CN104903259A - Manufacturing method for glass substrate and manufacturing apparatus for glass substrate - Google Patents
Manufacturing method for glass substrate and manufacturing apparatus for glass substrate Download PDFInfo
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- CN104903259A CN104903259A CN201480001960.8A CN201480001960A CN104903259A CN 104903259 A CN104903259 A CN 104903259A CN 201480001960 A CN201480001960 A CN 201480001960A CN 104903259 A CN104903259 A CN 104903259A
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- Prior art keywords
- glass
- temperature
- phase space
- gas
- melten glass
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- 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
- 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
-
- 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
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
- C03B5/04—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture in tank furnaces
-
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Glass Compositions (AREA)
Abstract
A glass treatment device has molten glass flow therethrough and processes said molten glass, the inner wall thereof at least partially comprising a material containing a platinum-group metal, and is constituted in such a manner that a gas-phase space is formed in the interior by the surface of the molten glass and the inner wall. The gas-phase space is formed along the direction of flow of the molten glass. When processing the molten glass, on the wall of the gas-phase space, a temperature gradient region having a temperature gradient along the upstream or downstream direction of the flow of molten glass from the high-temperature region of the wall is formed by heating and/or radiating heat from the glass processing device. In order to enable the minimization of agglomeration of volatilized platinum-group metals present in the gas-phase space, the temperature difference between the minimum and maximum temperature in the temperature gradient region is maintained so as not to exceed 150 DEG C.
Description
Technical field
The present invention relates to manufacture method and the glass substrate manufacturing installation of glass substrate.
Background technology
Glass substrate normally manufactures through making melten glass be shaped to the operation of glass substrate after generating melten glass by frit after carrying out clarification operation, agitating procedure (homogenize operation).But, in order to produce high-grade glass substrate in batches from the melten glass of high temperature, wish that the foreign matter of the defect essential factor considering glass substrate etc. is not mixed into melten glass from any glass treatment device manufacturing glass substrate.Therefore, in the manufacturing processed of glass substrate, the wall needs of the parts be connected with melten glass are made up of suitable material according to the quality etc. of the temperature of melten glass be connected with these parts, the glass substrate of requirement.Such as, melten glass between generating after melten glass to being supplied to molding procedure owing to being extremely very high temperature state, carry out melting, clarification, supply, stirring device can use containing the parts with the high platinum metals of thermotolerance and platinum (such as patent documentation 1).
Current art document
Patent documentation 1: JP 2010-111533 publication
Summary of the invention
Problem to be addressed by invention
But easily volatilize with the high temperature of melten glass in platinum metals.So, during the volatile matter aggegation of platinum metals, have a part for this agglutinator and crystallization to be mixed in melten glass the sorrow of the reduction of the quality causing glass substrate as micropartical.Especially because clarification operation be from melt operation to molding procedure period melten glass temperature reach the highest operation, so mainly carry out clarify operation finer in be heated to high temperature.Therefore, the volatilization of the platinum metals in finer is vigorous, special volatilization and the aggegation wishing minimizing platinum metals.
In addition, the foreign matter deriving from the agglutinator of the volatile matters such as above-mentioned platinum metals increases in the glass substrate for display with high-precision refinement in recent years representated by the liquid-crystal display of quality requirements increasingly stringent further to the problem that is mixed into of melten glass.
The object of the present invention is to provide and foreign matter can be suppressed to be mixed into manufacture method to the glass substrate of melten glass and glass substrate manufacturing installation by reducing the aggegation of the volatile matter being present in platinum metals in the gas-phase space of glass treatment device in the operation of the shaping pre-treatment melten glass of glass substrate.
For solving the method for problem
The present invention comprises with under type.
(mode 1)
A manufacture method for glass substrate, is characterized in that,
Have:
Melt frit and generate the melting operation of melten glass; And
Make melten glass in the internal flow of the glass treatment device be made up of the material comprising platinum metals at least partially of inwall, with the treatment process of melten glass described in the inter-process at described glass treatment device,
In the inside of described glass treatment device, form gas-phase space by the surface of described melten glass and described inwall,
Flow direction along described melten glass forms described gas-phase space,
In described treatment process, forming the described inwall of described gas-phase space, use at least one the formation temperature gradient region in the heat radiation of the heating of described glass treatment device and described glass treatment device, described thermal gradient zone has the thermograde of flow direction middle and upper reaches direction from the top temperature described inwall along described melten glass or downstream direction
In order to suppress the aggegation of the volatile matter of the platinum metals of the volatilization being present in described gas-phase space, the temperature head of the described top temperature in described thermal gradient zone and minimum temperature is made to be less than 150 DEG C.
(mode 2)
A manufacture method for glass substrate, is characterized in that,
Have:
Melt frit and generate the melting operation of melten glass; And
To the treatment process that described melten glass processes in glass treatment device, wherein, the liquid phase that described glass treatment device has the flowing of described melten glass and the gas-phase space formed by liquid level and the wall of described melten glass, and surround being made up of the material comprising platinum metals at least partially of the wall of described gas-phase space
Flow direction along described melten glass forms described gas-phase space,
In described treatment process, forming the described wall of described gas-phase space, use at least one the formation temperature gradient region in the heat radiation of the heating of described glass treatment device and described glass treatment device, described thermal gradient zone has thermograde from the top temperature described wall along the flow direction middle and upper reaches direction of described melten glass or downstream direction
In order to the aggegation of the volatile matter of the platinum metals of the volatilization being present in described gas-phase space can be suppressed, the temperature head of the described top temperature in described thermal gradient zone and minimum temperature is made to be less than 150 DEG C.
(mode 3)
The manufacture method of the glass substrate described in mode 1 or 2, wherein, described glass treatment device, in the way of described inwall on the flow direction of described melten glass, the ventpipe that described gas-phase space is communicated with air is set,
The position of the top temperature in described thermal gradient zone between the end of described gas-phase space and the position of described ventpipe,
Described thermal gradient zone is formed at the region between the position of region between the position of described top temperature and the end of described gas-phase space or described top temperature and the position of described ventpipe.
(mode 4)
The manufacture method of the glass substrate according to any one of mode 1 ~ 3, wherein, arrange the vibrating part extended from the outside of the described glass treatment device of the outer circumference of described glass treatment device in the end of described gas-phase space, the described minimum temperature position in described thermal gradient zone is the end of described gas-phase space.
(mode 5)
The manufacture method of the glass substrate according to any one of mode 1 ~ 4, wherein, described minimum temperature and described top temperature are 1500 ~ 1750 DEG C.
(mode 6)
The manufacture method of the glass substrate according to any one of mode 1 ~ 5, wherein, described glass treatment device is the clarifying plant of the clarification carrying out melten glass.
(mode 7)
A kind of glass substrate manufacturing installation, is characterized in that,
There is glass treatment device, described glass treatment device is being made up of the material comprising platinum metals at least partially of inwall and melten glass is flowed and processes the device of described melten glass, described glass treatment device is configured to form gas-phase space by the surface of described melten glass and described inwall in inside
Described glass substrate manufacturing installation is configured at the described inwall surrounding described gas-phase space, use at least one the formation temperature gradient region in the heat radiation of the heating of described glass treatment device and described glass treatment device, described thermal gradient zone has thermograde from the top temperature described inwall along the updrift side of the flow direction of described melten glass or downstream direction
In order to suppress the aggegation of the volatile matter of the platinum metals of the volatilization being present in described gas-phase space, the described top temperature in described thermal gradient zone and the temperature head of minimum temperature are less than 150 DEG C.
