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CN105431385B - Manufacturing method, glass substrate and the glass substrate laminate of glass substrate - Google Patents

Manufacturing method, glass substrate and the glass substrate laminate of glass substrate Download PDF

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Publication number
CN105431385B
CN105431385B CN201580000217.5A CN201580000217A CN105431385B CN 105431385 B CN105431385 B CN 105431385B CN 201580000217 A CN201580000217 A CN 201580000217A CN 105431385 B CN105431385 B CN 105431385B
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China
Prior art keywords
glass
melten glass
agglutinator
melten
glass substrate
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CN201580000217.5A
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CN105431385A (en
Inventor
藤本慎吾
铃木骏介
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Avanstrate Inc
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Avanstrate Inc
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Priority to CN201811176904.4A priority Critical patent/CN109534656B/en
Publication of CN105431385A publication Critical patent/CN105431385A/en
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B7/00—Distributors for the molten glass; Means for taking-off charges of molten glass; Producing the gob, e.g. controlling the gob shape, weight or delivery tact
    • C03B7/02—Forehearths, i.e. feeder channels
    • C03B7/06—Means for thermal conditioning or controlling the temperature of the glass
    • C03B7/07—Electric means
    • 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
    • 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)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Glass Compositions (AREA)
  • Surface Treatment Of Glass (AREA)
  • Glass Melting And Manufacturing (AREA)
  • Laminated Bodies (AREA)

Abstract

The manufacturing method of glass substrate is not easy in glass substrate generation strain, is not easy to form the bumps of the main surface of glass substrate, including：Melten glass processing step, at least part that gas-phase space and wall are formed due to the importing because of melten glass is to be present in gas-phase space, volatile matter from the platinum group metal that wall volatilizees agglutinator to be mixed into as foreign matter when handling melten glass in the glass treatment device made of platinum group metal；And agglutinator processing step, reduce the size of agglutinator so that be mixed into the agglutinator of melten glass in the melten glass processing step, maximum length is that the ratio of the number of 50 μm of agglutinators below is 70% or more.The volume of the glass substrate of glass substrate laminate adds up to 0.1m3More than, in whole platinum group metal agglutinators contained by glass substrate, maximum length is that the ratio of the number of 50 μm of agglutinators below is 70% or more.

Description

Manufacturing method, glass substrate and the glass substrate laminate of glass substrate
Technical field
The present invention relates to the manufacturing method of glass substrate, glass substrate and glass substrate laminates.
Background technology
Generally, after glass substrate is by generating melten glass from glass raw material, by clarification steps, homogenization step And melten glass is made to be configured to glass substrate and manufacture.But in order to from the melten glass volume production of high quality of high temperature Glass substrate, it is expected that considering to become foreign matter of defect main cause of glass substrate etc. not from any glass of manufacture glass substrate Reason device is mixed into melten glass.Therefore, the wall of the component contacted with melten glass in the manufacturing process of glass substrate is necessary It is made of material appropriate according to the temperature of the melten glass with the component contact, quality of required glass substrate etc..
For example, during after generating melten glass to supply to forming step, melten glass is high temperature state, because This, the device melted, clarified, supplied, stirred uses the component (example of the platinum containing the platinum group metal high as heat resistance Such as, patent document 1).
Existing technical literature
Patent document
Patent document 1：Special open 2010-111533 bulletins
Invention content
Technical problems to be solved by the inivention
However, platinum group metal is easy to volatilize because of high temperature.Moreover, when the volatile matter agglutination of platinum group metal, as the agglutination A part for the crystallization of object is mixed into the form of foreign matter in melten glass, there is the sorrow for leading to glass substrate quality decline.In particular, from Step is melted to the step of between forming step, clarification steps are the temperature highests of melten glass, therefore is substantially carried out clarification steps Finer be heated to high temperature.Therefore, in the melten glass after clarification steps, the platinum family to volatilize from finer is golden The part for belonging to agglutinator obtained by agglutination is easy to be mixed into wherein and becomes foreign matter.
It is as follows by leading to the problem of when being mixed into the foreign matter of platinum group metal in glass substrate manufacturing process：Due to platinum family The difference of the foreign matter of metal and the coefficient of thermal expansion of glass, generates strain in glass substrate, which can cause the aobvious of display Show bad；Alternatively, the main surface that platinum group metal can be present in glass substrate is nearby formed recessed in the main surface of glass substrate It is convex, to cannot equably carry out the formation for the thin film transistor (TFT) (TFT) being set in main surface, lead to the display for generating display It is bad.In recent years, with the high-definition that the picture of image display device is shown, for the glass substrate for display, Further it is strongly required to reduce the foreign matter for being mixed into the platinum group metal in glass substrate.
In this way, it is preferred that reducing the amount of the foreign matter (agglutinator) for the platinum group metal for being mixed into glass substrate.However, molten before forming Melting the extreme temperatures of glass cannot be from the gas-phase space atmosphere of finer especially in the finer for carrying out clarification steps It excludes as oxygen the reason of inducing platinum group metal volatilization, therefore the volatilization of platinum group metal cannot be completely eliminated.In addition, in finer In, cannot make as generate platinum group metal volatile matter agglutination the reason of device internal face temperature difference be 0, can not be complete It totally disappeared the volatilization except platinum group metal.Accordingly, it is difficult to which the foreign matter (agglutinator) of platinum group metal is prevent completely to be mixed into the fabrication process In melten glass.
Thus, though the object of the present invention is to provide a kind of be mixed into glass substrate platinum group metal foreign matter it is (solidifying Collection object) it is also difficult to generate manufacturing method, glass substrate and the glass substrate laminate of the glass substrate of the above problem.
Solution for solving technical problems
As described above, in view of being difficult to prevent completely the foreign matter (agglutinator) of platinum group metal in the manufacturing process of glass substrate It is mixed into melten glass, then, even if present inventor couple is mixed into the foreign matter (agglutination of platinum group metal in melten glass Object) it is not easy to strain on the glass substrate, is not easy to form the form progress of the concave-convex foreign matter of the main surface of glass substrate Grope.As a result following opinion has been obtained：The maximum length of platinum group metal is 50 μm below for being not easy on the glass substrate The bumps for occurring to strain, be not easy to form the main surface of glass substrate are effective, in addition, be mixed into the platinum group metal of glass substrate In foreign matter (agglutinator), the number ratio of foreign matter (agglutinator) that the maximum length of platinum group metal is 50 μm of platinums group metal below be 70% or more is effective.In particular, having obtained reducing the different of the platinum group metal for being mixed into melten glass when manufacturing glass substrate The size of object (agglutinator) is for the bumps for being not easy to strain on the glass substrate, being not easy to be formed the main surface of glass substrate This effective opinion.This is from order to inhibit to generate the absolute number for showing foreign matter (agglutinator) bad and that reduce platinum group metal The opinion that can not be readily apparent that in the prior art.
That is, one aspect of the present invention is the manufacturing method of glass substrate.The manufacturing method of the glass substrate includes following Mode.
(the 1st mode)
The manufacturing method of glass substrate, including：
Step is melted, glass raw material is melted and generates melten glass；And
Melten glass processing step handles the melten glass, the glass treatment device tool in glass treatment device There is space, is formed by the surface of the melten glass and glass treatment dress as the melten glass imports the space The gas-phase space that the wall set surrounds, at least part of the wall are made of the material comprising platinum group metal, described molten handling When melting glass, agglutinator that be present in the gas-phase space, volatile matter from the platinum group metal that the wall volatilizees is as foreign matter It is mixed into the melten glass,
The manufacturing method of the glass substrate includes agglutinator processing step, is reduced in the agglutinator processing step mixed Enter the size of the agglutinator of the melten glass so that be mixed into the agglutinator of the melten glass, maximum length be 50 μm with Under agglutinator number ratio be 70% or more.
(the 2nd mode)
The manufacturing method of glass substrate, including：
Step is melted, glass raw material is melted and generates melten glass；
Melten glass processing step handles the melten glass, the glass treatment device tool in glass treatment device There is the liquid phase being made of the melten glass and gas-phase space is formed by by the liquid level and wall of the melten glass, surrounds At least part of the wall of the gas-phase space is made of the material comprising platinum group metal, when handling the melten glass, is deposited Agglutinator that be the gas-phase space, volatile matter from the platinum group metal that the wall volatilizees is mixed into the melting as foreign matter In glass；And
Agglutinator processing step reduces the agglutinator that the melten glass is mixed into the melten glass processing step Size so that be mixed into the agglutinator of melten glass, maximum length is that the ratio of the number of 50 μm of agglutinators below is 70% More than.
(the 3rd mode)
The manufacturing method of glass substrate, including：
Step is melted, glass raw material is melted and generates melten glass；And
Melten glass processing step handles the melten glass, the glass treatment device tool in glass treatment device There is space, is formed by the surface of the melten glass and glass treatment dress as the melten glass imports the space The gas-phase space that the wall set surrounds, at least part of the wall are made of the material comprising platinum group metal, described molten handling When melting glass, agglutinator that be present in the gas-phase space, volatile matter from the platinum group metal that the wall volatilizees is as foreign matter It is mixed into the melten glass,
The manufacturing method of the glass substrate includes agglutinator processing step, and institute is adjusted in the agglutinator processing step The solubility for stating the agglutinator in melten glass makes the size reduction for being mixed into the agglutinator of the melten glass.
(the 4th mode)
The manufacturing method of glass substrate, including：
Step is melted, glass raw material is melted and generates melten glass；And
Melten glass processing step handles the melten glass, the glass treatment device tool in glass treatment device There is the liquid phase being made of the melten glass and gas-phase space is formed by by the liquid level and wall of the melten glass, surrounds At least part of the wall of the gas-phase space is made of the material comprising platinum group metal, when handling the melten glass, is deposited Agglutinator that be the gas-phase space, volatile matter from the platinum group metal that the wall volatilizees is mixed into the melting as foreign matter In glass,
The manufacturing method of the glass substrate further includes agglutinator processing step, is controlled in the agglutinator processing step It is supplied to the heat of the agglutinator so that it is that can reduce to be mixed into the melten glass to be supplied to the heat of the agglutinator It is more than the minimum heat of the size of the agglutinator.
(the 5th mode)
The manufacturing method of glass substrate according to either type in the mode of the 1st mode~the 4th,
In the manufacturing method of the glass substrate, make the maximum temperature of the wall contacted with the gas-phase space with most The difference of low temperature is 5 DEG C or more, and the gas-phase space is oxygen-containing.
(the 6th mode)
The manufacturing method of glass substrate according to either type in the 1st mode~the 5th mode,
It heats up in the agglutinator processing step, makes the temperature ratio of the melten glass containing the agglutinator There is the temperature for the melten glass that agglutinator is mixed into the region of melten glass high in the melten glass processing step.Alternatively, In the agglutinator processing step, the temperature of the melten glass is maximum temperature.
