG and be cooled to the temperature range of 1600 ℃ to 1500 ℃ with the cooling rate more than 2 ℃/minute.
Fig. 8 means the figure of following measurement result, and this measurement result is illustrated in the experimental furnace of temperature history of the melten glass MG shown in mimic diagram 5 the bubble rank that produces while making sheet glass and the relation of cooling rate.Cooling rate is the V-bar in the temperature range of 1600 ℃ to 1500 ℃.The sheet glass of made has the glass identical with glass substrate for display with alkali-metal poor liquid crystal and forms, and uses SnO 2as finings.The liquid crystal display glass substrate that the glass that while particularly, using the measurement result that has and obtain Fig. 6, the sheet glass of made is identical forms.
If known cooling rate is less than 2 ℃/minute, the bubble rank sharply rises.It should be noted that, so-called bubble rank means that the number of bubbles of the per unit glass quality when cooling rate is made as 10 ℃/minute is as benchmark, and number of bubbles is deteriorated is for which kind of degree.For example, bubble rank 3 means the number of bubbles that the number of bubbles when cooling rate is made as to 10 ℃/minute is 3 times.Therefore, known in the situation that cooling rate is less than 2 ℃/minute, number of bubbles sharply rises.
According to Fig. 8, in order to reduce number of bubbles, preferably making cooling rate is more than 2 ℃/minute.
(embodiment 1)
Fig. 9 means the figure of following measurement result, when the device that this measurement result is illustrated in the manufacture sheet glass utilized shown in Fig. 2 is manufactured sheet glass, is present in number of bubbles in sheet glass and the relation of cooling rate.Through after melting operation, clarification operation, agitating procedure, utilize overflow downdraw to manufacture sheet glass.Now, the temperature history of melten glass MG adopts the course shown in Fig. 5 except cooling rate.So-called cooling rate is the V-bar in the temperature range of 1600 ℃ to 1500 ℃.The sheet glass of made has the glass identical with glass substrate for display with alkali-metal poor liquid crystal and forms, and uses SnO 2as finings.The liquid crystal display glass substrate that the glass that while particularly, using the measurement result that has and obtain Fig. 6, the sheet glass of made is identical forms.The number of bubbles of the per unit mass when bubble rank shown in Fig. 9 means to using cooling rate is made as to 8.4 ℃/minute is as benchmark, and number of bubbles is deteriorated is for which kind of degree.For example bubble rank 5 means the number of bubbles that the number of bubbles when cooling rate is made as to 8.4 ℃/minute contains 5 times.The bubble rank that cooling rate is 7.9 ℃/minute is 1.1, and the bubble rank that cooling rate is 4.9 ℃/minute is 1.6, and the bubble rank that cooling rate is 4.2 ℃/minute is 1.8, and the bubble rank that cooling rate is 3.0 ℃/minute is 1.8.On the other hand, the bubble rank that cooling rate is 1.8 ℃/minute is 3.0, and the bubble rank that cooling rate is 0.5 ℃/minute is 83, and all the number of bubbles when cooling rate is made as to 8.4 ℃/minute contains the bubble more than 3 times.
Known according to Fig. 9, if cooling rate is less than 2 ℃/minute, the bubble rank sharply rises, so number of bubbles sharply rises.Therefore known, if with more than 2 ℃/minute, more preferably the cooling rate more than 2.5 ℃/minute makes melten glass MG be cooled to the temperature range of 1600 ℃ to 1500 ℃, number of bubbles reduces.Known according to Fig. 9, from reducing the viewpoint of number of bubbles, for example to be 3 ℃/minute～8 ℃/minute be more effective to cooling rate.It should be noted that to there is SiO 2: 60 quality %, Al 2o 3: 19.5 quality %, B 2o 3: 10 quality %, CaO:5.3 quality %, SrO:5 quality %, SnO 2: 0.15 quality %, Fe 2o 3: in the sheet glass of 0.05 quality %, although number of bubbles integrally reduces on a small quantity, obtained roughly the same result.In addition, there is SiO 2: 61 quality %, Al 2o 3: 19.5 quality %, B 2o 3: 10 quality %, CaO:9 quality %, SnO 2: 0.3 quality %, R 2o (R is total composition contained in the sheet glass among Li, Na, K): in the manufacture of the sheet glass of 0.2 quality % (700 ℃ of strain points), also obtained result same as described above.
(embodiment 2)
Figure 10 means the figure of the relation that is present in the interior number of bubbles of sheet glass and heat-up rate.The sheet glass of made has the glass identical with glass substrate for display with alkali-metal poor liquid crystal and forms, and uses SnO 2as finings.The liquid crystal display glass substrate that the glass that while particularly, using the measurement result that has and obtain Fig. 6, the sheet glass of made is identical forms.After 1580 ℃ (=T3) will concoct the frit melting formed into described glass, be warming up to 1640 ℃ (=T4).After 1640 ℃ keep certain hour, be cooled to 1600 ℃ (=T6) with the speed of 10 ℃/minute, further, with the speed of 5 ℃/minute, be cooled to 1500 ℃ (=T5).Now, heat-up rate is become to 0.5 ℃/minute, 1 ℃/minute, 1.5 ℃/minute, 2 ℃/minute, 3 ℃/minute, 4 ℃/minute, 5 ℃/minute, 6 ℃/minute, and observe the variation of number of bubbles.The number of bubbles of the per unit mass when bubble