(mode 8)
The manufacture method of the glass substrate according to any one of mode 1 ~ 6 or the described glass substrate manufacturing installation described in mode 7 wherein, are 1630 DEG C ~ 1750 DEG C in the top temperature of the melten glass of the internal flow of described treatment unit.
(mode 9)
The manufacture method of the glass substrate according to any one of mode 1 ~ 6 and 8 or the described glass substrate manufacturing installation described in mode 7 or 8, wherein, the content of the stannic oxide of described glass substrate is 0.01 % by mole ~ 0.3 % by mole.
(mode 10)
The manufacture method of the glass substrate according to any one of mode 1 ~ 6,8 and 9 or the described glass substrate manufacturing installation according to any one of mode 7 ~ 9, wherein, the vapour pressure of the platinum metals in described gas-phase space is 0.1Pa ~ 15Pa.
(mode 11)
The manufacture method of the glass substrate according to any one of mode 1 ~ 6,8,9 and 10 or the described glass substrate manufacturing installation according to any one of mode 7 ~ 10, wherein, the oxygen concn of described gas-phase space is 0 ~ 10%.
(mode 12)
The manufacture method of the glass substrate according to any one of mode 1 ~ 6,8 ~ 11 or the glass substrate manufacturing installation according to any one of mode 7 ~ 11, wherein, the agglutinator such as maximum length generated due to the aggegation of the volatile matter of described platinum metals is more than 100 relative to the ratio of minimum length and long-width ratio.
In addition, such as, the maximum length of the agglutinator of platinum metals is 50 μm ~ 300 μm, and minimum length is 0.5 μm ~ 2 μm.Herein, the maximum length of the agglutinator of so-called platinum metals refers to be external in and takes the agglutinator of platinum metals and greatly enhance the length on limit in the bounding rectangle of foreign matter image that obtains most, and so-called minimum length refers to the length of the minimum minor face of described bounding rectangle.
Or, as the aggegation of the volatile matter due to described platinum metals and the agglutinator generated, maximum length is more than 100 relative to the ratio of minimum length and long-width ratio, and the maximum length of the agglutinator of platinum metals is defined as more than 100 μm, is preferably defined as 100 μm ~ 300 μm.
(mode 13)
The manufacture method of the glass substrate according to any one of mode 1 ~ 6,8 ~ 12 or the glass substrate manufacturing installation according to any one of mode 7 ~ 12, wherein, described glass substrate is glass substrate for display.
In addition, oxide semiconductor glass substrate for display or LTPS glass substrate for display is suitable for.
Invention effect
According to manufacture method and the glass substrate manufacturing installation of glass substrate involved in the present invention, in the operation that the melten glass before glass substrate forming is processed, the aggegation of the volatile matter of the platinum metals be present in the gas-phase space of glass treatment device can be suppressed.Thereby, it is possible to suppress foreign matter to be mixed in melten glass.
Accompanying drawing explanation
Fig. 1 is the schema of the operation of the method for manufacturing glass substrate illustrated involved by embodiment.
Fig. 2 is the mode chart of the formation of the glass substrate manufacturing installation illustrated involved by embodiment.
Fig. 3 is the outside drawing of the finer mainly represented involved by embodiment.
Fig. 4 is the schematic diagram of an example of the sectional view of the inside of the finer represented involved by embodiment and the temperature curve of finer.
Fig. 5 is the schematic diagram of an example of the result of experimental example.
Embodiment
(manufacture method of glass substrate and glass substrate manufacturing installation)
The manufacture method of the glass substrate that the present invention relates to and the embodiment of glass substrate manufacturing installation are described with reference to accompanying drawing.Fig. 1 is the schema of an example of the operation of the method for manufacturing glass substrate illustrated involved by present embodiment.The manufacture method of glass substrate mainly possesses melting operation S1, clarification operation S2, agitating procedure S3, molding procedure S4, annealing operation S5 as shown in Figure 1, cuts off operation S6.
Fig. 2 is the mode chart of an example of the formation of the glass substrate manufacturing installation 200 illustrated involved by present embodiment.Glass substrate manufacturing installation 200 possesses melting groove 40, finer 41, whipping appts 100, shaped device 42, transfer tube 43a, 43b, 43c.Transfer tube 43a connects melting groove 40 and finer 41.Transfer tube 43b connects finer 41 and whipping appts 100.Transfer tube 43c connects whipping appts 100 and shaped device 42.
In melting operation S1, melt frit and generate melten glass.Melten glass is accumulated in and melts in groove, is heated to the temperature with expectation.Melten glass contains finings.From the view point of minimizing carrying capacity of environment, preferably use stannic oxide as finings.
In melting groove 40, frit is heated to the temperature corresponding to its composition etc. and melts.Thus, in melting groove 40, such as, the high temperature molten glass G of 1500 DEG C ~ 1620 DEG C is obtained.Further, in melting groove 40, by streaming current between at least one pair of electrode, interelectrode melten glass G can electrified regulation, and additionally by the flame giving roasting kiln auxiliary on the basis of electrified regulation, frit can heat.
In clarification operation S2, can carry out in the inside of transfer tube and finer.Being made up of the material comprising platinum metals at least partially of finer inwall, makes melten glass flow in the inside of finer, gas-phase space is formed on the top on the surface of melten glass, and clarifies in the inside of gas treatment equipment.The top of so-called molten glass surface refers to the part being positioned at vertical direction relative to surface.The inside of so-called gas treatment equipment refers to the space of the inner side surrounded by inwall.At first, the temperature of melten glass is made to increase by transfer tube and finer.Finings utilizes intensification to cause reduction reaction, releases oxygen.The bubble that comprises in melten glass absorbs the oxygen of releasing and the enlarged-diameter of steeping, and floats up to the surface (liquid level) of the melten glass be connected with the gas-phase space in finer, follicular rupture and disappearing.Then, in clarification operation S2, the temperature of melten glass is reduced.Thus, the finings be reduced causes oxidizing reaction, and absorption of residual is stored in the gaseous constituents such as the oxygen in melten glass.
Specifically, the melten glass G obtained in melting groove 40 flows into finer 41 from melting groove 40 by transfer tube 43a.Finer 41 and transfer tube 43a, 43b, 43c are the pipes of platinum metals.Further, platinum metals refers to the alloy of the metal that single platinum family element is formed and the metal that platinum family element is formed.Platinum family element is platinum (Pt), palladium (Pd), rhodium (Rh), ruthenium (Ru), osmium (Os) and iridium (Ir) six kinds of elements.Platinum metals fusing point is high, relative to the corrosion resistance excellent of melten glass.In finer 41, groove 40 is same is provided with heating unit with melting.In addition, at least transfer tube 43a is provided with heating unit.In clarification operation S2, melten glass G is made to clarify by heating up further.Such as, the temperature of the melten glass G in finer 41 is 1600 DEG C ~ 1720 DEG C.
The melten glass G of clarification in finer 41 flows into whipping appts 100 from finer 41 by transfer tube 43b.Melten glass G is by cooled during transfer tube 43b.
In agitating procedure S3, the melten glass of clarification is stirred, and the composition of melten glass homogenizes.Thus, the reason such as brush line of glass substrate and the composition inequality of melten glass are reduced.The melten glass homogenized is sent to molding procedure S4.
Specifically, in whipping appts 100, at the temperature of the temperature lower than the melten glass G by finer 41, stir melten glass G.Such as, in whipping appts 100, the temperature of melten glass G is 1250 DEG C ~ 1450 DEG C.Such as, in whipping appts 100, the viscosity of melten glass G is that 500 pool ~ 1300 are moored.Melten glass G is stirred at whipping appts 100 and homogenizes.