(the 7th mode)
The manufacturing method of glass substrate according to either type in the mode of the 1st mode~the 6th, in the agglutination In object processing step, make the agglutinator be dissolved in melten glass solubility ratio have in the melten glass processing step it is solidifying Collection object is mixed into the height of the solubility in the region of melten glass.Alternatively, appointing according in the 1st mode~the 6th mode The manufacturing method of glass substrate described in one mode is dissolved in the agglutinator processing step by improving the agglutinator The size for the agglutinator for being mixed into the melten glass is reduced in the solubility of melten glass.Specifically, according to the 1st side The manufacturing method of glass substrate in formula~the 6th mode described in either type passes through in the agglutinator processing step Computer heating control melten glass improves the solubility that the agglutinator is dissolved in melten glass, and the melting glass is mixed into reduce The size of the agglutinator of glass.
(the 8th mode)
The manufacturing method of glass substrate according to either type in the 1st mode~the 7th mode,
The glass treatment device is the clarifier for having finer,
The melten glass flows in the finer,
The gas-phase space in the finer is formed along the flow direction of the melten glass, at the agglutinator Reason step carries out in the finer.
(the 9th mode)
The manufacturing method of glass substrate according to either type in the 1st mode~the 8th mode,
In the melten glass processing step, using the tin oxide for including in the melten glass reduce described molten Melt the clarifying treatment of the number of bubbles in glass, the melten glass flows in the glass treatment device, with the gas phase The Temperature Distribution along the flow direction of the melten glass is formed on the wall of space contact, is formed in the gas-phase space Oxygen concentration along the flow direction of the melten glass is distributed.
(the 10th mode)
The manufacturing method of glass substrate according to either type in the 1st mode~the 9th mode,
The agglutinator processing step carries out in the glass treatment device, and the melten glass is in the glass treatment It flows, is in the melten glass flowed in the glass treatment device in device, along melting glass in the gas-phase space On the flow direction of glass, the melten glass flowed on pair position corresponding with the highest region of oxygen concentration carries out at the agglutinator Manage step.
(the 11st mode)
The manufacturing method of glass substrate according to either type in the 1st mode~the 10th mode,
Make the oxygen concentration in the gas-phase space be more than 0% and 1.0% hereinafter, making to contact with the gas-phase space The maximum temperature of the wall and the difference of minimum temperature are 5 DEG C or more and 100 DEG C or less.
(the 12nd mode)
The manufacturing method of glass substrate according to either type in the 1st mode~the 11st mode,
Control the temperature of melten glass so that the temperature of the melten glass in the agglutinator processing step is 1670 DEG C~1730 DEG C within the temperature range of.
(the 13rd mode)
The manufacturing method of glass substrate according to either type in the 1st mode~the 12nd mode,
Control the temperature of melten glass so that there is agglutinator to be mixed into melten glass in the melten glass processing step Within the temperature range of the temperature of the melten glass in region is 1580 DEG C~1660 DEG C.
(the 14th mode)
The manufacturing method of glass substrate according to either type in the 1st mode~the 13rd mode,
The melten glass processing step includes the agglutinator processing step.
(the 15th mode)
The manufacturing method of glass substrate according to either type in the 1st mode~the 14th mode,
The glass substrate is glass substrate for display.
(the 16th mode)
The manufacturing method of glass substrate according to either type in the 1st mode~the 15th mode,
A concentration of 0.05 of the platinum group metal being dissolved in the melten glass when agglutinator processing step being made to start ~20ppm.
(the 17th mode)
The manufacturing method of glass substrate according to either type in the 1st mode~the 16th mode,
In the agglutinator processing step, in [the Fe of glass substrate3+]/([Fe2+]+[Fe3+]) be 0.2~0.5 model Enclose the saturation solubility of the platinum group metal of the interior adjustment melten glass.
(the 18th mode)
The manufacturing method of glass substrate according to either type in the 1st mode~the 17th mode,
The content of alkali metal oxide is 0~0.5 mass % in the glass substrate.
(the 19th mode)
A kind of manufacturing method of glass substrate, which is characterized in that including：
Step is melted, glass raw material is melted and generates melten glass；
Melten glass processing step handles the melten glass, the glass treatment device tool in glass treatment device There is space, is formed by the surface of the melten glass and glass treatment dress as the melten glass imports the space The gas-phase space that the wall set surrounds, at least part of the wall are made of the material comprising platinum group metal, described molten handling When melting glass, agglutinator that be present in the gas-phase space, volatile matter from the platinum group metal that the wall volatilizees is as foreign matter It is mixed into the melten glass；And
Agglutinator processing step makes to be mixed into the agglutinator of the melten glass extremely in the melten glass processing step A few part is dissolved in the melten glass,
A concentration of 0.05 of the platinum group metal being dissolved in the melten glass when agglutinator processing step being made to start ~20ppm.
(the 20th mode)
A kind of manufacturing method of glass substrate, which is characterized in that including：
Step is melted, glass raw material is melted and makes melten glass；
Melten glass processing step handles the melten glass using glass treatment device, the glass treatment device because The importing of the melten glass and formed by the surface of the melten glass and wall encirclement gas-phase space, with the gas-phase space At least part of the wall of contact is made of the material comprising platinum group metal, when handling the melten glass, is present in described Gas-phase space, from the agglutinator of volatile matter for the platinum group metal that the wall volatilizees be mixed into the melten glass；And
Agglutinator processing step makes to be mixed into the agglutinator of the melten glass extremely in the melten glass processing step A few part is dissolved in the melten glass,
In the agglutinator processing step, based on being detected in using glass substrate made of the glass treatment device To the defect number of the agglutinator adjust the temperature of the melten glass, to adjust the agglutinator platinum group metal Saturation solubility makes the defect number for the agglutinator for including in the glass substrate of new production be in permissible level.
Here, in the agglutinator processing step, in order to adjust the saturation solubility of the agglutinator, preferably 1660 The temperature of the melten glass is adjusted in the range of~1750 DEG C.
(the 21st mode)
A kind of manufacturing method of glass substrate, which is characterized in that including：
Step is melted, glass raw material is melted and makes melten glass；
Melten glass processing step handles the melten glass using glass treatment device, the glass treatment device because The importing of the melten glass and formed by the surface of the melten glass and wall encirclement gas-phase space, with the gas-phase space At least part of the wall of contact is made of the material comprising platinum group metal, when handling the melten glass, is present in described Gas-phase space, from the agglutinator of volatile matter for the platinum group metal that the wall volatilizees be mixed into the melten glass；And
Agglutinator processing step makes to be mixed into the agglutinator of the melten glass extremely in the melten glass processing step A few part is dissolved in the melten glass,
In the agglutinator processing step, by [the Fe for adjusting glass substrate in the range of 0.2~0.53+]/ ([Fe2+]+[Fe3+]) come adjust the melten glass the platinum group metal saturation solubility so that include in glass substrate The agglutinator defect number in permissible level.
Here, the described [Fe3+]/([Fe2+]+[Fe3+]) preferably by adjusting the tin oxide contained by the glass substrate It is at least any in the content of the oxide contained in content and glass raw material to be adjusted.
In addition, another aspect of the present invention is the glass substrate laminate for being laminated with multiple glass substrates.At this point, include with Under the 22nd mode.
(the 22nd mode)
A kind of glass substrate laminate, which is characterized in that
The volume of glass substrate in the glass substrate laminate adds up to 0.1m3More than, the glass substrate contains In the agglutinator for the whole platinums group metal having, maximum length is that the ratio of the number of 50 μm of agglutinators below is 70% or more.
In addition, another aspect of the present invention is glass substrate, including the 23rd mode below.
(the 23rd mode)
A kind of glass substrate, which is characterized in that
In the agglutinator of platinum group metal contained by glass substrate, maximum length is the number of 50 μm of agglutinators below Ratio is 70% or more.
In turn, another aspect of the invention is glass substrate manufacturing device.The glass substrate manufacturing device includes with lower section Formula.
(the 24th mode)
Glass substrate manufacturing device, including：
Fusing device melts glass raw material and generates melten glass；
Glass treatment device for handling the melten glass, and has space, described in melten glass importing Space and formed by the surface of the melten glass and wall encirclement gas-phase space, at least part of the wall is by including platinum family The material of metal is constituted, when handling the melten glass, platinum family gold being present in the gas-phase space, volatilizing from the wall The agglutinator of the volatile matter of category is mixed into the melten glass as foreign matter；And
Processing unit reduces the size for the agglutinator for being mixed into the melten glass so that is walked in melten glass processing It is mixed into the agglutinator of melten glass in rapid, maximum length is that the ratio of the number of 50 μm of agglutinators below is 70% or more.
In turn, another aspect of the invention or glass substrate manufacturing device.The glass substrate manufacturing device includes following Mode.
(the 25th mode)
Glass substrate manufacturing device, including：
Fusing device melts glass raw material and generates melten glass；And
Glass treatment device for handling the melten glass, and has space, described in melten glass importing Space and formed by the surface of the melten glass and wall encirclement gas-phase space, at least part of the wall is by including platinum family The material of metal is constituted, when handling the melten glass, platinum family gold being present in the gas-phase space, volatilizing from the wall The agglutinator of the volatile matter of category is mixed into the melten glass as foreign matter,
The glass substrate manufacturing device includes adjustment unit, for adjusting the agglutinator in the melten glass Solubility makes the size reduction for being mixed into the agglutinator of the melten glass.
(the 26th mode)
In addition, the glass of the manufacturing method of the glass substrate of the 1st mode~the 21st mode, the 22nd mode It is any in substrate laminated body, the glass substrate of the 23rd mode and described 24th, 25 modes glass substrate manufacturing devices The glass substrate of mode is the glass substrate with 650 DEG C or more of strain point.
The manufacturing method of the glass substrate of 1st mode~the 21st mode, the glass substrate of the 22nd mode Either type in laminated body, the glass substrate of the 23rd mode and described 24th, 25 modes glass substrate manufacturing devices The glass substrate is used as liquid crystal display glass substrate, organic EL (Electro-Luminescence：Electroluminescent) Glass substrate for display or use LTPS (Low Temperature Poly-silicon：Low temperature polycrystalline silicon) film half The glass substrate for display of conductor.
Invention effect
It is manufactured and is filled according to the manufacturing method of above-mentioned glass substrate, glass substrate, glass substrate laminate and glass substrate It sets, can be not easy to answer on the glass substrate if even if being mixed into foreign matter (agglutinator) of platinum group metal in glass substrate Become, can be not easy to form the bumps of the main surface of glass substrate.Yield rate when manufacturing glass substrate as a result, is improved.
Description of the drawings
Fig. 1 is flow chart the step of showing the manufacturing method of the glass substrate involved by embodiment.
Fig. 2 is the schematic diagram for the composition for showing the glass substrate manufacturing device involved by embodiment.