rank shown in Figure 10 means take heat-up rate is made as to 2 ℃/minute is benchmark, and number of bubbles is deteriorated is for which kind of degree.For example bubble rank 5 means the number of bubbles that the number of bubbles when heat-up rate is made as to 2 ℃/minute contains 5 times.The bubble rank that heat-up rate is 2 ℃/minute is 1, the bubble rank that heat-up rate is 3 ℃/minute is 0.8, the bubble rank that heat-up rate is 4 ℃/minute is 0.7, and the bubble rank bubble that heat-up rate is 5 ℃/minute is 0.7, and the bubble rank that heat-up rate is 6 ℃/minute is 0.6.On the other hand, the bubble rank that heat-up rate is 0.5 ℃/minute is 4.8, the bubble rank that heat-up rate is 1 ℃/minute is 2.3, and the bubble rank that heat-up rate is 1.5 ℃/minute is 1.6, and all the number of bubbles when making heat-up rate be 2 ℃/minute contains the bubble more than 1.5 times.
Known according to Figure 10, if heat-up rate is less than 2 ℃/minute, the bubble rank sharply rises, and number of bubbles sharply rises.Therefore known, after melting operation, if with more than 2 ℃/minute, more preferably the heat-up rate more than 2.5 ℃/minute is warming up to more than 1630 ℃ melten glass MG, number of bubbles reduces.Therefore be preferably 2 ℃/minute～10 ℃/minute, more preferably 3 ℃/minute～8 ℃/minute, more preferably 3 ℃/minute～6.5 ℃/minute.In addition, known according to Figure 10, from reducing the viewpoint of number of bubbles, for example to be 3 ℃/minute～8 ℃/minute, 3 ℃/minute～6 ℃/minute, 4 ℃/minute～6 ℃/minute or 4 ℃/minute～10 ℃/minute be effective to heat-up rate.It should be noted that to there is SiO 2: 60 quality %, Al 2o 3: 19.5 quality %, B 2o 3: 10 quality %, CaO:5.3 quality %, SrO:5 quality %, SnO 2: 0.15 quality %, Fe 2o 3: in the sheet glass of 0.05 quality %, number of bubbles integrally reduces on a small quantity, but has obtained roughly the same result.In addition, there is SiO 2: 61 quality %, Al 2o 3: 19.5 quality %, B 2o 3: 10 quality %, CaO:9 quality %, SnO 2: 0.3 quality %, R 2o (R is total composition contained in the sheet glass among Li, Na, K): in the manufacture of the sheet glass of 0.2 quality % (700 ℃ of strain points), also obtained result same as described above.
As mentioned above, can reduce the SO in melten glass according to present embodiment 2number of bubbles, therefore also can reduce the bubble of the core that becomes the cavitation erosion produced because of the rotation of the stirring rake in agitating procedure, result can reduce the number of bubbles in sheet glass.This effect is more remarkable in the manufacture method of the poor glass substrate of the BaO formed as glass or SrO.
More specifically, MgO, the CaO, SrO, the BaO that as the glass composition, contain are added to mainly with the form of carbonate in raw material, and about its decomposition temperature, MgO is minimum, and uprises according to the order of CaO, SrO, BaO.That is, decomposition temperature is higher, starts to discharge CO 2temperature higher.As shown in the above, if melten glass MG cooling after deaeration is processed, the material that decomposition temperature is higher more starts to absorb CO with higher temperature 2.For example BaO starts to absorb CO near 1300 ℃ 2.
Yet, as glass, forming and starting to absorb CO in higher temperature province 2baO or the manufacture of the poor sheet glass of SrO in, CO 2the temperature that is absorbed in melten glass MG reduce after, be to start after the viscosity of melten glass MG uprises.Herein, when the viscosity of melten glass MG is hanged down, CO 2diffusion rapidly in melten glass MG.Therefore, after the viscosity of melten glass MG uprises, (after the temperature step-down) starts CO 2the manufacture method of sheet glass of absorption in, CO 2easily as bubble, remain in melten glass MG.
As in the embodiment described in, if can be reduced in melten glass as the gaseous constituent of bubble and the SO existed 2even if be easy residual CO as mentioned above 2the manufacture of sheet glass, also can suppress to become the generation of bubble of the core of cavitation corrosion, result also can reduce as the number of bubbles in the sheet glass of the finished product.From above content, the manufacture of the glass substrate that the content of the applicable BaO of present embodiment is 0 quality %～1.0 quality %, further be applicable to not containing in fact the manufacture method of the glass substrate of BaO.In addition, the manufacture of the glass substrate that the content of the applicable SrO of present embodiment is 0 quality %～3.0 quality %, and further be applicable to not containing in fact the manufacture method of the glass substrate of SrO.
Above, the manufacture method of sheet glass of the present invention is explained, but the present invention is not limited to above-mentioned embodiment, without departing from the spirit and scope of the invention, can carry out various improvement or change, this is from needn't.
Nomenclature
200 fusing devices
201 melt groove
202 clarifying tanks
203 steel basins
The 203a agitator
204,205,206 glass supply-pipes
300 shaped devices
310 formed bodys
312 supply with groove
313 lower end
320 atmosphere spacer member
330 cooling rollers
335 cooling units
350a～350d carrying roller
340 forming furnaces
350 Slow cooling stoves
400 cutting units