Shaped device 42 is flowed into from whipping appts 100 by transfer tube 43c by the melten glass G homogenized at whipping appts 100.Melten glass G is by being cooled to the shaping viscosity being suitable for melten glass G during transfer tube 43c.Such as, melten glass G is cooled to 1100 ~ 1300 DEG C.
In molding procedure S4, utilize overflow downdraw or sink and float method, sheet glass is continuously shaped from melten glass.
Specifically, the melten glass G flowing into shaped device 42 is provided to the formed body 52 of the inside being arranged at forming furnace (not shown).Groove is formed with along the length direction of formed body 52 on formed body 52.Melten glass G is provided to the groove above formed body 52.From groove overflow melten glass G along a pair side of formed body 52, flow down downwards.The a pair melten glass G flowing down the side of formed body 52 converges in the lower end of formed body 52, and sheet glass GR is shaping continuously.
In annealing operation S5, sheet glass continuously shaped in molding procedure S4 has the thickness of expectation, and in order to not produce distortion and warpage, and sheet glass is annealed.
In cut-out operation S6, the sheet glass of annealing in annealing operation S5 is cut to the length of regulation, obtains the glass of tabular.The glass of tabular is cut to the size of regulation further, obtains glass substrate.
Like this, the manufacture method of the glass substrate of present embodiment has and melts frit and generate the melting operation of melten glass, the treatment process processing melten glass in glass treatment device, the clarification operation that such as makes melten glass clarify in clarifying plant.Glass treatment device is configured to make melten glass flow and form gas-phase space in the upper surface of melten glass.Thus, glass treatment device is provided with the liquid phase that melten glass flows, the gas-phase space formed by surface (liquid level) and the wall of the melten glass be connected with gas-phase space.Surround being made up of the material comprising platinum metals at least partially of the inwall of this gas-phase space.
Use the clarifying plant comprising finer 41 to be described as glass treatment device below, as long as but glass treatment device be arranged at and melt between groove 40 and shaped device 42 that just there is no particular limitation to the device of the process that melten glass G specifies.Glass treatment device can also with the transfer tube of such as whipping appts or transfer melten glass for object except clarifying plant.Thus, the process of melten glass G also comprises the process that melten glass is homogenized, the process etc. transferring melten glass except the process making melten glass clarify.
(application examples of glass substrate)
Be arranged in the agglutinator of the platinum metals of glass baseplate surface when the surface using the panel manufacturing process of glass substrate from glass substrate departs from, the surface portion departed from is recess, the film be formed on glass substrate is formed uneven, there is the problem causing the display defect of picture.Further, when there is the agglutinator of platinum metals in glass substrate, owing to producing distortion because of the thermal expansion rate variance of glass and platinum metals in annealing operation, there is the problem causing the display defect of picture.Therefore, present embodiment is suitable for the manufacture to the strict glass substrate for display of the requirement of the display defect of picture.Especially present embodiment is suitable for the fine glass substrate for display such as the LTPS glass substrate for display of more strict to the requirement of the display defect of picture, to use the oxide semiconductors such as IGZO (indium, gallium, zinc, oxygen) oxide semiconductor glass substrate for display and use LTPS (low temperature polycrystalline silicon) semi-conductor.
According to above content, the glass substrate of the manufacture method manufacture of the glass substrate of present embodiment is utilized to be suitable for the glass substrate of the few panel display glass substrate such as liquid-crystal display, plasma display, OLED display of the content of requirement alkalimetal oxide or flat-panel monitor (FPD).In addition, oxide semiconductor glass substrate for display and the LTPS glass substrate for display of IGZO is also preferably.Further, as protecting the cover plate of indicating meter, disk glass, solar cell glass substrate to be also suitable for.Glass substrate as panel display or flat-panel monitor can use non-alkali glass or the glass containing micro-alkali.Panel display or the viscosity of panel display glass substrate when high temperature high.Such as, 10 are had
2.5the temperature of the melten glass of the viscosity of pool is more than 1500 DEG C.
(glass composition)
In melting groove 40, utilize not shown heating unit to melt frit, generate melten glass.Frit is modulated to the glass that can obtain in fact expecting composition.As an example of glass composition, as panel display or panel display glass substrate and preferred non-alkali glass contains SiO
2: 50 quality % ~ 70 quality %, Al
2o
3: 10 quality % ~ 25 quality %, B
2o
3: 0 quality % ~ 15 quality %, MgO:0 quality % ~ 10 quality %, CaO:0 quality % ~ 20 quality %, SrO:0 quality % ~ 20 quality %, BaO:0 quality % ~ 10 quality %.Herein, the total content of MgO, CaO, SrO and BaO is 5 quality % ~ 30 quality %.
Or the glass substrate being suitable for oxide semiconductor glass substrate for display and LTPS glass substrate for display comprises SiO
2: 55 quality % ~ 70 quality %, Al
2o
3: 15 quality % ~ 25 quality %, B
2o
3: 0 quality % ~ 15 quality %, MgO:0 quality % ~ 10 quality %, CaO:0 quality % ~ 20 quality %, SrO:0 quality % ~ 20 quality %, BaO:0 quality % ~ 10 quality %.Herein, the total content of MgO, CaO, SrO and BaO is 5 quality % ~ 30 quality %.Now, be more preferably containing SiO
2: 60 quality % ~ 70 quality %, BaO:3 quality % ~ 10 quality %.
Glass substrate as panel display or flat-panel monitor can also use containing the alkali-metal glass containing micro-alkali of trace except non-alkali glass.The glass of glass substrate be the non-alkali glass containing stannic oxide or the glass containing micro-alkali containing stannic oxide time, suppress the volatilization of the platinum metals of the inwall due to the glass treatment device for present embodiment described later and the agglutinator foreign matter of platinum metals that produces is mixed into the Be very effective in melten glass.Non-alkali glass or high containing glass glass viscosity compared with alkali glass of micro-alkali.Owing to improving melt temperature in melting operation, most stannic oxide is reduced in melting operation, needs to improve the melten glass temperature in clarification operation, the reduction of accelerating oxidation tin, and molten glass viscosity is reduced in order to obtain clarifying effect.In addition, stannic oxide, owing to promoting that the temperature of reduction reaction is high compared with the current white arsenic as finings or antimony, promoting clarification to improve the temperature of melten glass, needing the inner wall temperature improving finer 120.In a word, when the glass substrate manufacturing the alkali-free glass substrate containing stannic oxide or the glass containing micro-alkali containing stannic oxide, because need to improve the melten glass temperature clarified in operation, so the easy volatilization that platinum metals occurs.
Further, so-called alkali-free glass substrate refers in fact not containing alkalimetal oxide (Li
2o, K
2o and Na
2o) glass.In addition, the so-called glass containing micro-alkali refers to the content (Li of alkalimetal oxide
2o, K
2o and Na
2the total amount of O) be greater than 0 and be less than the glass of 0.8 % by mole.Comprise the alkalimetal oxide of such as 0.1 quality % ~ 0.5 quality % containing the glass of micro-alkali as composition, preferably comprise the alkalimetal oxide of 0.2 quality % ~ 0.5 quality %.Herein, alkalimetal oxide is at least one be selected from Li, Na and K.The total of the content of alkalimetal oxide can be less than 0.1 quality %.The content of the alkalimetal oxide in glass substrate can be 0 ~ 0.8 % by mole, utilizes method described later that the agglutinator of platinum metals can be suppressed to be mixed in melten glass as foreign matter.
The glass substrate manufactured according to the present embodiment can also contain SnO on the basis of mentioned component
20.01 quality % ~ 1 quality % (being preferably 0.01 quality % ~ 0.5 quality %), Fe
2o
30 quality % ~ 0.2 quality % (being preferably 0.01 quality % ~ 0.08 quality %).The glass substrate manufactured according to the present embodiment is considered carrying capacity of environment and does not preferably contain As
2o
3, Sb
2o
3and PbO or do not contain in fact.