Fig. 3 is the main outside drawing for indicating the finer involved by embodiment.
Fig. 4 is an example of the sectional view for the inside for indicating the finer involved by embodiment and the Temperature Distribution of finer Schematic diagram.
Fig. 5 is the chart of the relationship of the maximum temperature for indicating melten glass and the ratio of foreign matter.
Specific implementation mode
The manufacturing method of the glass substrate of present embodiment handles melten glass (at melten glass in glass treatment device Manage step), the glass treatment device has space, and the surface for being melted glass is formed as melten glass imports the space The gas-phase space surrounded with the wall of glass treatment device, at least part of the wall are made of the material comprising platinum group metal, For example, the glass treatment device has the liquid phase that is formed by melten glass and is formed by the liquid level and wall of melten glass Gas-phase space, at least part for surrounding the wall of gas-phase space are made of the material comprising platinum group metal.In the melten glass When processing, agglutinator that be present in gas-phase space, volatile matter from the platinum group metal that the wall volatilizees will be mixed into as foreign matter In melten glass.Reduce the processing of the size for the agglutinator for being mixed into melten glass so that be mixed into the described solidifying of melten glass Collect in object, maximum length is that the ratio of the number of 50 μm of agglutinators below is 70% or more (agglutinator processing step).Alternatively, Adjust the solubility of the foreign matter (agglutinator) in melten glass so that the size for being mixed into the agglutinator of melten glass becomes smaller.For example, Control is supplied to the heat of foreign matter (agglutinator) so that it is that can reduce to be mixed into melten glass to be supplied to the heat of foreign matter (agglutinator) Foreign matter (agglutinator) size minimum heat more than (agglutinator processing step).
In this way, the size of the foreign matter (agglutinator) by reducing the platinum group metal for being mixed into glass substrate, so as to be not easy It strains on the glass substrate, and is not easy to form the bumps of the main surface of glass substrate.Therefore, existing problem will be improved, Improve the fabrication yield of glass substrate.
In the following description, the condition as control adjustment solubility makes dissolving of the agglutinator relative to melten glass Degree, which is agglutinator, can be dissolved in melten glass and can reduce the example of the minimal solubility of size or more, enumerate control and be supplied to The heat of agglutinator makes the minimum for being supplied to the heat of agglutinator to be the size that can reduce the agglutinator for being mixed into melten glass More than heat example illustrates.
(manufacturing method and glass substrate manufacturing device of glass substrate)
Fig. 1 is the flow chart of example the step of showing the method for manufacturing glass substrate involved by present embodiment. As shown in Figure 1, the manufacturing method of glass substrate includes mainly：Melt step S1, clarification steps S2, whipping step S3, forming step Rapid S4, slow cooling step S5 and cut-out step S6.
Fig. 2 is the signal of an example of the composition for showing the glass substrate manufacturing device 200 involved by present embodiment Figure.Glass substrate manufacturing device 200 includes melting slot 40, finer 41, agitating device 100, building mortion 42 and delivery pipe 43a、43b、43c.Delivery pipe 43a connections melt slot 40 and finer 41.Delivery pipe 43b connections finer 41 and agitating device 100.Delivery pipe 43c connections agitating device 100 and building mortion 42.
In melting step S1, melts the raw material of glass and generate melten glass.Melten glass, which is accumulated in, to be melted in slot 40, And it is heated to desired temperature.Melten glass contains fining agent.From the viewpoint of reducing environmental pressure, it is suitble to use Tin oxide is as fining agent.
In melting slot 40, glass raw material, which is heated to, corresponding temperature such as to be formed with it and is melted.It is melting as a result, In slot 40, such as obtain the melten glass G of 1500 DEG C~1620 DEG C of high temperature.It, can be with it should be noted that in melting slot 40 By the way that galvanization is come the interelectrode melten glass G of electrified regulation at least 1 between of electrode, in addition, also can be in electrified regulation On the basis of, the flame of burner is secondarily provided to heat glass raw material.
The inside for the delivery pipe 43a and finer 41 that clarification steps S2 is flowed in melten glass carries out.First, make melting glass The temperature rise of glass.Fining agent releases oxygen because reduction reaction occurs for heating.What the bubble absorption being contained in melten glass was released Oxygen and expand, float to the surface that melten glass is contacted with gas-phase space, rupture and disappear.That is, carrying out defoaming treatment step S2A.In turn, since the midway of defoaming treatment step S2A or after defoaming treatment step S2A terminates, agglutinator is carried out Processing step S2B, wherein improve the temperature of melten glass, reduce the agglutinator of mixed platinum group metal in defoaming treatment Size.Then, the temperature of melten glass is reduced.Oxidation reaction occurs for the fining agent being reduced as a result, and absorption remains on melting glass The gas componants such as the oxygen in glass.That is, carrying out absorbing processing step S2C.
Specifically, flowing into finer by delivery pipe 43a from slot 40 is melted melting the melten glass G that slot 40 obtains 41.Finer 41 has the sky for the gas-phase space that the surface for being melted glass G and wall encirclement are formed because of the importing of melten glass G Between, at least part of the wall is constituted with the material comprising platinum group metal.For example, with melten glass flowing liquid phase and by The gas-phase space that the liquid level and wall of melten glass are formed, surrounds at least part of the wall of gas-phase space by comprising platinum group metal Material is constituted.Delivery pipe 43a, 43b, 43c are the pipes of platinum group metal.It should be noted that platinum group metal is meant by single The metal of platinum family element composition and the alloy for the metal being made of platinum family element.Platinum family element is platinum (Pt), palladium (Pd), rhodium (Rh), this 6 kinds of elements of ruthenium (Ru), osmium (Os) and iridium (Ir).In the present embodiment, for example, being suitble to using platinum content be 70% The alloy of above platinum and rhodium.The fusing point of platinum group metal is high, to the corrosion resistance excellent of melten glass.In finer 41 and melting slot 40 are similarly provided with heating unit.In addition, being at least also provided with heating unit in delivery pipe 43a.
In clarification steps S2, follow the steps below：Defoaming treatment step is defoamed by so that melten glass G is heated up；It is solidifying Collect object processing step, by adjusting the heat provided to the foreign matter for the platinum group metal for being mixed into melten glass (agglutinator), to disconnected The foreign matter (agglutinator) of platinum group metal is opened or melted to reduce the size of the foreign matter (agglutinator) of platinum group metal；And at absorption Step is managed, so that melten glass is absorbed the bubble in melten glass by so that melten glass is cooled down.In agglutinator processing step, The size for reducing the foreign matter (agglutinator) of platinum group metal to disconnect or melt the foreign matter (agglutinator) for being mixed into melten glass needs Make the heat for being supplied to foreign matter (agglutinator) more than regulation heat (minimum heat).In this case, control is supplied to The heat of foreign matter (agglutinator) in melten glass makes to be supplied to the heat of foreign matter (agglutinator) to be the minimum heat or more.On Stating minimum heat can be by carrying out testing etc. by pre research in advance.In the feelings for controlling minimum heat with the temperature of melten glass G Under condition, for example, control finer 41 in melten glass G temperature in the range of 1580 DEG C~1730 DEG C, preferably 1670 DEG C~1730 DEG C in the range of.
In clarification steps S2, from the viewpoint of the clarification for fully carrying out melten glass G, preferably delivery pipe 43a's The temperature of the melten glass G of internal flow does not cool down, and gradually heats up.It is preferred that after melting step S1, melten glass G It is warming up to 1630 DEG C or more with 3 DEG C/min or more of speed.
It is 1620 DEG C~1690 DEG C in the maximum temperature of the melten glass G of delivery pipe 43a flowing, preferably 1640 DEG C~ 1670℃.In addition, in the temperature as connecting conveying pipe 43a and the melten glass G of the finer inlet in the region of finer 41 Degree is 1610 DEG C~1680 DEG C, preferably 1630 DEG C~1660 DEG C.In turn, as connection finer 41 and delivery pipe 43b The temperature of the melten glass G in the finer exit in region is 1530 DEG C~1600 DEG C, preferably 1540 DEG C~1580 DEG C.
Melten glass G after being clarified in finer 41 flows into agitating device 100 from finer 41 by delivery pipe 43b. Melten glass G is cooled down when by delivery pipe 43b.
In whipping step S3, the melten glass after stirring clarification makes the ingredient of melten glass homogenize.It reduces as a result, Cause the composition of the melten glass of striped of glass substrate etc. irregular.Melten glass after homogenizing is sent to forming step S4。
Specifically, in agitating device 100, at the temperature lower than the temperature of the melten glass G by finer 41 Stir melten glass G.For example, in agitating device 100, the temperature of melten glass G is 1250 DEG C~1450 DEG C.For example, stirring It mixes in device 100, the viscosity of melten glass G is that 500 pools~1300 are moored.Melten glass G be stirred in agitating device 100 and by It homogenizes.
Melten glass G after homogenizing in agitating device 100 flows into forming from agitating device 100 by delivery pipe 43c Device 42.When melten glass G is by delivery pipe 43c, it is cooled to the viscosity of the forming suitable for melten glass G.For example, melten glass G is cooled to 1100~1300 DEG C.
It should be noted that the whipping step S3 of present embodiment is carried out after clarification steps S2, but whipping step S3 It can also be carried out before clarification steps S2.In this case, the temperature of melten glass G when whipping step S3 can with it is clear The temperature of melten glass G in pigging 41 is equal or higher.
In forming step S4, plate glass is continuously moltened glass into using overflow downdraw or float method.
Specifically, the melten glass G for flowing into building mortion 42, which is supplied to, is set to forming furnace inside (not shown) Formed body 52.In the upper surface of formed body 52 slot is formed with along the length direction of formed body 52.Melten glass G is fed into forming The slot of the upper surface of body 52.The melten glass G overflowed from slot passes through a pair of of side of formed body 52, flows down downwards.Along forming A pair of of melten glass G that the side of body 52 flows down collaborates in the lower end of formed body 52, is continuously configured to plate glass GR.
In slow cooling step S5, the plate glass of progressive forming has desired thickness in forming step S4, and with not The mode for generating strain and warpage slowly cools down.
In cutting off step S6, the plate glass of slow cooling is cut to specific length in slow cooling step S5, obtains glass Plate.Glass plate is further cut to defined size, obtains glass substrate.
(glass substrate laminate and glass substrate)
Present embodiment provides the glass substrate laminate and glass substrate that multiple glass substrates are laminated and are formed.
The glass substrate laminate of present embodiment is characterized in that, total volume 0.1m3More than, the glass substrate layer In the agglutinator for all platinums group metal that stack contains, maximum length is that the ratio of the number of 50 μm of agglutinators below is 70% More than.As described later, such glass substrate laminate can be not easy to generate strain on the glass substrate, can be not easy to form glass The bumps of the main surface of glass substrate.Therefore, each glass substrate of above-mentioned laminated body is suitable as glass substrate for display, especially Be, for being shown in picture in terms of require the high-definition display pannel with glass substrate to be effective.