Claims (8)

1. the manufacture method of a sheet glass, it is the method for manufacturing sheet glass, and this manufacture method is characterised in that, and it comprises:
Melt operation, wherein, at least utilize the energising heating will contain SnO 2frit as finings melts and the making melten glass;
The clarification operation, it comprises: deaeration is processed, and wherein, after described melting operation, with the heat-up rate more than 2 ℃/minute, the temperature of described melten glass is warming up to more than 1630 ℃, thereby generate thus bubble in described melten glass, carries out deaeration; And absorb processing, and wherein, after described deaeration is processed, make described melten glass cooling, thus the bubble in described melten glass is absorbed to described melten glass; And
Molding procedure, wherein, be shaped to plate glass by the described melten glass after described clarification operation.
2. the manufacture method of sheet glass as claimed in claim 1, in described molding procedure, utilize overflow downdraw to form plate glass by described melten glass.
3. the manufacture method of sheet glass as claimed in claim 1 or 2, wherein, the metal tube be connected between the melting groove that carries out described melting operation and the clarifying tank that carries out described clarification operation is at least used in the intensification of the described melten glass in described clarification operation, and is undertaken by the electric current that control flows into described metal tube.
4. as the manufacture method of the described sheet glass of claim 1～3 any one, wherein, the viscosity of the described melten glass in the temperature of 1630 ℃ is 130 pools～350 pools.
5. as the manufacture method of the described sheet glass of claim 1～4 any one, wherein, the R ' of described sheet glass 2the content of O is 0 quality %～2.0 quality %, described R ' 2o is Li 2o, Na 2o and K 2the total of contained composition among O.
6. as the manufacture method of the described sheet glass of claim 1～5 any one, wherein, described sheet glass contains:
SiO 2: 50 quality %～70 quality %,
B 2o 3: 5 quality %～18 quality %,
Al 2o 3: 10 quality %～25 quality %,
MgO:0 quality %～10 quality %,
CaO:0 quality %～20 quality %,
SrO:0 quality %～20 quality %,
BaO:0 quality %～10 quality %,
RO:5 quality %～20 quality %
Wherein, R is at least a kind that is selected from Mg, Ca, Sr and Ba, and the RO total that is composition contained among MgO, CaO, SrO and BaO.
7. as the manufacture method of the described sheet glass of claim 1～6 any one, in described absorption is processed, with the cooling rate more than 2.5 ℃/minute, make described melten glass be cooled to the scope of 1600 ℃ to 1500 ℃.
8. as the manufacture method of the described sheet glass of claim 1～7 any one, wherein,
Comprise the agitating procedure that the composition of melten glass is stirred in heterogeneity between described clarification operation and described molding procedure;
In described melting operation, the temperature that the temperature while starting with the melting than described melten glass is higher is supplied to described clarification operation by described melten glass;
In described clarification operation, with the lower temperature of temperature after processing than described absorption, described melten glass is supplied to described agitating procedure;
In described molding procedure, the viscosities il (pool) of described melten glass of take is supplied with described melten glass as the temperature of log η=4.3～5.7, then is shaped to plate glass.
CN201280003108.5A 2011-10-11 2012-10-11 The manufacture method of sheet glass Active CN103168010B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201510086677.6A CN104724908B (en) 2011-10-11 2012-10-11 The manufacture method of glass plate