In addition, can also illustrate as the glass substrate manufactured in the present embodiment with the glass substrate of lower-glass composition.Thus, allotment frit, makes glass substrate have and forms with lower-glass.
Such as, with % by mole to represent, containing SiO
255 ~ 75 % by mole, Al
2o
35 ~ 20 % by mole, B
2o
30 ~ 15 % by mole, RO 5 ~ 20 % by mole (RO is the total amount of MgO, CaO, SrO and BaO), R '
2o 0 ~ 0.4 % by mole (R ' be Li
2o, K
2o and Na
2the total amount of O), SnO
20.01 ~ 0.4 % by mole.Now, SiO is comprised
2, Al
2o
3, B
2o
3and in RO (R is the whole elements described in Mg, Ca, Sr and Ba contained by glass substrate) at least any one, mol ratio ((2 × SiO
2)+Al
2o
3)/((2 × B
2o
3)+RO) can be more than 4.0.That is, mol ratio ((2 × SiO
2)+Al
2o
3)/((2 × B
2o
3)+RO) and be more than 4.0 glass be an example of the glass that high temperature viscometrics is high.The glass that high temperature viscometrics is high is because usually need to improve the melten glass temperature in clarification operation, so easily there is the volatilization of platinum metals.In a word, when manufacturing the glass substrate with like this composition, namely the effect of present embodiment described later suppresses the agglutinator of platinum metals to be mixed into Be very effective in melten glass as foreign matter.Further, the viscosity of glass when so-called high temperature viscometrics represents that melten glass is high temperature, so-called pyrometer example is as more than 1300 DEG C herein.
The melten glass used in the present embodiment can be viscosity is 10
2.5temperature during pool is the glass composition of 1500 ~ 1700 DEG C.Such glass is the glass that high temperature viscometrics is high, and the glass that high temperature viscometrics is high is because usually need to improve the melten glass temperature in clarification operation, so easily there is the volatilization of platinum metals.That is, even high temperature viscometrics is high glass composition, namely the effect of present embodiment described later suppresses the agglutinator of platinum metals to be mixed into Be very effective in melten glass as foreign matter.
The strain point of the melten glass used in the present embodiment can be more than 650 DEG C, is more preferably more than 660 DEG C, more preferably more than 690 DEG C, is particularly preferably more than 730 DEG C.In addition, it is 10 that the glass that strain point is high has viscosity
2.5the tendency of the melten glass increase in temperature of pool.In a word, when the glass substrate that manufacture strain point is high, the effect that namely effect of present embodiment described later suppresses the agglutinator of platinum metals to be mixed in melten glass as foreign matter is more remarkable.In addition, the glass that strain point is high, due to for fine indicating meter, therefore stricter to the requirement of the problem that the agglutinator of platinum metals is mixed into as foreign matter.Therefore, the glass substrate of high strain-point, the present embodiment that the agglutinator foreign matter of platinum metals can be suppressed to be mixed into is more applicable.
In addition, melt frit and become and comprise stannic oxide, viscosity 10
2.5time the temperature of melten glass during pool is the glass of more than 1500 DEG C, the above-mentioned effect of present embodiment is more remarkable, and viscosity is 10
2.5the temperature of melten glass during pool is such as 1500 DEG C ~ 1700 DEG C, preferably 1550 DEG C ~ 1650 DEG C.
If the content of the finings that melten glass comprises such as stannic oxide, then the discharging amount being discarded to the oxygen of gas-phase space from melten glass also changes.From this respect, from the aspect of volatilization suppressing platinum metals, the oxygen concn preferably controlled in (adjustment) gas-phase space according to the content of stannic oxide.Thus, from the aspect suppressing the volatilization such as platinum or platinum alloy, the content of restriction stannic oxide is 0.01 ~ 0.3 % by mole, preferably 0.03 ~ 0.2 % by mole.Then in melten glass, the problem of the secondary crystal of stannic oxide and not preferred is there is because produce when the content of stannic oxide is too much.In addition, when the content of stannic oxide is too much, then produce from melten glass be discarded to gas-phase space oxygen increases, the oxygen concn of gas-phase space excessively rises, the problem that increases from the volatile quantity of the platinum metals for the treatment of unit.When the content of stannic oxide is very few, the deaeration of the bubble of melten glass is insufficient.
(formation of finer)
Then, the formation of the finer 41 of clarifying plant is described in detail.Further, clarifying plant comprises ventpipe 41a, heating electrode 41b and surrounds not shown refractory protection and the refractory brick of finer 41 periphery except finer 41.Fig. 3 is the outside drawing mainly representing finer 41.Fig. 4 is the schematic diagram of an example of the sectional view of the inside representing finer 41 and the temperature curve of finer.Finer 41 is preferably platinum metals system, platinum, strengthening platinum or platinum alloy system.
In finer 41, ventpipe 41a and a pair heating electrode 41b is installed.Be formed with the liquid phase of melten glass G flowing in finer 41 therein, be formed with the gas-phase space formed by surface (liquid level) and the wall of the melten glass G be connected with gas-phase space.Along melten glass G flow direction and be formed with gas-phase space 41c.Surround being made up of the material comprising platinum metals at least partially of the wall of gas-phase space 41c.In the present embodiment, the whole wall surrounding gas-phase space 41c is made up of the material comprising platinum metals.
Ventpipe 41a is arranged on the wall that is connected with gas-phase space 41c in the way of melten glass G flow direction, and gas-phase space 41c is communicated with the air in the outside of finer 41.Ventpipe 41a is same with finer 41 preferred shaping by platinum metals.The temperature of ventpipe 41a ventpipe 41a due to heat sinking function easily reduces, so can arrange the heating arrangements for heating ventpipe 41a.
A pair heating electrode 41b is the battery lead plate of the flange shape at the two ends being arranged at finer 41a.Heating electrode 41b makes the electric current provided by not shown power supply flow in finer 41, due to this electric current, and electrified regulation finer 41.In addition, in order to suppress the breakage of heating, a pair heating electrode 41b is cooled.Time as finings use stannic oxide, such as hot defecation pipe 41, top temperature is made to be 1600 DEG C ~ 1750 DEG C, be more preferably 1630 DEG C ~ 1750 DEG C, heating and melting glass G, make top temperature be the temperature of the reduction reaction causing stannic oxide, such as 1600 DEG C ~ 1720 DEG C, be more preferably 1620 DEG C ~ 1720 DEG C.By controlling the electric current flowed in finer 41, the temperature of the melten glass G of the internal flow in finer 41 can be controlled.The temperature of preferred molten glass is 1630 DEG C ~ 1750 DEG C, and the aspect reducing the quantity of remaining bubble from suppressing the volatile quantity of platinum metals is preferably 1650 DEG C ~ 1750 DEG C.
Heating electrode 41b can arrange a pair in finer 41, but the quantity of finer 41 is not particularly limited.By the electrified regulation of heating electrode 41b, the temperature of the inwall be connected with gas-phase space 41c of finer 41 is such as in the scope of 1500 DEG C ~ 1750 DEG C.