In addition, the glass substrate of present embodiment is characterized in that, in the agglutinator for the platinum group metal that glass substrate contains, Maximum length is that the ratio of the number of 50 μm of agglutinators below is 70% or more.Glass substrate with this configuration, as after It is described, it can be not easy to generate strain on the glass substrate, enable to the bumps for being less susceptible to be formed the main surface of glass substrate.
In addition, in the agglutinator of the platinum group metal of glass substrate laminate and glass substrate further preferably, maximum length Ratio for the number of 50 μm of agglutinators below is 90% or more.In addition, glass substrate laminate and glass substrate are more preferable In the agglutinator for the platinum group metal contained, maximum length is that the ratio of the number of 30 μm of agglutinators below is 90% or more.
About the glass for glass substrate, the glass that strain point is 600 DEG C or more is suitable for the system of aftermentioned glass substrate Make method.Above-mentioned strain point is more preferably 650 DEG C or more, especially preferably 690 DEG C or more, particularly preferably 730 DEG C or more.
(application examples of glass substrate)
The glass substrate manufactured by the manufacturing method of the glass substrate of present embodiment is be especially suitable for liquid crystal display The glass substrate of the displays such as device, plasma scope, organic el display or the protective glass for protecting display.It uses The display of glass substrate for display further includes organic EL aobvious other than the flat-panel monitor with flat display surface Show the flexible displays of the display surface as device, liquid crystal display with bending.As high-clear display glass base Plate, glass substrate are preferably used as such as liquid crystal display glass substrate, organic EL (Electro-Luminescence：It is electroluminescent Shine) glass substrate for display, use LTPS (Low Temperature Poly-silicon：Low temperature polycrystalline silicon) film half Conductor or IGZO (Indium, Gallium, Zinc, Oxide：Indium gallium zinc oxide) etc. oxide semiconductors display use Glass substrate.
As glass substrate for display, using alkali-free glass or the glass containing micro alkali.Glass substrate for display exists Viscosity when high temperature is high.For example, having 102.5The temperature of the melten glass of the viscosity of pool is at 1500 DEG C or more.It needs to illustrate It is that alkali-free glass is that essence is free of alkali metal oxide (R2O the glass of composition).It is substantive to refer to without alkali metal oxide, It removes from the mixed impurity such as raw material, glass of the alkali metal oxide as the composition of glass raw material is not added with, for example, alkali metal The content of oxide is less than 0.1 mass %.
(glass composition)
In melting slot 40, glass raw material is melted using heating unit (not shown), generates melten glass G.Glass raw material It is deployed into the glass that can substantially obtain and it is expected composition.One example of the composition as glass, is suitable for FPD Device (FPD) contains SiO with the alkali-free glass of the glass substrate for display such as glass substrate250 mass of mass %~70 %；Al2O30 The mass of quality %~25 %；B2O30 mass of mass %~15 %；0 mass of mass %~10 % of MgO；0 matter of mass %~20 of CaO Measure %；0 mass of mass %~20 % of SrO；0 mass of mass %~10 % of BaO.It should be noted that can also be BaO be 0 The mass % of quality %~20, rather than BaO is 0 mass of mass %~10 %.Here, the total content of MgO, CaO, SrO and BaO are 5 mass of mass %~30 %.
In addition, as glass substrate for display, can also use containing micro alkali metal oxide containing micro alkali Glass.Glass containing micro alkali includes the R ' of 0.1 mass of mass %~0.5 %2O preferably comprises 0.2 mass % as its ingredient The R ' of~0.5 mass %2O is as its ingredient.Here, R ' is that at least one kind of, R ' is selected from Li, Na and K2O is Li2O、 Na2O、K2The total of the content of O.In addition, R '2The total of the content of O also can be less than 0.1 mass %.Accordingly, with respect to this embodiment party The glass substrate of formula is also suitable for using alkali metal oxide (R ' in addition to alkali-free glass2O content) is 0~0.5 mass % Glass.
The glass manufactured according to the present embodiment can also contain SnO on the basis of mentioned component20.01 matter of mass %~1 Measure % (the preferably 0.01 mass % of mass %~0.5)；Fe2O30 mass of mass %~0.2 % (preferably 0.01 matter of mass %~0.08 Measure %).Additionally, it is contemplated that if environmental pressure, glass preferably made according to the present invention does not contain As substantially2O3、Sb2O3And PbO.In order to mitigate environmental pressure, preferably by tin oxide (SnO2) it is used as fining agent.
Present embodiment be as clarification steps, melten glass processing unit using melten glass processing step include finer 41 Clarifier mode for be illustrated, but as long as carry out melten glass processing step device be provided at melt slot 40 Carry out to carry out melten glass the device of predetermined processing between building mortion 42, there is no particular restriction.Glass treatment device in addition to It is other than clarifier, such as can also be the delivery pipe of agitating device or transferring of molten glass.Therefore, melten glass Processing further includes the processing to homogenize to melten glass, transporting molten other than the processing including fining molten glass The processing etc. of glass.The example of agglutinator processing step S2B is also carried out in clarification steps S2 to be said in addition, enumerating It is bright, but for example can also whipping step S3, with delivery pipe transferring of molten glass G the step of in carry out agglutinator processing step S2B.It should be noted that in the case of even progress in clarification steps S2 in agglutinator processing step S2B, institute as above It states, agglutinator processing step S2B need not also be carried out before absorbing processing step S2C, can be after absorbing processing step S2C It carries out.
(composition of finer)
Then, the composition of the finer 41 of the clarifier in present embodiment is described in detail.Also, clarifier in addition to Further include the refractory protection (not shown) of the periphery of snorkel 41a, heating electrode 41b and encirclement finer 41 outside finer 41 Layer and refractory brick.Fig. 3 is the main outside drawing for indicating finer 41.Fig. 4 is the sectional view for the inside for indicating finer 41 and shows Go out the figure of an example of the Temperature Distribution of finer.
Snorkel 41a and a pair of of heating electrode 41b is installed in finer 41.The inside of finer 41 has because of melting The importing of glass G and the space for forming the gas-phase space 41c that the surface for being melted glass G and wall surround.For example, finer 41 The gas-phase space that inside has the liquid phase of melten glass G flowings and formed by the liquid level and wall of melten glass G.Gas-phase space 41c It is formed along the flow direction of melten glass G.At least part of the wall of gas-phase space 41c is surrounded by the material comprising platinum group metal It constitutes.In the present embodiment, the entire wall for surrounding gas-phase space 41c is made of the material comprising platinum group metal.
Snorkel 41a is set to the wall contacted with gas-phase space 41c in the midway of the flow direction of melten glass G, makes gas phase The atmosphere of space 41c and the outside of finer 41.Snorkel 41a preferably in the same manner as finer 41 with platinum group metal at Shape.Snorkel 41a is because of heat sinking function so that the temperature of snorkel 41a is easy to decline, therefore can also be arranged for heating ventilation The heating mechanism of pipe 41a.
A pair of heating electrode 41b is provided at the electrode plate of the flange shape at the both ends of finer 41a.Heating electrode 41b makes The current direction finer 41 supplied from power supply (not shown), using the electric current, finer 41 is energized heating.Using oxidation In the case that tin is as fining agent, for example, finer 41 wall be heated to maximum temperature be 1670 DEG C~1750 DEG C, more preferably It is 1690 DEG C~1750 DEG C.The maximum temperature of the wall of finer 41 and the difference of minimum temperature are 5 DEG C or more, and gas-phase space has oxygen Gas.The temperature of melten glass G is heated to the temperature for the reduction reaction for promoting tin oxide.In turn, melten glass G is preferably heated To disconnect or melt platinum group metal foreign matter (agglutinator) temperature, such as 1670 DEG C or more, be more preferably heated to 1680 DEG C or more.More specifically, 1670 DEG C~1730 DEG C are preferably heated to, is more preferably heated to 1680 DEG C~1700 DEG C.It is molten If melting the maximum temperature of glass G more than 1730 DEG C, the easy melting loss of tube capacity that the platinum group metal by constituting finer 41a is formed.This Outside, the maximum temperature of melten glass G can be calculated according to the measured value of the thermocouple (not shown) set on finer 41.
The melting in the internal flow of such finer 41 can be controlled by controlling the electric current flowed in finer 41 The temperature of glass G.
A pair of of heating electrode 41b is set in finer 41, but there is no particular restriction for the quantity of heating electrode 41b.Pass through control The magnitude of current of system heating electrode 41b, to which the temperature for the wall of finer 41 contacted with gas-phase space 41c is for example controlled in In the range of 1500~1750 DEG C.
It is anti-using the fining agent, the redox of such as tin oxide that contain in melten glass G in the inside of finer 41 It answers, include in removing melten glass G contains CO2Or SO2Bubble.Specifically, first, increasing the temperature of melten glass G makes Fining agent restores so that generates oxygen bubbles in melten glass G.Include in melten glass G contains CO2、N2、SO2Equal gases at The bubble divided and the oxygen bubbles generated by the reduction reaction of fining agent are fit.With the bubble floating after oxygen bubbles zoarium to gas Phase space contact melten glass G surface and discharge bubble, i.e. rupture disappearance (defoaming treatment).Melting in the defoaming treatment The temperature of glass G is 1610 DEG C~1730 DEG C, preferably 1640 DEG C~1710 DEG C.For above range temperature when, platinum group metal It largely volatilizees from the wall of finer 41.Oxygen is discharged to gas-phase space due to defoaming, therefore is carrying out the gas-phase space of defoaming treatment Part oxygen concentration is got higher, as a result, the volatilization of platinum group metal is more active.Along with this, the platinum family gold contained in gas-phase space The concentration of the volatile matter of category is got higher, and therefore, easy tos produce the agglutination of the volatile matter for the platinum group metal contained in gas-phase space.Especially It, the volatile matter of platinum group metal is easy to be aggregated in the position of the Local cooling of wall, for example in the wall of the entrance of finer 41. Therefore, being attached to a part for the agglutinator of the platinum group metal of the wall of finer 41 can fall off, and be easy as foreign matter to be mixed into melting In glass G.For example, after melten glass flows into finer 41, it is easy in the temperature of melten glass G to be 1580 DEG C~1660 DEG C Region is contained in the agglutination of the volatile matter of the platinum group metal in gas-phase space and agglutinator is mixed into melten glass G.
Therefore, from the midway of defoaming treatment or after defoaming treatment terminates, reduce being mixed into melten glass G's The agglutinator processing step of the size of the foreign matter (agglutinator) of platinum group metal.