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2011-223685 2011-10-11
JP2011223685 2011-10-11
PCT/JP2012/006537 WO2013054531A1 (en) 2011-10-11 2012-10-11 Method for manufacturing glass plate

Related Child Applications (2)

Application Number Title Priority Date Filing Date
CN201510086677.6A Division CN104724908B (en) 2011-10-11 2012-10-11 The manufacture method of glass plate
CN201310293448.2A Division CN103382077B (en) 2011-10-11 2012-10-11 Method for manufacturing glass plate

Publications (2)

Publication Number Publication Date
CN103168010A true CN103168010A (en) 2013-06-19
CN103168010B CN103168010B (en) 2015-12-23

Family

ID=48081597

Family Applications (3)

Application Number Title Priority Date Filing Date
CN201280003108.5A Active CN103168010B (en) 2011-10-11 2012-10-11 The manufacture method of sheet glass
CN201510086677.6A Active CN104724908B (en) 2011-10-11 2012-10-11 The manufacture method of glass plate
CN201310293448.2A Active CN103382077B (en) 2011-10-11 2012-10-11 Method for manufacturing glass plate

Family Applications After (2)

Application Number Title Priority Date Filing Date
CN201510086677.6A Active CN104724908B (en) 2011-10-11 2012-10-11 The manufacture method of glass plate
CN201310293448.2A Active CN103382077B (en) 2011-10-11 2012-10-11 Method for manufacturing glass plate

Country Status (5)

Country Link
JP (2) JP5329725B1 (en)
KR (2) KR101328333B1 (en)
CN (3) CN103168010B (en)
TW (2) TWI538889B (en)
WO (1) WO2013054531A1 (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105621858A (en) * 2016-03-17 2016-06-01 东旭科技集团有限公司 Bubble absorbing system and degassing method for molten glass and glass production line
CN114641457A (en) * 2019-11-06 2022-06-17 日本电气硝子株式会社 Glass plate and method for manufacturing glass plate
CN115784571A (en) * 2022-12-09 2023-03-14 彩虹显示器件股份有限公司 Supporting structure of substrate glass channel temperature rise section

Families Citing this family (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013054531A1 (en) * 2011-10-11 2013-04-18 ＡｖａｎＳｔｒａｔｅ株式会社 Method for manufacturing glass plate
JP5719797B2 (en) * 2012-04-06 2015-05-20 ＡｖａｎＳｔｒａｔｅ株式会社 Glass plate manufacturing method and glass plate manufacturing apparatus
KR101868195B1 (en) * 2014-06-16 2018-06-15 주식회사 엘지화학 Method for fabricating glass comprising preheating step of glassmaking materials
US20170218195A1 (en) * 2014-09-08 2017-08-03 Mitsubishi Gas Chemical Company, Inc. Thermoplastic resin composition and molded body using same
TW201711967A (en) 2015-08-26 2017-04-01 美商．康寧公司 Glass melting system and method for increased homogeneity
CN106396365B (en) * 2016-08-31 2019-07-05 江苏新悦华节能玻璃科技有限公司 The clarification process of tempered glass
CN106396367B (en) * 2016-08-31 2019-06-25 山西利虎玻璃（集团）有限公司 The clarification process of glass
CN106396366B (en) * 2016-08-31 2019-07-23 浙江九龙山实业有限公司 The preparation method of tempered glass
CN106430945B (en) * 2016-08-31 2019-03-12 佛山市南海蓝碟羽五金制品有限公司 The preparation method of glass
CN106380071B (en) * 2016-08-31 2018-12-25 绍兴市亿跃智能科技有限公司 The defecation method of glass
JP6792821B2 (en) * 2016-12-14 2020-12-02 日本電気硝子株式会社 Support structure of glass supply pipe, flat glass manufacturing equipment, flat glass manufacturing method, and preheating method of glass supply pipe
CN109748481A (en) * 2017-11-07 2019-05-14 彩虹显示器件股份有限公司 A kind of method and apparatus melting sample for experimental glass
CN109455903B (en) * 2018-10-29 2022-02-22 彩虹（合肥）液晶玻璃有限公司 TFT base plate glass production passageway rapid cooling device
CN109626831A (en) * 2019-01-16 2019-04-16 河南光远新材料股份有限公司 A method of reducing residual microbubbles in electronic glass fibers
CN109896724A (en) * 2019-04-23 2019-06-18 蚌埠中光电科技有限公司 A kind of glass platinum channel clarifier
KR102687148B1 (en) * 2019-06-13 2024-07-24 주식회사 엘지화학 Method for manufacturing glass plate