In the inside of finer 41, by being added into the redox reaction of the finings such as stannic oxide of melten glass G, removing is contained in the CO of melten glass G
2or SO
2bubble.Specifically, at first, by improving the temperature of melten glass G, finings being reduced, in melten glass G, makes the bubble of oxygen produce.Comprise CO contained in melten glass G
2, N
2, SO
2the oxygen produced due to the reduction reaction of finings is absorbed etc. the bubble of gaseous constituent.Absorb the surface (liquid level) releasing that bubble that oxygen and bubble diameter expand floats up to the melten glass G be connected with gas-phase space to steep, i.e. follicular rupture and disappearing.The gas contained by bubble disappeared is discarded to gas-phase space 41c, is discarded to the outside of finer 41 via ventpipe 41a.Then, reduce the temperature of melten glass G, the finings of reduction is oxidized.Thus, the oxygen residuing in the bubble in melten glass G is absorbed into melten glass G (absorbing process).Like this, remaining bubble reduces and disappears.Like this, by the redox reaction of finings, the bubble contained by removing melten glass G.
Like this, improve the temperature of inwall by the upstream portion of the flow direction of the melten glass in finer 41 and the reduction reaction of finings produced, reduce the temperature of inwall in downstream part and the oxidizing reaction of finings is produced, the temperature of the melten glass of upstream portion increases compared with downstream part, and the discharging amount that its result is adjusted to the oxygen of releasing from melten glass to gas-phase space increases compared with downstream part.Herein, so-called upstream portion refers to the part of the upstream side being positioned at the flow direction of melten glass relative to downstream part, so-called downstream part refers to the part in the downstream side being positioned at the flow direction of melten glass relative to upstream portion, such as, upstream portion refers to the part of melten glass from the upstream side of the flow direction of the middle position of the flow direction of the melten glass of finer 41, and downstream part refers to the part of melten glass from the downstream side of the flow direction of the middle position of the flow direction of the melten glass of finer 41.
The oxygen concn (average oxygen concentration) of gas-phase space 41c can be more than 0%, but is preferably adjusted to more than 0.1%.In addition, the oxygen concn of gas-phase space 41c can be less than 30%, but is preferably adjusted to less than 10%.As made oxygen concn be 0%, then because the volatilization of platinum metals can be controlled, so from the aspect of volatilization controlling platinum metals, preferred oxygen concn is 0%.Oxygen concn for gas-phase space 41c is always 0%, extremely reduce the content of finings owing to existing or need the problem of cost, therefore steep the suppression of volatilizing in minimizing, low cost and platinum metals to realize, the oxygen concn of gas-phase space 41c is preferably more than 0.01%.When the oxygen concn of gas-phase space excessively reduces, then increased by the difference in oxygen concentration of melten glass and gas-phase space and the oxygen increase of releasing from melten glass to gas-phase space 120a, by making melten glass over reduction, there is the sorrow of the bubbles such as the remaining oxysulfide of glass substrate after shaping or nitrogen in result.On the other hand, when oxygen concn is excessive, promote the volatilization of platinum metals, there is the sorrow of the amount of precipitation increase of the platinum metals of volatilization.From above, the upper limit of oxygen concn is preferably 10%.That is, oxygen concn is preferably 0 ~ 10%, is more preferably less than more than 0% 3%, 0% ~ 1%, is particularly preferably less than more than 0.01% 1%.
In order to the vapour pressure suppressing the volatilization of platinum metals preferably to adjust the platinum metals in gas-phase space 41c.From the suppression volatilization of platinum metals and the aspect of aggegation, the vapour pressure of the platinum metals in gas-phase space 41c is preferably 0.1Pa ~ 15Pa, is preferably 3Pa ~ 10Pa.
Do not illustrate, but refractory protection is arranged at the outside wall surface of finer 41.In the outside of refractory protection, also refractory brick is set.Refractory brick is placed with at base station (not shown).
In such clarification operation, form the thermal gradient zone along the flow direction of melten glass G and X-direction (with reference to Fig. 4) middle and upper reaches direction or downstream direction from the top temperature this inwall with thermograde at the inwall of the finer 41 forming gas-phase space 41c.Updrift side refers in the flow direction of melten glass G and to observe and towards melting the direction of groove 40 side from finer 41.Downstream direction refers in the flow direction of melten glass G and to observe and towards the direction of shaped device 42 side from finer 41.This thermal gradient zone uses at least one of the heating of finer 41 and heat radiation and is formed.Then, in order to suppress the aggegation of the volatile matter of the platinum metals of the volatilization being present in gas-phase space 41c, the top temperature in thermal gradient zone and the temperature head of minimum temperature are adjusted to less than 150 DEG C.Herein, the suppression of the aggegation of so-called volatile matter refers to that the aggegation except volatile matter is except 0, and the aggegation amount of volatile quantity comprises reduce the poor situation of said temperature compared with the situation more than 150 DEG C.
By being adjusted to such temperature head, the aggegation of the volatile matter of the platinum metals of the wall volatilization formed from the platinum metals of the volatile matter such as finer 41 by the platinum metals be present in gas-phase space 41c can be suppressed.Volatilize as volatile matter according to the saturation vapour pressure determined according to temperature in platinum metals, but temperature this saturation vapour pressure lower is lower.Therefore, a part for volatile matter becomes easy aggegation in the region that temperature is low., by making the temperature head in the wall of finer 41 be less than 150 DEG C, according to the temperature dependent curve (saturated vapor pressure curve) of saturation vapour pressure, the quantity of aggegation reduces volatile matter.Therefore, the agglutinator being formed at the platinum metals of gas-phase space 41c is few, and a part for this agglutinator departs from and becomes micropartical, and the situation dropping down onto melten glass G reduces.Thereby, it is possible to suppress the foreign matter of platinum metals to be mixed into melten glass G.
When finer 41 of present embodiment, there is heating electrode (vibrating part) 41b of flange shape because there is high heat sinking function, so the wall near electrode (vibrating part) 41b easily becomes low temperature compared with the peripheral part of this wall.Further, such as, in order to suppress overheated breakage, heating electrode 41b liquid or gas cooling.In addition, ventpipe 41a is also because give prominence to from finer 41, so the wall of the finer 41 connected with gas-phase space 41c near ventpipe 41a also easily becomes low temperature compared with this wall periphery.Therefore, the temperature of the wall of the finer 41 be connected with gas-phase space 41c must have temperature curve along the X direction.In other words, present embodiment finer 41 when, the temperature of finer 41 is not fixed, and inevitably produces temperature head.Wall near wall near the two ends of the finer 41 i.e. end of a pair heating electrode 41b and the wall near ventpipe 41a become the low low-temperature region of temperature in X-direction, and the middle portion between ventpipe 41a and heating electrode 41b becomes the high high-temperature area of temperature in X-direction.Even the temperature minimum temperature of such temperature curve also becomes the temperature of high temperature such as more than 1500 DEG C by finer 41 electrified regulation of heating electrode 41b.Therefore, at gas-phase space 41c, form the platinum metals volatilization of finer 41, there is the volatile matter of platinum metals.Or, there is the volatile matter of the platinum metals of volatilizing from other part.Therefore, above-mentioned volatile matter along with platinum metals move to low-temperature region, the easy aggegation according to the saturated vapor pressure curve of platinum metals., in the present embodiment, as mentioned above, because the temperature head of the top temperature in thermal gradient zone and minimum temperature is adjusted to less than 150 DEG C, so the aggegation of the volatile matter of platinum metals can be suppressed.Therefore, the agglutinator being formed at the platinum metals of gas-phase space 41c is few.