When carrying out agglutinator processing step after defoaming treatment terminates, melten glass G is preferably set to heat up so as to include The temperature of the melten glass G of the foreign matter (agglutinator) of platinum group metal is than there is the foreign matter of platinum group metal (agglutinator) to be mixed into melten glass The temperature of melten glass in the region of G is high.
In addition, when carrying out agglutinator processing step from the midway of defoaming treatment step, it is carried out at the same time defoaming treatment step With agglutinator processing step.From the midway of defoaming treatment step carry out agglutinator processing step in the case of, sometimes simultaneously into Row defoaming treatment step and agglutinator processing step.When carrying out agglutinator processing step from the midway of defoaming treatment step, Melten glass is maximum temperature in agglutinator processing step.That is, defoaming treatment step (melten glass processing step) can also wrap Include agglutinator processing step.
In agglutinator processing step, preferably by controlling the foreign matter (agglutinator) to the platinum group metal for being mixed into melten glass The heat of application, specifically, by make melten glass G temperature be 1670 DEG C or more, to disconnect, melt the different of platinum group metal Object (agglutinator).At this point, in the foreign matter (agglutinator) for passing through the platinum group metal to be mixed into melten glass G, maximum length be 50 μm The ratio of the number of the foreign matter of following size carries out agglutinator processing step in 70% or more mode, to make glass substrate produce Raw should become smaller, and also less form bumps in the main surface of glass substrate.In order to form this level of foreign matter, preferably make to melt Melt the temperature of glass G to maintain 10 minutes in 1670 DEG C or more of state or more, more preferably maintain 30 minutes or more.That is, contracting In the agglutinator diminution processing of the size of the foreign matter (agglutinator) of small platinum group metal, by being kept at 1670 DEG C or more of temperature 10 minutes or more, the size of the foreign matter (agglutinator) of platinum group metal can be reduced.
In addition, in present embodiment, in above-mentioned agglutinator processing step, solubility is further preferably controlled so that be mixed into molten The solubility ratio that the foreign matter (agglutinator) for melting the platinum group metal of glass is dissolved in melten glass has in melten glass processing step The foreign matter (agglutinator) of platinum group metal is mixed into the height of the solubility in the region of melten glass.Foreign matter (agglutinator) is being improved to melting In the case of the solubility of glass G, by making the temperature rise of melten glass G, so as to improve agglutinator to melten glass Solubility, alternatively, by making the temperature rise of melten glass G and/or extending processing time, so as to improve foreign matter (agglutinator) To the meltage of melten glass G.
It should be noted that the foreign matter (agglutinator) of platinum group metal is thread elongated in one direction.Therefore, platinum The maximum length of the agglutinator (foreign matter) of race's metal external (circumscribed) foreign matter when referring to foreign matter (agglutinator) for shooting platinum group metal Picture bounding rectangle long side length.
Before agglutinator processing step, the ratio of the foreign matter (agglutinator) for the platinum group metal that maximum length is 100 μm or more More than 80%.In addition, in the present embodiment, the foreign matter (agglutinator) of the platinum group metal before agglutinator processing step refers to, most The ratio between long length and minimum length, i.e. aspect ratio are more than the foreign matter of 100 platinum group metal.For example, foreign matter (the agglutination of platinum group metal Object) maximum length be 50 μm~300 μm, minimum length be 0.5 μm~2 μm.
Then, the temperature for reducing melten glass G, makes the fining agent of reduction aoxidize.Remain on as a result, in melten glass G The oxygen of bubble is melted glass G and absorbs (absorption processing).In this way, remaining bubble becomes smaller and disappears.In this way, utilizing fining agent Redox reaction removes the bubble for including in melten glass G.In addition, in absorbing processing step S2C, the temperature of melten glass G The temperature of degree and the wall of finer 41 is down to 1580 DEG C hereinafter, compared with defoaming treatment step S2A, the oxygen contained in gas-phase space Concentration declines, therefore is difficult to carry out the volatilization and agglutination of platinum group metal.Therefore, it in absorbing processing step S2C, is walked with defoaming treatment Rapid S2A is compared, the agglutinator of new platinum group metal become foreign matter and be mixed into melten glass G possibility it is extremely low.
Although not shown, but in the outside wall surface of finer 41 it is equipped with refractory protection.It is additionally provided on the outside of refractory protection Refractory brick.Refractory brick is placed in base station (not shown).It should be noted that refractory protection and/or refractory brick can also be passed through Heat dissipation capacity of the adjustment from finer 41 controls the temperature for the wall of finer 41 contacted with gas-phase space 41c and/or clear The melten glass temperature flowed in pigging 41.
Fig. 4 show the finer 41 of expression corresponding with the position of the X-direction of finer 41 Temperature Distribution (finer 41 With the Temperature Distribution of the X-direction of the gas-phase space 41c walls contacted) an example.In Temperature Distribution, in the molten of finer 41 Melt between the end 41d (entrance) of the inflow sides glass G and snorkel 41a, temperature becomes maximum temperature Tmax.It is formed from the highest Temperature TmaxPosition P play the temperature gradients declined towards the end 41d temperature of finer 41.Equally, it is formed from maximum temperature TmaxPosition P play the temperature gradient declined towards the position temperature of the X-direction of snorkel 41a.In addition, although not shown, but in addition to Other than above-mentioned, also in the end 41e (outlet) of the position of the X-direction of snorkel 41a and the outflow sides melten glass G of finer 41 Between form thermal gradient zone.In such thermal gradient zone, in any thermal gradient zone, in thermal gradient zone Maximum temperature and minimum temperature temperature difference more than 0 DEG C and at 150 DEG C hereinafter, more preferably above 0 DEG C and at 100 DEG C or less. As shown in figure 4, becoming maximum temperature T in the temperature continued to wallmaxThe first half in temperature rise section start at defoaming Reason, at least continues to maximum temperature Tmax.In addition, including maximum temperature TmaxThe latter half in temperature rise section start to coagulate Collect object processing step, at least continues to maximum temperature Tmax.Agglutinator processing step is for example 1670 in the temperature of melten glass G DEG C or more start.It, can be with it should be noted that about the time point that defoaming treatment step terminates to terminate with agglutinator processing step Be either one formerly, but the object from the foreign matters of all platinums group metal that will be mixed into melten glass as agglutinator processing step From the point of view of aspect, preferably the end of the end of agglutinator processing step and defoaming treatment step is simultaneously or after which.
In this way, in the present embodiment, carrying out defoaming treatment to the bubble in melten glass G, but at this point, from wall volatilization The agglutinator of the volatile matter of platinum group metal is mixed into as foreign matter in melten glass G.Reduce the big of the agglutinator for being mixed into melten glass G It is small so as to be mixed into the foreign matter (agglutinator) of melten glass G, the number that maximum length is 50 μm of foreign matters (agglutinator) below Ratio is 70% or more.Alternatively, control is applied to the heat of the foreign matter of platinum group metal, to reduce the foreign matter of mixed platinum group metal Size.Even if can be not easy to strain on the glass substrate if the foreign matter of platinum group metal is mixed into glass substrate as a result, energy It is enough not easy to form the bumps of the main surface of glass substrate.
In addition, the maximum temperature of the temperature of the wall contacted with gas-phase space in above-mentioned finer 41 and minimum temperature it Difference be 5 DEG C or more, even if even gas-phase space be oxygen containing atmosphere, i.e., easy to produce platinum group metal agglutinator condition, Also the size of the foreign matter for the platinum group metal for including in melten glass can be reduced or maximum length can be made to be 50 μm of platinum families below The ratio of the number of the foreign matter of metal is 70% or more.Therefore, even if the foreign matter of platinum group metal can not being mixed into glass substrate yet It easily strains on the glass substrate, can be not easy to form the bumps of the main surface of glass substrate.
In addition, when carrying out agglutinator processing step, preferably heat up so that the temperature of the melten glass G comprising agglutinator Than in melten glass processing step the foreign matter (agglutinator) of platinum group metal be mixed into the melten glass in the region of melten glass G Temperature is high.Thermal cutoff can be utilized as a result, or melt the foreign matter (agglutinator) of platinum group metal, can reliably reduce the different of platinum group metal The size of object (agglutinator).
In addition, glass treatment device is the clarifier for having finer 41, the gas-phase space in finer 41 is along melting The flow direction of glass is formed, and agglutinator processing step is preferably carried out in finer 41.It is clear during until forming step The temperature of melten glass G in pigging 41 is maximum temperature, so as to easily by heat by the (agglutination of the foreign matter of platinum group metal Object) it disconnects or melts.
In the glass treatment step of present embodiment, reduction melting is carried out using the tin oxide for including in melten glass G The clarifying treatment of number of bubbles in glass G makes the wall contacted with gas-phase space in glass treatment device be formed along melting glass The Temperature Distribution of the flow direction of glass makes gas-phase space be formed and is distributed along the oxygen concentration of the flow direction of melten glass G.At this In the device of sample, due to the oxygen concentration distribution for thering is the volatilization to platinum group metal to have an impact, so easy ting produce platinum group metal The agglutinator of volatile matter, the agglutinator are easy as foreign matter to be mixed into melten glass.Even if can be easily if in this case The size for the foreign matter (agglutinator) for reducing platinum group metal can be not easy shape so as to be not easy to strain on the glass substrate At the bumps of the main surface of glass substrate.
It is preferred that agglutinator processing step carries out in glass treatment device, by what is flowed in the glass treatment device Melting glass in melten glass, being flowed on the position of flow direction corresponding with the highest region of oxygen concentration in gas-phase space The mode that glass is included carries out agglutinator processing step.In Temperature Distribution shown in Fig. 4, the defoaming treatment of melten glass G In maximum temperature TmaxPlace carries out most active.As a result, due to the oxygen discharged from bubble, in maximum temperature TmaxNeighbouring gas phase is empty In interior region, oxygen concentration becomes highest.For example, to by corresponding with the region in the highest gas-phase space of the oxygen concentration The melten glass of the position of flow direction carries out agglutinator processing step.Therefore, even if platinum group metal makes because of maximum oxygen concentration The volatilization of platinum group metal is active, and result leads to the agglutinator for easy ting produce platinum group metal and makes the agglutinator conduct of platinum group metal When foreign matter is mixed into melten glass, the size of the foreign matter also can be efficiently reduced.
It is preferred that the oxygen concentration in the gas-phase space of finer 41 be more than 0% and 1.0% hereinafter, the wall of finer 41 The difference of maximum temperature and minimum temperature is 5 DEG C or more and 100 DEG C or less.The volatilization that can inhibit platinum group metal as a result, inhibits to be mixed into The foreign matter of the platinum group metal of melten glass G.However, even if in this case, the foreign matter of platinum group metal can not be made completely It is zero.Therefore, by reducing the size of the foreign matter of platinum group metal, so that being not easy to strain on the glass substrate, being not easy The effect for forming the concave-convex present embodiment of the main surface of glass substrate is more notable.In addition, since platinum group metal can be inhibited Volatilization, so as to improve the service life for the device that finer 41 etc. is made of platinum group metal.