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010111533A (en) * 2008-11-05 2010-05-20 Avanstrate Inc Method of producing glass plate
JP2010523457A (en) * 2007-04-03 2010-07-15 コーニング インコーポレイテッド Method for reducing gaseous inclusions in a glass manufacturing process
WO2010093571A2 (en) * 2009-02-10 2010-08-19 Corning Incorporated Apparatus and method for reducing gaseous inclusions in a glass

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4946216B2 (en) * 2005-07-06 2012-06-06 旭硝子株式会社 Method for producing alkali-free glass
CN101213148B (en) * 2005-07-06 2012-04-11 旭硝子株式会社 Manufacturing method of alkali-free glass and alkali-free glass plate
JP5359271B2 (en) * 2006-07-13 2013-12-04 旭硝子株式会社 Non-alkali glass substrate, method for producing the same, and liquid crystal display panel
JPWO2012133467A1 (en) * 2011-03-31 2014-07-28 ＡｖａｎＳｔｒａｔｅ株式会社 Manufacturing method of glass plate
WO2013054531A1 (en) * 2011-10-11 2013-04-18 ＡｖａｎＳｔｒａｔｅ株式会社 Method for manufacturing glass plate

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010523457A (en) * 2007-04-03 2010-07-15 コーニング インコーポレイテッド Method for reducing gaseous inclusions in a glass manufacturing process
JP2010111533A (en) * 2008-11-05 2010-05-20 Avanstrate Inc Method of producing glass plate
WO2010093571A2 (en) * 2009-02-10 2010-08-19 Corning Incorporated Apparatus and method for reducing gaseous inclusions in a glass

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105621858A (en) * 2016-03-17 2016-06-01 东旭科技集团有限公司 Bubble absorbing system and degassing method for molten glass and glass production line
CN105621858B (en) * 2016-03-17 2018-04-13 东旭科技集团有限公司 Bubble absorption system and degasification method and glass production line for glass metal
CN114641457A (en) * 2019-11-06 2022-06-17 日本电气硝子株式会社 Glass plate and method for manufacturing glass plate
CN115784571A (en) * 2022-12-09 2023-03-14 彩虹显示器件股份有限公司 Supporting structure of substrate glass channel temperature rise section

Also Published As

Publication number Publication date
TWI417256B (en) 2013-12-01
CN103168010B (en) 2015-12-23
CN103382077B (en) 2015-03-25
JPWO2013054531A1 (en) 2015-03-30
JP5491665B2 (en) 2014-05-14
CN104724908A (en) 2015-06-24
JP2013212991A (en) 2013-10-17
KR20130069767A (en) 2013-06-26
KR20130087023A (en) 2013-08-05
WO2013054531A1 (en) 2013-04-18
CN104724908B (en) 2018-05-01
KR101328333B1 (en) 2013-11-11
JP5329725B1 (en) 2013-10-30
TW201345847A (en) 2013-11-16
TWI538889B (en) 2016-06-21
CN103382077A (en) 2013-11-06
TW201323357A (en) 2013-06-16
KR101538242B1 (en) 2015-07-20

Similar Documents

Publication Publication Date Title
CN103382077B (en) Method for manufacturing glass plate
CN103168009B (en) The manufacture method of sheet glass
KR101296484B1 (en) Methood of reducing gaseous inclusions in a glass making process
KR101508050B1 (en) Method and apparatus for making glass sheet
KR101486133B1 (en) Method and apparatus for making glass sheet
CN203498246U (en) Glass substrate making device and glass supply pipe
CN103080026A (en) Method for producing glass plate
CN103359910B (en) The manufacture method of sheet glass
JP2014205581A (en) Method and apparatus for producing glass substrate

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