Fig. 4 illustrates and the example of the temperature curve (temperature curve of the X-direction of the wall be connected with gas-phase space 41c of finer 41) of finer 41 that represents of the position consistency of the X-direction of finer 41 ground.In temperature curve, between the end 41d and ventpipe 41a of the melten glass G inflow side of finer 41, temperature is top temperature T
max.From this top temperature T
maxposition P start the thermograde that reduces towards the end 41d formation temperature of finer 41.Equally, from top temperature T
maxthe thermograde that reduces towards the position formation temperature of the X-direction of ventpipe 41a of position P.In addition, thermal gradient zone is not shown, but except as described, between the end 41e that also can be formed at the X-direction position of ventpipe 41a and the melten glass G outflow side of finer 41.In such thermal gradient zone, in arbitrary thermal gradient zone, the top temperature in thermal gradient zone and the temperature head of minimum temperature are 150 DEG C.In gas-phase space 41c, because thermal gradient zone is formed on the wall be connected with gas-phase space 41c of finer 41, so form air-flow from the position P of top temperature to finer 41d.Or, form air-flow from the position P of top temperature to the position of ventpipe 41a.Now, even if comprise the volatile matter of platinum metals from the air-flow of position P to the end 41d of finer 41 of temperature or the position P from top temperature to the air-flow of the position of ventpipe 41a, because the temperature head of above-mentioned top temperature and above-mentioned minimum temperature is adjusted to less than 150 DEG C, so volatile matter can be suppressed in the wall aggegation of gas-phase space 41c.In addition, even if comprise the volatile matter of platinum metals to the air-flow of the position of ventpipe 41a from the position P of top temperature, because be vented rapidly from ventpipe 41a to the outside of finer 41, so the aggegation in gas-phase space 41a of the volatile matter of platinum metals can be suppressed.
The vibrating part comprising heating electrode 41b extending to the outside of finer 41 from the periphery of finer 41 is provided with at end 41d, 41e of the finer 41 of present embodiment.Vibrating part heat sinking function is high.Minimum temperature position in said temperature gradient region is the wall near the end of finer 41.Even if at this moment, because the temperature head of above-mentioned top temperature and above-mentioned minimum temperature is adjusted to less than 150 DEG C, so the wall aggegation of platinum family volatile matter near end 41d can be suppressed.
Minimum temperature in said temperature gradient region and top temperature T
maxsuch as being 1500 ~ 1750 DEG C when finings use stannic oxide, for platinum metals holds volatile temperature.Even in this case, because top temperature T
maxbe less than 150 DEG C with the temperature head of the minimum temperature in said temperature gradient region, be more preferably less than 100 DEG C, so suppress the wall aggegation of volatile matter at gas-phase space 41c of platinum metals.Further, such as, minimum temperature is 1500 ~ 1650 DEG C, is preferably 1530 DEG C ~ 1620 DEG C.
The heating of wall of finer 41 of adjustment clarifying plant and the heat radiation of this wall at least one and form such temperature head.That is, said temperature difference is added heat by what utilize electrified regulation to give finer 41, can be realized from the adjustment of the heat dissipation capacity of the outer outer circumferential heat radiation of finer 41.In addition, also by making thermal conduction to the low-temperature region comprising minimum temperature by refractory protection or refractory brick from the high-temperature area of the top temperature comprising thermal gradient zone and reducing temperature head, said temperature difference can be realized.
Reduce to make the temperature head of above-mentioned top temperature and above-mentioned minimum temperature, by adjusting the electric current for electrified regulation flowed in X-direction at the circumferentially each several part (top, sidepiece and bottom) of finer 41, the adjustment adding heat of electrified regulation can be carried out.Such as, by reducing the sectional area of the water composite cooling pipe of the heating electrode 41b being arranged at flange shape, make the top of the electric current deflection finer 41 near heating electrode 41b, the temperature of the inwall be connected with gas-phase space 41c near the heating electrode 41b of flange shape can be made to increase.Thereby, it is possible to make the temperature head of above-mentioned top temperature and above-mentioned minimum temperature be less than 150 DEG C.But when reducing the sectional area of water composite cooling pipe, the temperature of the inwall be connected with gas-phase space 41c near the heating electrode 41b being replaced by finer 41 rises, and reduces in the ability of heating electrode 41b periphery heating and melting glass.Therefore, preferably the sectional area of adjustment water composite cooling pipe, make the temperature head of gas-phase space be less than 150 DEG C, and the temperature of melten glass is more than the temperature of the clarifying effect that can obtain finings.And, the top of so-called finer 41 refers to that the highest portion along short transverse during high uniformity trisection by finer 41 of the short transverse of finer 41 and vertical direction is divided, the lowermost portion of short transverse when so-called bottom refers to trisection, so-called sidepiece refers to remainder during trisection.
Especially because the inwall near heating electrode 41b and ventpipe 41a is the low-temperature region comprising minimum temperature, so it is effective for making said temperature difference be less than 150 DEG C by the temperature improving low-temperature region.
In addition, surround the refractory protection of periphery of finer 41 or the insulating characteristics (thermal conductivity etc.) of refractory brick or thermal impedance (=(thickness of refractory protection or refractory brick)/thermal conductivity) etc. by adjustment and carry out the adjustment of the heat dissipation capacity in the outside of the outer circumferential finer 41 from finer 41.Make especially by utilizing heat radiation to comprise top temperature T
maxthe temperature of high-temperature area to decline and to make said temperature difference be less than 150 DEG C be effective.
In addition; the adjustment of amount of thermal conduction uses by the refractory protection of the surrounding to coated finer 41 or refractory brick the material that a part of thermal conductivity is high; configure this material; make it between above-mentioned high-temperature area and above-mentioned low-temperature region in X-direction continuously and extend, form the hot-fluid from above-mentioned high-temperature area to above-mentioned low-temperature region.Thereby, it is possible to make the temperature head of above-mentioned top temperature and above-mentioned minimum temperature be less than 150 DEG C.Certainly, preferably use in the outside of the high material of conductivity the refractory brick that heat insulating ability is high, suppress heat radiation.
The computer simulation that the thermal conduction of the heating and heat radiation that make to comprise clarifying plant is reproduced, can determine to adjust for making such temperature head be the condition of the heating, heat radiation etc. of the inwall of the finer 41 of less than 150 DEG C.
In computer simulation; make the refractory protection around coated finer 41, finer 41, ventpipe 41a, heating electrode 41b, vibrating part, melten glass modeling respectively, model is given to the specific heat of the parts of these modelings, the material data of thermal conductivity.So, make finer 41 produce heat, outside the model of refractory protection and the model of melten glass carry out heat conducting sight reproduction.
Further, for making said temperature difference be that the method for less than 150 DEG C is not limited to aforesaid method.
In the present embodiment, as glass treatment device with the clarifying plant comprising finer 41 for preferred implementation is illustrated.Present embodiment replaces finer 41 also can be applicable to the steel basin of whipping appts 100, but the application of finer that the temperature head of inwall easily increases is compared with the application of steel basin, that the effect of present embodiment plays more significantly and preferred from the viewpoint of making.The temperature of the inwall in finer 41 is higher than the temperature of the inwall in steel basin, and the top temperature of inwall and the temperature head of minimum temperature easily increase.And, in finer because carry out in order to the reduction reaction of finings the upstream portion heated internal wall of the flow direction of the melten glass of finer, make the temperature of inwall reduce in order to the oxidizing reaction of finings in downstream part temperature adjust, so in the upstream portion of finer and downstream part, the temperature head of inwall easily increases.Such upstream portion and the temperature head of downstream part are not set up in steel basin.And, when as finings use stannic oxide, in order to make the reduction reaction of finings enliven, need to improve top temperature compared with using the situation of white arsenic or antimony.Therefore, in finer, compared with steel basin, said temperature difference easily increases.In the present embodiment, even if the temperature of inwall is high, also poor because reduce said temperature, so in the easy finer increased of said temperature difference, the effect of the platinum metals aggegation of volatilizing can be suppressed to increase compared with steel basin.