In addition, at least part of melten glass processing step by the temperature of melten glass G control 1580 DEG C~ The temperature of 1660 DEG C of temperature range, melten glass G when by agglutinator processing step is controlled at 1670 DEG C~1730 DEG C, thus Defoaming treatment can reliably be carried out and can reliably reduce the size of the foreign matter (agglutinator) of platinum group metal.That is, can be simultaneous Care for reduction of reduction and the maximum length for the number of bubbles for including in glass substrate for the foreign matter of 50 μm or more of platinum group metal.Separately Outside, when the oxygen concentration of the gas-phase space of finer 41 has the distribution different because of place, it is higher than the area of specified value in oxygen concentration It in domain, is easy to be mixed into the foreign matter (agglutinator) of platinum group metal to melten glass G, it is therefore preferable that the temperature of melten glass G is adjusted For can reduce being mixed into foreign matter (agglutinator) of platinum group metal platinum group metal foreign matter (agglutinator) size degree Temperature, such as 1680 DEG C or more of temperature.It is further preferred that by the control of melten glass temperature for along the oxygen concentration of gas-phase space point Cloth forms the Temperature Distribution of melten glass.
In the above-described embodiment, the example of the condition of the solubility of the agglutinator in melten glass is adjusted as control, The example that control is supplied to the heat of agglutinator has been illustrated.However, about by solubility be adjusted to solubility be it is above-mentioned most Condition more than small solubility can enumerate the following conditions controlled including above-mentioned heat.By controlling these conditions or combination These conditions are controlled, so as to adjust solubility.
(condition of the solubility of adjustment agglutinator)
As the condition of the solubility for adjusting agglutinator, such as can enumerate：
(a) it is dissolved in the concentration of the platinum group metal of melten glass；
(b) temperature or Temperature Distribution (heat that agglutinator is provided) of melten glass；
(c) pressure of gas-phase space；
(d) oxygen activity of melten glass.
(a) it is dissolved in the concentration of the platinum group metal of melten glass
The concentration of the platinum group metal for being dissolved in melten glass when agglutination processing step starts is lower, then in platinum processing step In, the solubility of the foreign matter dissolving of the platinum group metal in melten glass more rises.The concentration example of the platinum group metal of melten glass It can such as crush after cooling, acquired using ICP quantitative analyses to measure by being sampled to the melten glass in finer.
If the concentration of platinum group metal is too low, the solubility of the agglutinator of platinum group metal becomes larger, and there is platinum group metal instead The case where making finer melting loss from the dissolution of the wall of the finer contacted with melten glass to melten glass.
For the viewpoint for inhibiting the such defect of generation, the concentration of platinum group metal is adjusted.
It should be noted that the platinum group metal for being dissolved in melten glass when the agglutinator processing step in finer 41 starts It is mainly derived from from the platinum group metal that the wall surface of finer 41, delivery pipe 43a etc. contacted with melten glass dissolves out.From the wall surface The amount of the platinum group metal of dissolution start dependent on delivery pipe 43a, agglutinator processing step before defoaming treatment step in melting The temperature of the wall surface of the temperature of glass or the finer 41 contacted with melten glass.Therefore, by adjusting delivery pipe 43a, clear The temperature or Temperature Distribution of the wall surface of pigging 41, so as to adjust the platinum family of melten glass when agglutinator processing step starts The concentration of metal.For example, can by adjusting flowed in finer 41 electric current, adjustment to configure around finer 41 plus The electric current or be adjusted by combination thereof that hot device supplies.It is molten when being started by reducing agglutinator processing step Concentration in the platinum group metal of melten glass, the foreign matter of platinum group metal when starting to agglutinator processing step in melten glass The solubility of dissolving rises.From this point of view, the platinum family for being dissolved in melten glass when preferably starting agglutinator processing step The concentration of metal is adjusted to 0.05~20ppm.
As a result, in the manufacturing step of glass substrate, even if the agglutinator of platinum group metal can manufacture if being mixed into melten glass Go out glass substrate of the defect number in permissible level of the agglutinator of platinum group metal.
(b) temperature or Temperature Distribution of melten glass
In finer 41, the solubility for being mixed into the agglutinator of the platinum group metal of melten glass can be by improving melten glass Temperature increase.The temperature of melten glass or Temperature Distribution are described above, therefore the description thereof will be omitted.
If the temperature of melten glass is excessively high, the meltage of the agglutinator of platinum group metal increases, and will produce following lack instead It falls into.
The increase of reboiling bubble
If the temperature of melten glass is excessively high in finer 41, it can excessively be defoamed in defoaming treatment step, cause to melt The oxygen activity of glass is lower, as a result, melten glass becomes reducing condition.When carrying out absorption processing step in this state, Due to following mechanism, exist and excessively generate reboiling bubble in melten glass, causes to remain reboiling bubble in glass substrate The case where bubble.Reboiling bubble specifically includes the sulphur or carbon because containing as impurity in melten glass due to generates SO2Or CO2Deng bubble.In the case where the reducing condition time of melten glass is elongated, it is dissolved in the SO of melten glass3、 CO3It is easy to be reduced, easily generates SO2、CO2.The SO2、CO2With SO3、CO3Compared to being difficult to be dissolved in melten glass, therefore easily become Bubble.If generating more such reboiling bubble, it is likely that remained as air blister defect in glass substrate, lead to glass The quality of glass substrate reduces.In addition, remaining in the bubble of glass substrate for example with laser microscope or visual detection.
The increase of the volatile quantity of glass ingredient
If the temperature of melten glass is excessively high in finer 41, the ingredient of melten glass, such as B2O3It can more evaporate into Gas-phase space.As a result, glass composition localized variation, the glass performances such as coefficient of thermal expansion, the viscosity of glass meeting localized variation, The lines such as striped are generated on the glass substrate.
The increase of the volatile quantity of platinum group metal
If the temperature of melten glass is excessively high in finer 41, the temperature of the gas-phase space contacted with melten glass also becomes Height, in turn, the oxygen amount discharged to gas-phase space due to the defoaming treatment of melten glass become more, as a result, platinum group metal is easy From the wall volatilization for the finer for surrounding gas-phase space.When the volatile quantity of platinum group metal increases, the platinum group metal of gas-phase space Concentration is got higher, and is easy to happen agglutination and agglutinator is mixed into melten glass.
The melting loss of finer
If the temperature of melten glass is excessively high in finer 41, there is the wall melting loss of the finer 41 contacted with melten glass The case where.
For the viewpoint for inhibiting such disadvantage to occur, the temperature or temperature point of the melten glass in finer 41 are carried out The adjustment of cloth.
(c) pressure of gas-phase space
The solubility of the agglutinator of platinum group metal can be increased by the pressure of the gas-phase space 41c of raising finer 41. The pressure of gas-phase space means the gross pressure of gas included in gas-phase space.
For example, the outside of finer 41 is attracted to by snorkel 41a by adjusting the gas in gas-phase space 41c Amount (traffic attraction), the gas released to the supply amount of gas, such as inactive gas in finer 41, from melten glass Discharging amount carries out the adjustment of the pressure of gas-phase space 41c.For example, the outlet and suction of the snorkel 41a by making finer 41 Leading-in device connects or makes above-mentioned narrow egress etc. to adjust the pressure difference of gas-phase space 41c and the air in the outside of finer 41 Size, so as to adjust traffic attraction.For example, matching by adjusting the amount of the fining agent for including in melten glass, glass ingredient Composition and division in a proportion, so as to adjust the discharging amount for the gas released from melten glass.It should be noted that for example can be according to from snorkel The gas flow that 41a is released is high or low come the atmospheric pressure for finding out the outside of the pressure ratio finer 41 of gas-phase space 41c.
To make the foreign matter in melten glass be dissolved in the method that melten glass improves the pressure of gas-phase space 41c, institute as above It states, it can be by adjusting the supply amount of supply amount, such as inactive gas to the gas in finer 41 or adjustment from melting The discharging amount for the gas that glass is released carries out.The pressure of gas-phase space 41c is preferably adjusted in the range of such as 0.8~1.2atm It is whole.
When the hypertonia of gas-phase space 41c, the meltage of the agglutinator of platinum group metal will increase, and generate instead following Disadvantage.
It clarifies bad
When hypertonia in gas-phase space 41c, it is possible to cause to generate in melten glass in defoaming treatment step Bubble be difficult to from the surface of melten glass discharge, so as to cause clarify it is bad.
The increase of the volatile quantity of platinum group metal
When hypertonia in gas-phase space 41c, become larger with the pressure difference of the air in 41 outside of finer, gas-phase space 41 The flow velocity of interior air-flow rises.Therefore, the concentration of the platinum group metal in gas-phase space 41c can not rise, it is difficult to become saturation shape State causes the volatile quantity of the platinum group metal of the wall from finer 41 to increase.
For the viewpoint for inhibiting such disadvantage to generate, the pressure adjustment of gas-phase space is carried out.
(d) oxygen activity of melten glass
In finer 41, increase the dissolving of the agglutinator of platinum group metal by so that the oxygen activity of melten glass is increased Degree.The oxygen activity of melten glass means that the oxygen amount for being dissolved in melten glass (removes and is present in melten glass as bubble Oxygen amount).In the present embodiment, [Fe is used3+]/([Fe2+]+[Fe3+]) index as oxygen activity.Here, [Fe2+] and [Fe3+] it is the Fe for including in melten glass2+And Fe3+Activity can make specifically, being the content indicated with mass percent It is measured with spectrophotometry.
For example, in defoaming treatment step in clarification steps, the temperature of melten glass is got higher, and is dissolved in melten glass Oxygen is defoamed as bubble, therefore the oxygen activity of melten glass declines.On the other hand, in clarification steps, when melten glass When temperature is lower, fining agent absorbs (Qu り Write む) oxygen, therefore oxygen activity increases.
For example, in addition in melting step adjust melten glass in include fining agent, oxide amount other than, in addition to adjust Other than the amount of the oxide of the fining agent or glass raw material that include in whole melten glass, moreover it is possible to solidifying by being adjusted in clarification steps Collect the temperature of the melten glass before object processing step starts or so that oxygen-containing gas is being melted before agglutinator processing step starts It is blistered in glass to adjust the oxygen activity of melten glass.
The adjustment of oxygen activity in melten glass can also be together with the adjustment of the temperature of melten glass or Temperature Distribution It carries out.In addition, the oxygen activity in adjustment melten glass can also be adjusted with the pressure of gas-phase space 41c and be carried out together.Institute as above It states, other than the amount except through the oxide of the fining agent or glass raw material that include in adjustment melten glass, moreover it is possible to by clear The temperature of the melten glass before agglutinator processing step starts is adjusted in clear step or is made before agglutinator processing step starts Oxygen-containing gas blisters to adjust the oxygen activity in melten glass in melten glass.In agglutinator processing step, preferably in example [Fe of the adjustment as the index of oxygen activity in the range of such as 0.2~0.53+]/([Fe2+]+[Fe3+])。
In the adjustment of the oxygen activity of melten glass, if keeping the oxygen activity of melten glass excessively high, the agglutination of platinum group metal The meltage of object increases, and generates following disadvantages instead.
The volatile quantity of platinum group metal increases
If keeping the oxygen activity of melten glass excessive, gas-phase space is discharged into from melten glass in defoaming treatment step Oxygen amount increases, and the oxygen concentration of gas-phase space rises, volatile to the easy oxidation in platinum group metal.Platinum group metal is volatile then easy The agglutinator of platinum group metal is generated, and is easy to be mixed into melten glass.
Oxygen bubbles remains in melten glass
If keeping the oxygen activity of melten glass excessive, in absorbing processing step, the fining agent being reduced will not absorb oxygen, Oxygen containing bubble (oxygen bubbles) is generated in melten glass, as under gas bubbles left in glass substrate, is easy to make glass The quality decline of substrate.
For the viewpoint for inhibiting such disadvantage to generate, preferably increase platinum family in the oxygen activity by adjusting melten glass Conditional parameter appropriate (temperature etc. of melten glass) is combined when the meltage of the agglutinator of metal to be adjusted.
Alternatively, can also the defect number based on agglutinator feedback adjustment is carried out to the adjustment of the temperature of melten glass.As The temperature of the melten glass of regulating object is either the temperature at the time point of beginning agglutinator processing step, can also be agglutination The temperature of object processing step midway.
By being carried out from oblique to light such as the surface of glass substrate injection laser in each position of glass substrate and receiving it Reflected light, and determine the region consistent with the shape of the agglutinator of platinum group metal according to image obtained by light is received, so as to examine Survey the defect of the agglutinator of the platinum group metal in glass substrate.The defect of agglutinator also can be with visual detection rather than making in this wise Use device.When the permissible level of the defect number of the agglutinator is indicated with unit mass, for example, 0.02/kg or less.It is above-mentioned Required by user of the permissible level with glass substrate with strain, main surface the relevant specification of bumps and change.
For example, in the case that the defect number detected in glass substrate is more than permissible level, melten glass is improved Temperature and the saturation solubility for improving the platinum group metal in melten glass promote the molten of the agglutinator for being mixed into melten glass as a result, Solution.On the other hand, in the case that the defect number detected in glass substrate is in permissible level, can than in allowing It is reduced in the high range of the temperature of the corresponding melten glass of upper limit value of horizontal defect number.It adjusts in this way molten Melt the temperature of glass, the saturation solubility of platinum group metal can be adjusted to range appropriate, can will include in glass substrate as a result, The defect number of agglutinator inhibits in permissible level, and can inhibit the product of the glass substrate generated by increase of reboiling bubble etc. Matter declines.
Specifically, in the case where it includes the clarifier of finer that glass treatment device, which is, by making current direction Finer carries out electrified regulation, so as to carry out the temperature adjustment of melten glass.It can be according to the voltage applied to heating electrode Size adjust the magnitude of current.In addition, also may replace electrified regulation or combined with electrified regulation and utilize configuration in finer Around heater (not shown) adjust the temperature of melten glass indirectly.Heater is for example configured in refractory protection, resistance to The inside or outside of firebrick.Alternatively, it is also possible to adjust the heat dissipation capacity from finer by using refractory protection, refractory brick And carry out the temperature adjustment of melten glass.
In agglutinator processing step, preferably instead of the adjustment of the temperature of melten glass or on the basis of temperature adjusts, [Fe of the adjustment as the glass substrate of the index of the oxygen activity of above-mentioned melten glass in the range of 0.2~0.53+]/([Fe2+] +[Fe3+]), to adjust the saturation solubility of above-mentioned platinum group metal, so that the defect of the agglutinator that includes in glass substrate Number is in permissible level.
(agglutinator of the platinum group metal after agglutinator processing step)
After agglutinator processing step, the platinum group metal that includes in melten glass, glass substrate or glass substrate laminate Foreign matter (agglutinator) in, maximum length be more than that 50 μm of the ratio of number of foreign matter (agglutinator) is reduced to less than 30%.
In present embodiment, in the case where improving the temperature of finer 41 to improve the temperature of melten glass G, energy Effectively play the said effect of present embodiment.
For example, in order to mitigate environmental pressure, it is preferable to use fining agent of the tin oxide as melten glass, but tin oxide with As2O3、Sb2O3It compares, the temperature for obtaining clarifying effect (oxidation reaction) is high.Therefore, feelings of the tin oxide as fining agent are being used Under condition, and As is used2O3、Sb2O3It is compared as the case where fining agent, needs the temperature for improving finer 41, improve melten glass The temperature of G.That is, due to the use of tin oxide as fining agent, so compared with the past, it is easier to the volatilization of finer 41 occur (oxidation), the problem of easy ting produce the volatilization and agglutination of platinum group metal.Even if like this due to the use of tin oxide as clarification Agent and make the foreign matter (agglutinator) of platinum group metal be mixed into melten glass amount increase when, can also reduce as in this embodiment The size of the foreign matter of platinum group metal, so as to be not easy to occur on the glass substrate strain, can be not easy to form glass substrate Bumps of main surface and other effects are notable.That is, the amount for causing to show bad such foreign matter (agglutinator) can be reduced fully.
In addition, sticky high melten glass ascent rate of bubble in clarification steps is slow, it is difficult to clarify.Also, it is stirring It mixes and is also difficult to equably stir the high melten glass of viscosity in device 100 in the whipping step carried out.Therefore, in order to fully To homogenizing for clarifying effect or melten glass, the temperature for improving melten glass is needed.For this purpose, when high in order to obtain temperature Melten glass and when also increasing the temperature of glass treatment device, in glass treatment step, the volatilization of platinum group metal becomes fierce, The amount that foreign matter (agglutinator) is mixed into melten glass is easy to increase.I.e. it is easy to lead to the problem of the volatilization and agglutination of platinum group metal.
For example, thin film transistor (TFT) is formed in the glass substrate for display pannel, but it is preferable to use alkali-frees for glass substrate Glass or glass containing micro alkali, in case the action to thin film transistor (TFT) generates bad influence.Alkali-free glass contains micro For the glass of alkali compared with the alkali-containing glass such as soda glass, viscosity is high, to which the ascent rate of bubble is slow in clarification steps, it is difficult to Clarification.For this purpose, in order to fully obtain clarifying effect, the temperature for improving finer 41 is needed, the temperature of melten glass G is improved. That is, since the object of manufacture is alkali-free glass or glass containing micro alkali, compared with alkali glass, it is more easy to clarify The volatilization (oxidation) of pipe 41, the problem of easy ting produce the volatilization and agglutination of platinum group metal.Even if like this in order to use alkali-free Glass or glass containing micro alkali and the temperature for improving finer 41, make the foreign matter (agglutinator) of platinum group metal be mixed into melting glass When the amount of glass increases, the size of the foreign matter of platinum group metal can also be reduced as in this embodiment, so as to be not easy in glass Strain occurs on glass substrate, can be not easy to be formed bumps of main surface of glass substrate and other effects significantly.Draw that is, can fully reduce Play the amount of the bad such foreign matter (agglutinator) of display.
Above-mentioned alkali-free glass or the glass containing micro alkali are the high glass of strain point.The high glass of strain point and strain The low glass of point is compared, and viscosity is high, to which the ascent rate of bubble is slow in clarification steps, it is difficult to clarify.For this purpose, in order to abundant Ground obtains clarifying effect, needs the temperature for improving finer 41, improves the temperature of melten glass G.That is, high in manufacture strain point In the case of glass, compared with the case where manufacturing strain point low glass, it is more easy to that the volatilization (oxidation) of finer occurs, is easy to produce The problem of volatilization and agglutination of raw platinum group metal.Even if improving finer 41 like this for the glass for using strain point high Temperature, make the foreign matter (agglutinator) of platinum group metal be mixed into melten glass amount increase when, can also be as in this embodiment The size for reducing the foreign matter of platinum group metal, so as to be not easy to occur on the glass substrate strain, can be not easy to form glass base Bumps of main surface of plate and other effects are notable.That is, the amount for causing to show bad such foreign matter (agglutinator) can be reduced fully.
It should be noted that for glass substrate for display, it is desirable that the strain point of glass substrate 600 DEG C or more, more It is preferred that at 650 DEG C or more, when the strain point of glass substrate is at 600 DEG C or more, capable of fully reducing for present embodiment causes to show Show the significant effect of the amount of the foreign matter (agglutinator) of undesirable size.In addition, for high-clear display glass substrate, it is desirable that answer Height higher, preferably strain point are 690 DEG C or more, more preferably 730 DEG C or more.When crustal strain point like this is 690 DEG C or more, At 730 DEG C or more, the said effect of present embodiment is more notable.
In addition, the viscosity about the melten glass comprising tin oxide used in present embodiment, preferably 1500 DEG C with On temperature, for example at a temperature of 1500 DEG C~1700 DEG C or 1550 DEG C~1650 DEG C, viscosity 102.5Pool.In this way In the case of, the said effect of present embodiment becomes more notable.
In addition, the plate thickness in the glass substrate manufactured with present embodiment is 0.005mm~0.8mm, preferably 0.01mm In the case of~0.5mm, more preferably 0.01mm~0.2mm, the said effect of present embodiment becomes more notable.Work as manufacture When the thin glass substrate of such plate thickness, foreign matter (agglutinator) easily occurs in glass surface, forms concave-convex surface.In this implementation In mode, it can solve the problems, such as to cause because of such plate thickness by said effect.
[experimental example]
In order to confirm the effect of present embodiment, by the manufacturing step for including agglutinator processing step S2B shown in FIG. 1 Make glass substrate (embodiment).In agglutinator processing step S2B, the control for being supplied to the heat of agglutinator is carried out.
The manufacturing conditions of glass substrate are as described below.
The group of the glass of glass substrate becomes：SiO260.7 quality %；Al2O317 mass %；B2O311.5 quality %；MgO 2 mass %；5.6 mass % of CaO；3 mass % of SrO；SnO20.2 mass %, strain point are 660 DEG C, plate thickness 0.4mm.
In addition, without agglutinator processing step S2B shown in FIG. 1, by being inhaled after defoaming treatment step S2A The existing manufacturing step for receiving processing step S2C makes glass substrate by above-mentioned manufacturing conditions.Specifically, shown in following table 1 Example 1~5 in, make the melten glass G in finer 41 maximum temperature be 1670 DEG C~1720 DEG C, make the temperature of melten glass G It is 40 minutes to spend in 1670 DEG C or more of time.On the other hand, in example 6,7, make the maximum temperature of melten glass G less than 1670 DEG C, make the temperature of melten glass G in 1670 DEG C or more of time be 0 minute.