In addition, the oxygen concn increasing, release from melten glass to gas-phase space when using stannic oxide as finings oxygen and gas-phase space from the volatile quantity of the high therefore platinum metals of the temperature of the inwall compared with steel basin of the aspect due to finer increases and promotes the volatilization of platinum metals and the easy aggegation in platinum metals of volatilizing due to temperature distribution in finer, the application of finer is compared with the application of steel basin, that the effect of present embodiment plays more significantly and preferred from the viewpoint of making.
Manufacture method involved by present embodiment when platinum metal alloy finer 41 use stannic oxide as finings, especially effectively.In recent years, from the view point of carrying capacity of environment, replace white arsenic or antimony and use stannic oxide as finings.Need to make melten glass at higher temperature in finer 41 than using when white arsenic or antimony owing to using when stannic oxide, therefore the volatilization problems of platinum metals is remarkable.So when promoting the volatilization of platinum metals, then the volatile matter of platinum metals is attached to the inwall of finer 41 and the inwall of ventpipe 41a as the easy aggegation of foreign matter.In this respect, the manufacture method of present embodiment is effective.
The manufacture method of present embodiment can be applicable to the manufacture of the manufacture of panel display or glass substrate for plane display device, the manufacture of cover plate of protection indicating meter, the manufacture of disk glass or solar cell glass substrate.The manufacture method of present embodiment is effective especially when the melten glass clarification making to be generated by the frit of the manufacture being suitable for the panel displays such as liquid-crystal display, plasma display and OLED display or glass substrate for plane display device to the finer 41 be made up of platinum metals.
In finer 41, by the numerical value regulating the bubble of viscosity contained by melten glass G of melten glass G easily to float up to the surface (liquid level) of the melten glass be connected with gas-phase space, melten glass G is clarified., be suitable for the non-alkali glass of panel display or glass substrate for plane display device and when high temperature, there is high viscosity containing the glass of micro-alkali.Such as, for making non-alkali glass and being 10 containing the melten glass G of glass ware forming of micro-alkali in viscosity
2.5there is when poise the temperature of more than 1500 DEG C.Therefore, in clarification operation, owing to needing the melten glass temperature making the temperature of melten glass higher than common alkali glass, the volatilization problems of above-mentioned platinum metals is remarkable.So when promoting the volatilization of platinum metals, then the agglutinator of platinum metals is easily attached to the inwall of finer 41 and the inwall of ventpipe 41a as foreign matter.In this respect, the manufacture method of present embodiment is effective.
(experimental example 1)
Stannic oxide is used as finings, use the finer 41 shown in Fig. 3, along with the clarification carrying out melten glass, after clarification, be shaped to 2270mm × 2000mm, thickness is the sheet glass of 0.5mm, make 100 glass substrates (embodiment 1 ~ 5, comparative example 1 ~ 3).
The adjustment of the wall temperature of finer 41 is carried out in the adjustment of the electrified regulation of the change by the flange shape of above-mentioned heating electrode 41b and the ventpipe 41a to platinum metals, the wall temperature keeping the finer 41 of heating electrode 41b and ventpipe 41a periphery is more than 1550 DEG C, and the temperature head of the top temperature of heating electrode 41b and ventpipe 41a and finer 41 remains on the temperature of setting.Settling time is 1 hour.In addition, the glass of glass substrate consists of SiO
266.6 % by mole, Al
2o
310.6 % by mole, B
2o
311.0 % by mole, the total amount 11.4 % by mole of MgO, CaO, SrO and BaO, SnO
20.15 % by mole, Fe
2o
30.05 % by mole, the total amount 0.2 % by mole of alkalimetal oxide, strain point is 660 DEG C, viscosity is 10
2.5the temperature of melten glass during pool is 1570 DEG C.
On the other hand, except not carrying out the aspect of the change of the flange shape of heating electrode 41b and the adjustment to the electrified regulation of ventpipe, same with above-described embodiment, carry out the clarification (comparative example 1) of melten glass.In comparative example 1, heating electrode during clarification and the temperature of ventpipe are about 1300 DEG C, and the temperature head between the top temperature part of heating electrode and ventpipe and finer is about 350 DEG C.
With with presence or absence of the platinum foreign matter of the glass substrate of visual confirmation embodiment 1 ~ 5 and comparative example 1 time, in embodiment 1 ~ 5, confirm that the quantity of the glass substrate of platinum foreign matter can control at less than 1/6 of comparative example 1.Further, as platinum foreign matter, to long-width ratio be more than 100, maximum length is more than 100 μm persons countings.
Further, as comparative example 2,3, temperature head is made to carry out various change.
In following table 1, temperature head and result are more specifically shown.Time the temperature head of the heating electrode 41b of minimum temperature or the finer 41 of ventpipe 41a and top temperature is 10 DEG C, 50 DEG C, 80 DEG C, 100 DEG C, 120 DEG C, 170 DEG C, 200 DEG C, to the platinum foreign matter number count of the every 1kg of glass substrate.Further, platinum foreign matter quantity when being 120 DEG C with the temperature head of top temperature and minimum temperature, for 1.0, represents the platinum foreign matter quantity under various condition by ratio.Known is the situation (comparative example 2,3) of 170 DEG C, 200 DEG C relative to temperature head, in the situation (embodiment 1 ~ 5) that temperature head is 10 DEG C, 50 DEG C, 80 DEG C, 100 DEG C, 120 DEG C, the amount of the platinum foreign matter in glass substrate can be suppressed.Further, control temperature difference be 10 DEG C, 50 DEG C, 80 DEG C, 100 DEG C, 120 DEG C manufacture glass substrate in, the platinum foreign matter that can control glass substrate is 0.001/below kg.Fig. 5 is the schematic diagram of an example of result of embodiment 1 ~ 5, comparative example 2,3.The longitudinal axis of the chart shown in Fig. 5 is ratio when being 1.0 with platinum foreign matter quantity when temperature head 120 DEG C.When ratio is more than 1.5, then because the yield rate of the glass substrate scope of not allowing, in Figure 5, be threshold value with ratio 1.5 and represented by dashed line.And temperature head more than 150 DEG C time, ratio sharply rises, and the yield rate of glass substrate sharply worsens.
Table 1
| Temperature head (DEG C) | Confirm the ratio having the quantity of the glass substrate of platinum foreign matter | |
| Embodiment 1 | 10 | 0.22 |
| Embodiment 2 | 50 | 0.38 |
| Embodiment 3 | 80 | 0.57 |
| Embodiment 4 | 100 | 0.76 |
| Embodiment 5 | 120 | 1.0 |
| Comparative example 2 | 170 | 2.0 |
| Comparative example 3 | 200 | 3.0 |
(experimental example 2)
Relative to experimental example 1, except the glass of glass substrate composition is changed to SiO
270 % by mole, Al
2o
312.9 % by mole, B
2o
32.5 % by mole, MgO 3.5 % by mole, CaO 6 % by mole, SrO1.5 % by mole, BaO 3.5 % by mole, SnO
2the external application method similarly to Example 1 of 0.1 % by mole makes glass substrate.Now, the strain point of glass substrate is 745 DEG C.
Its result, same with experimental example 1, the known platinum foreign matter that can suppress in glass substrate.
Above the manufacture method of glass substrate of the present invention and glass substrate manufacturing installation have been described in detail, but the present invention is not limited to above-mentioned embodiment, certainly can carry out various improvement or change without departing from the spirit and scope of the invention.
Nomenclature
40 melt groove; 41 finer; 41a ventpipe; 41b heating electrode; 41c gas-phase space; 42d holds; 42 shaped devices; 52 formed bodys; 43a, 43b, 43c transfer tube; 100 whipping apptss; 200 glass substrate manufacturing installations; G melten glass.