Using light microscope to the 0.1m that makes in this way3Multiple glass substrates in platinum group metal foreign matter (agglutination Object) statistical magnitude, and measure the maximum length of the foreign matter (agglutinator) of platinum group metal.Then, the institute for being mixed into glass substrate is found out Have in the foreign matter (agglutinator) of platinum group metal, the ratio for the number that maximum length is 50 μm of foreign matters below.The ratio that finds out with Maximum temperature is shown in following tables 1 together.The ratio of foreign matter about example 1~5, which glass substrate all 70% or more, close In the ratio of the foreign matter of example 6,7, which glass substrate is all below 35%.Fig. 5 is to indicate the maximum temperature of melten glass and different The chart of the relationship of the ratio of object.As shown in Figure 5, by making the maximum temperature of melten glass from 1660 DEG C to 1670 DEG C or more, Maximum length is that the ratio of 50 μm of foreign matters below steeply rises, and is 70% or more at 1670 DEG C or more of temperature.1690 DEG C or more when, maximum length, which is the ratio of 50 μm of foreign matters below, becomes 92% or more, maximum in particular, at 1700 DEG C or more Length, which is the ratio of 50 μm of foreign matters below, becomes 100%.It follows that under conditions of this experimental example, when control is to foreign matter When the heat of offer, it is preferred that make the maximum temperature of melten glass be 1670 DEG C or more, preferably 1690 DEG C or more, is more excellent 1700 DEG C or more are selected as to provide heat to foreign matter.Under conditions of this experimental example, 1670 DEG C of maximum temperature is to make maximum length The lower limit temperature for the maximum temperature that ratio for 50 μm of foreign matters below is 70%, but be not necessarily to that maximum temperature is made to be 1670 DEG C or more, by adjusting the solubility of agglutinator (foreign matter) with other methods, can also realize makes maximum length be 50 μm below The ratio of foreign matter is 70%.
[table 1]
More than, manufacturing method, glass substrate and the glass substrate laminate of the glass substrate of the present invention is described in detail, but Present invention is not limited to the embodiments described above, undoubtedly, can carry out various improvement without departing from the scope of the subject in the invention Or change.
Reference sign
40 melt slot
41 finers
41a snorkels
41b heats electrode
41c gas-phase spaces
42 building mortions
52 formed bodies
43a, 43b, 43c delivery pipe
100 agitating devices
200 glass substrate manufacturing devices

Claims (17)

1. a kind of manufacturing method of glass substrate, which is characterized in that including：
Step is melted, glass raw material is melted and generates melten glass；And
Melten glass processing step handles the melten glass, the glass treatment device tool in the pipe of glass treatment device There is space, is formed by the surface of the melten glass and glass treatment dress as the melten glass imports the space The gas-phase space that the wall set surrounds, at least part of the wall are made of the material comprising platinum group metal, described molten handling When melting glass, agglutinator that be present in the gas-phase space, volatile matter from the platinum group metal that the wall volatilizees is as foreign matter It is mixed into the melten glass,
The manufacturing method of the glass substrate includes agglutinator processing step, reduces being mixed into institute in the agglutinator processing step State the size of the agglutinator of melten glass so that when the respective periphery for the agglutinator for setting and being mixed into the melten glass is circumscribed When the length of circumscribed rectangular long side is maximum length, it is mixed into the agglutinator of the melten glass, the maximum length is The ratio of the number of 50 μm of agglutinators below is 70% or more,
Setting is connected to the outside of the gas-phase space and the glass treatment device on the pipe of the glass treatment device Air snorkel, flow through the temperature of the melten glass of the pipe of the glass treatment device in the melten glass Import the position of the entrance and the snorkel, melten glass flow direction of the pipe of the glass treatment device Between reach maximum temperature.
2. a kind of manufacturing method of glass substrate, which is characterized in that including：
Step is melted, glass raw material is melted and generates melten glass；
Melten glass processing step handles the melten glass, the glass treatment device tool in the pipe of glass treatment device There is the liquid phase being made of the melten glass and gas-phase space is formed by by the liquid level and wall of the melten glass, surrounds At least part of the wall of the gas-phase space is made of the material comprising platinum group metal, when handling the melten glass, is deposited Agglutinator that be the gas-phase space, volatile matter from the platinum group metal that the wall volatilizees is mixed into the melting as foreign matter In glass；And
Agglutinator processing step reduces the big of the agglutinator that the melten glass is mixed into the melten glass processing step It is small so that when the length of the circumscribed circumscribed rectangular long side in the respective periphery for the agglutinator for setting and being mixed into the melten glass For maximum length when, be mixed into the agglutinator of melten glass, the maximum length be 50 μm of agglutinators below number ratio Example is 70% or more,
Setting is connected to the outside of the gas-phase space and the glass treatment device on the pipe of the glass treatment device Air snorkel, flow through the temperature of the melten glass of the pipe of the glass treatment device in the melten glass Import the position of the entrance and the snorkel, melten glass flow direction of the pipe of the glass treatment device Between reach maximum temperature.
3. a kind of manufacturing method of glass substrate, which is characterized in that including：
Step is melted, glass raw material is melted and generates melten glass；And
Melten glass processing step handles the melten glass, the glass treatment device tool in the pipe of glass treatment device There is space, is formed by the surface of the melten glass and glass treatment dress as the melten glass imports the space The gas-phase space that the wall set surrounds, at least part of the wall are made of the material comprising platinum group metal, described molten handling When melting glass, agglutinator that be present in the gas-phase space, volatile matter from the platinum group metal that the wall volatilizees is as foreign matter It is mixed into the melten glass,
The manufacturing method of the glass substrate includes agglutinator processing step, is adjusted in the agglutinator processing step described molten The solubility for melting the agglutinator in glass makes the size reduction for being mixed into the agglutinator of the melten glass,
Setting is connected to the outside of the gas-phase space and the glass treatment device on the pipe of the glass treatment device Air snorkel, flow through the temperature of the melten glass of the pipe of the glass treatment device in the melten glass Import the position of the entrance and the snorkel, melten glass flow direction of the pipe of the glass treatment device Between reach maximum temperature.
4. a kind of manufacturing method of glass substrate, which is characterized in that including：
Step is melted, glass raw material is melted and generates melten glass；And
Melten glass processing step handles the melten glass, the glass treatment device tool in the pipe of glass treatment device There is the liquid phase being made of the melten glass and gas-phase space is formed by by the liquid level and wall of the melten glass, surrounds At least part of the wall of the gas-phase space is made of the material comprising platinum group metal, when handling the melten glass, is deposited Agglutinator that be the gas-phase space, volatile matter from the platinum group metal that the wall volatilizees is mixed into the melting as foreign matter In glass,
The manufacturing method of the glass substrate further includes agglutinator processing step, controls and provides in the agglutinator processing step To the heat of the agglutinator so that it is that can reduce to be mixed into the described of the melten glass to be supplied to the heat of the agglutinator It is more than the minimum heat of the size of agglutinator,
Setting is connected to the outside of the gas-phase space and the glass treatment device on the pipe of the glass treatment device Air snorkel, flow through the temperature of the melten glass of the pipe of the glass treatment device in the melten glass Import the position of the entrance and the snorkel, melten glass flow direction of the pipe of the glass treatment device Between reach maximum temperature.
5. the manufacturing method of glass substrate according to any one of claims 1 to 4, wherein
The difference of the maximum temperature and minimum temperature that make the wall contacted with the gas-phase space is 5 DEG C or more,
The gas-phase space is oxygen-containing.
6. the manufacturing method of glass substrate according to any one of claims 1 to 4, wherein
It heats up in the agglutinator processing step, makes the temperature ratio of the melten glass containing the agglutinator in institute It is high to state the temperature for having agglutinator to be mixed into the melten glass in the region of melten glass in melten glass processing step.
7. the manufacturing method of glass substrate according to any one of claims 1 to 4, wherein
In the agglutinator processing step, the agglutinator is made to be dissolved in the solubility ratio of melten glass in the melten glass There is the solubility that agglutinator is mixed into the region of melten glass high in processing step.
8. the manufacturing method of glass substrate according to any one of claims 1 to 4, wherein
The glass treatment device is the clarifier for having finer,
The melten glass flows in the finer,
The gas-phase space in the finer is formed along the flow direction of the melten glass,
The agglutinator processing step carries out in the finer.
9. the manufacturing method of glass substrate according to any one of claims 1 to 4, wherein
In the melten glass processing step, carry out reducing the melting glass using the tin oxide for including in the melten glass The clarifying treatment of number of bubbles in glass,
The melten glass flows in the glass treatment device,
The Temperature Distribution along the flow direction of the melten glass is formed on the wall contacted with the gas-phase space,
The oxygen concentration along the flow direction of the melten glass is formed in the gas-phase space to be distributed.
10. the manufacturing method of glass substrate according to any one of claims 1 to 4, wherein
The melten glass flows in the glass treatment device,
The agglutinator processing step carries out in the glass treatment device, is to flow in the glass treatment device molten Melt in glass, in the gas-phase space along the flow direction of melten glass in position corresponding with the highest region of oxygen concentration The melten glass of upper flowing carries out the agglutinator processing step.
11. the manufacturing method of glass substrate according to any one of claims 1 to 4, wherein
Make the oxygen concentration in the gas-phase space be more than 0% and 1.0% hereinafter, described in making to contact with the gas-phase space The maximum temperature of wall and the difference of minimum temperature are 5 DEG C or more and 150 DEG C or less.
12. the manufacturing method of glass substrate according to any one of claims 1 to 4, wherein
Control melten glass temperature so that the temperature of the melten glass in the agglutinator processing step 1670 DEG C~ Within the temperature range of 1730 DEG C.
13. the manufacturing method of glass substrate according to any one of claims 1 to 4, wherein
Control the temperature of melten glass so that have the region that agglutinator is mixed into melten glass in the melten glass processing step In the melten glass temperature be 1580 DEG C~1660 DEG C within the temperature range of.
14. the manufacturing method of glass substrate according to any one of claims 1 to 4, wherein
The melten glass processing step includes the agglutinator processing step.
15. the manufacturing method of glass substrate according to any one of claims 1 to 4, wherein
The glass substrate is glass substrate for display.
16. the manufacturing method of glass substrate according to any one of claims 1 to 4, wherein
A concentration of 0.05 of the platinum group metal being dissolved in the melten glass when agglutinator processing step being made to start~ 20ppm。
17. the manufacturing method of glass substrate according to any one of claims 1 to 4, wherein
In the agglutinator processing step, in [the Fe of glass substrate3+]/([Fe2+]+[Fe3+]) be 0.2~0.5 in the range of Adjust the saturation solubility of the platinum group metal of the melten glass.
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