Claims (7)
1. a manufacture method for glass substrate, is characterized in that,
Have:
Melt frit and generate the melting operation of melten glass; And
Make melten glass in the internal flow of the glass treatment device be made up of the material comprising platinum metals at least partially of inwall, with the treatment process of melten glass described in the inter-process at described glass treatment device,
In the inside of described glass treatment device, form gas-phase space by the surface of described melten glass and described inwall,
Flow direction along described melten glass forms described gas-phase space,
In described treatment process, forming the described inwall of described gas-phase space, use at least one the formation temperature gradient region in the heat radiation of the heating of described glass treatment device and described glass treatment device, described thermal gradient zone has the thermograde of updrift side in from the top temperature described inwall along the flow direction of described melten glass or downstream direction
In order to suppress the aggegation of the volatile matter of the platinum metals of the volatilization being present in described gas-phase space, the temperature head of the described top temperature in described thermal gradient zone and minimum temperature is made to be less than 150 DEG C.
2. a manufacture method for glass substrate, is characterized in that,
Have:
Melt frit and generate the melting operation of melten glass; And
To the treatment process that described melten glass processes in glass treatment device, wherein, the liquid phase that described glass treatment device has the flowing of described melten glass and the gas-phase space formed by liquid level and the wall of described melten glass, and surround being made up of the material comprising platinum metals at least partially of the wall of described gas-phase space
Flow direction along described melten glass forms described gas-phase space,
In described treatment process, forming the described wall of described gas-phase space, use at least one the formation temperature gradient region in the heat radiation of the heating of described glass treatment device and described glass treatment device, described thermal gradient zone from the top temperature described wall along the flow direction of described melten glass in updrift side or downstream direction there is thermograde
In order to the aggegation of the volatile matter of the platinum metals of the volatilization being present in described gas-phase space can be reduced, the temperature head of the described top temperature in described thermal gradient zone and minimum temperature is made to be less than 150 DEG C.
3. the manufacture method of the glass substrate according to claims 1 or 2, wherein,
Described glass treatment device, in the way of described inwall on the flow direction of described melten glass, the ventpipe that described gas-phase space is communicated with air is set,
The position of the top temperature in described thermal gradient zone between the end of described gas-phase space and the position of described ventpipe,
Described thermal gradient zone is formed at the region between the position of region between the position of described top temperature and the end of described gas-phase space or described top temperature and the position of described ventpipe.
4. the manufacture method of the glass substrate according to any one of claims 1 to 3, wherein, arrange the vibrating part extended from the outside of the described glass treatment device of the outer circumference of described glass treatment device in the end of described gas-phase space, the described minimum temperature position in described thermal gradient zone is the end of described gas-phase space.
5. the manufacture method of the glass substrate according to any one of Claims 1 to 4, wherein, described minimum temperature and described top temperature are 1500 ~ 1750 DEG C.
6. the manufacture method of the glass substrate according to any one of Claims 1 to 5, wherein, described glass treatment device is the clarifying plant of the clarification carrying out melten glass.
7. a glass substrate manufacturing installation, is characterized in that,
There is glass treatment device, described glass treatment device is being made up of the material comprising platinum metals at least partially of inwall and melten glass is flowed and processes the device of described melten glass, described glass treatment device is configured to form gas-phase space by the surface of described melten glass and described inwall at inwall
Described glass substrate manufacturing installation is configured at the described inwall surrounding described gas-phase space, use at least one the formation temperature gradient region in the heat radiation of the heating of described glass treatment device and described glass treatment device, described thermal gradient zone has thermograde from the top temperature described inwall along the updrift side of the flow direction of described melten glass or downstream direction
In order to suppress the aggegation of the volatile matter of the platinum metals of the volatilization being present in described gas-phase space, the described top temperature in described thermal gradient zone and the temperature head of minimum temperature are less than 150 DEG C.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013-268962 | 2013-12-26 | ||
| JP2013268962 | 2013-12-26 | ||
| PCT/JP2014/084541 WO2015099133A1 (en) | 2013-12-26 | 2014-12-26 | Manufacturing method for glass substrate and manufacturing apparatus for glass substrate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104903259A true CN104903259A (en) | 2015-09-09 |
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| JP (1) | JP5937704B2 (en) |
| KR (1) | KR101740159B1 (en) |
| CN (1) | CN104903259B (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109970319A (en) * | 2017-12-27 | 2019-07-05 | 安瀚视特控股株式会社 | The manufacturing method and glass substrate manufacturing device of glass substrate |
| CN110944949A (en) * | 2017-09-13 | 2020-03-31 | 日本电气硝子株式会社 | Method for manufacturing glass article |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111747634B (en) * | 2020-06-08 | 2022-03-15 | 中建材蚌埠玻璃工业设计研究院有限公司 | High-generation TFT-LCD glass substrate production line |
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|---|---|---|---|---|
| WO2012132471A1 (en) * | 2011-03-31 | 2012-10-04 | ＡｖａｎＳｔｒａｔｅ株式会社 | Glass sheet production method |
| CN103118993A (en) * | 2010-09-30 | 2013-05-22 | 安瀚视特控股株式会社 | Method for producing glass sheet |
| JP2013212942A (en) * | 2012-03-30 | 2013-10-17 | Avanstrate Inc | Method for producing glass plate and apparatus for producing glass plate |
| JP2013216531A (en) * | 2012-04-06 | 2013-10-24 | Avanstrate Inc | Manufacturing method of glass plate and manufacturing apparatus of glass plate |
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| JP4790783B2 (en) | 2008-11-05 | 2011-10-12 | ＡｖａｎＳｔｒａｔｅ株式会社 | Manufacturing method of glass plate |
| JP5488865B2 (en) * | 2009-03-03 | 2014-05-14 | 旭硝子株式会社 | Glass melting furnace and glass melting method |
| TWI494283B (en) * | 2010-02-25 | 2015-08-01 | Corning Inc | Apparatus for making a glass article and methods |
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| CN103118993A (en) * | 2010-09-30 | 2013-05-22 | 安瀚视特控股株式会社 | Method for producing glass sheet |
| WO2012132471A1 (en) * | 2011-03-31 | 2012-10-04 | ＡｖａｎＳｔｒａｔｅ株式会社 | Glass sheet production method |
| JP2013212942A (en) * | 2012-03-30 | 2013-10-17 | Avanstrate Inc | Method for producing glass plate and apparatus for producing glass plate |
| JP2013216531A (en) * | 2012-04-06 | 2013-10-24 | Avanstrate Inc | Manufacturing method of glass plate and manufacturing apparatus of glass plate |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110944949A (en) * | 2017-09-13 | 2020-03-31 | 日本电气硝子株式会社 | Method for manufacturing glass article |
| CN109970319A (en) * | 2017-12-27 | 2019-07-05 | 安瀚视特控股株式会社 | The manufacturing method and glass substrate manufacturing device of glass substrate |
| CN109970319B (en) * | 2017-12-27 | 2021-11-09 | 安瀚视特控股株式会社 | Method for manufacturing glass substrate, and glass substrate manufacturing apparatus |
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| Publication number | Publication date |
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| CN104903259B (en) | 2017-09-29 |
| WO2015099133A1 (en) | 2015-07-02 |
| JP5937704B2 (en) | 2016-06-22 |
| JPWO2015099133A1 (en) | 2017-03-23 |
| KR20160093536A (en) | 2016-08-08 |
| KR101740159B1 (en) | 2017-05-25 |
| TW201532991A (en) | 2015-09-01 |
| TWI588108B (en) | 2017-06-21 |
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