CN103708706A - Method and apparatus for producing glass substrate - Google Patents
Method and apparatus for producing glass substrate Download PDFInfo
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- CN103708706A CN103708706A CN201310205311.7A CN201310205311A CN103708706A CN 103708706 A CN103708706 A CN 103708706A CN 201310205311 A CN201310205311 A CN 201310205311A CN 103708706 A CN103708706 A CN 103708706A
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- China
- Prior art keywords
- glass substrate
- glass
- value
- cullet
- frit
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
- C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
- C03B5/235—Heating the glass
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B18/00—Shaping glass in contact with the surface of a liquid
- C03B18/02—Forming sheets
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- 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
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Abstract
The invention provides a method and apparatus for producing glass substrate capable of suppressing non-uniform thermal contraction rate of glass substrates. The method for producing patterned glass substrate is characterized by comprising a fusing step, where glass raw material and glass chips are fused to producing melted glass, and a forming step, where melted glass is shaped into plate-shaped glass. The method controls the beta-OH value of the glass substrate to a beta-OH target value by controlling the ratio of glass chips to the mixture of the glass raw material and glass chips.
Description
Technical field
The present invention relates to a kind of manufacture method and manufacturing installation of glass substrate.
Background technology
Liquid-crystal display, organic EL (Electroluminescence, electroluminescent) in the flat-panel monitor of indicating meter etc., in recent years, require to show the image of fine, as the glass substrate using in indicating meter, requirement is applicable to low temperature polycrystalline silicon (Low-temperature Poly Silicon, below, be called LTPS) TFT (Thin Film Transistor, thin film transistor), but not α-SiTFT (Amorphous Silicon Thin Film Transistor, amorphous silicon film transistor).When the panel of LTPSTFT is manufactured, compare with α-SiTFT, need the more thermal treatment of high temperature.Yet if implement the thermal treatment of such high temperature to forming the glass substrate of TFT, glass substrate, because thermal contraction is shunk, produces the skew that is formed at the TFT circuit on glass substrate so.Such skew in the indicating meter of liquid crystal panel etc., can cause show bad.Therefore, the glass substrate that is forming LTPSTFT requires percent thermal shrinkage less, and the inequality of the percent thermal shrinkage of each glass substrate is less.
Generally speaking, the viscosity in the low temperature district of glass is higher, that is, the strain point of glass is higher, and the percent thermal shrinkage of glass substrate is less.Therefore, in the past, proposed to improve strain point by adjusting the composition of frit, thus, reduced the technology (patent documentation 1) of the percent thermal shrinkage of glass substrate.
[prior art document]
[patent documentation]
[patent documentation 1] Japanese Patent Laid-Open 2011-126728 communique
Summary of the invention
[inventing problem to be solved]
Yet, when manufacturing glass substrate, even if the cooling conditions of slow cooling sometimes but time fix, also can be in because production different each glass substrates that obtain in period produce percent thermal shrinkages inequality.As the uneven reason that produces percent thermal shrinkage, can enumerate the amount of moisture comprising in melten glass due to production difference in period and change, the amount of moisture of each glass substrate is different thus, and result strain point is different, and percent thermal shrinkage is different.The inequality of such percent thermal shrinkage is not good enough for being applicable to the glass substrate of LTPSTFT.
This is because the absolute value of percent thermal shrinkage is compared with the problem of the skew of the TFT circuit causing greatly, and in the time of can manufacturing by the panel at LTPSTFT, change device is set and reduced.With respect to this, even if the uneven impact of the percent thermal shrinkage of each glass substrate is because change device setting is also difficult to minimizing so particularly important.
Yet, in the technology that patent documentation 1 discloses, even if can make the absolute value of thermal contraction reduce, also cannot fully suppress the inequality of the percent thermal shrinkage of each glass substrate.
The object of the present invention is to provide a kind of manufacture method and manufacturing installation of uneven glass substrate of the percent thermal shrinkage that suppresses each glass substrate.
[technique means of dealing with problems]
An aspect of the present invention is characterised in that, it is a kind of manufacture method of glass substrate, and comprises
Melt step, it melts frit and cullet and making melten glass; And forming step, it is configured as plate glass by described melten glass;
And then, so that becoming the mode of target beta-OH value, β-OH value of described glass substrate controls the allotment ratio with respect to the described cullet of the mixture of described frit and cullet.
According to this manufacture method, by so that β-OH value of glass substrate becomes target beta-OH value, and control is with respect to the allotment ratio of the cullet of the mixture of frit and cullet, even if the variation of creating conditions that β-OH value of glass is impacted, β-OH value that also can suppress the glass substrate of manufacturing changes, thereby can reduce the inequality of β-OH value of each glass substrate.Therefore, the inequality of the strain point of each glass substrate can be reduced, thereby the inequality of the percent thermal shrinkage of each glass substrate can be reduced.
In preferred the 1st form of the manufacture method of described glass substrate, in described melting step, the allotment ratio determining according to β-OH value of the glass substrate based on manufacturing, is fed into described frit and cullet in melting groove.
In addition, described allotment is than the change actual achievement of creating conditions or predetermined decision more preferably based on affecting β-OH value amount in glass.
So, while secondly manufacturing glass substrate by β-OH value of glass substrate is reflected in, carry out feedback control, can precision control well β-OH value of glass substrate.
In preferred the 2nd form of the manufacture method of described glass substrate, the strain point of described glass substrate is more than 680 degree.
In preferred the 3rd form of the manufacture method of described glass substrate, in described glass substrate, Li
2o, Na
2o, K
2the total content of O is 0～2 quality %.
In preferred the 4th form of the manufacture method of described glass substrate, described glass substrate is glass substrate for plane display device.
In preferred the 5th form of the manufacture method of described glass substrate, described glass substrate is that LTPSTFT carries glass substrate for display.
In addition, in preferred the 6th form of the manufacture method of described glass substrate, described glass substrate is liquid crystal display glass substrate or OLED display glass substrate.
In preferred the 7th form of the manufacture method of described glass substrate, frit and cullet are melted and made in the melting step of melten glass in melting groove, use utilize combustion heating in the gas phase of combustion mechanism, with by the energising that melten glass circulating current is carried out, heat, to become, comprise SnO
2, viscosity is 10
2.5temperature during pool is the mode of 1580 ℃ of above glass and frit is melted, so that be more than 1.5 mode below 2.8 with respect to the ratio of the thermal value of the described combustion heating of described logical electrically heated thermal value, and carry out described combustion heating and described energising is heated.
Thus, β-OH value that can suppress glass substrate uprises, strain point diminishes, thereby can reduce the inequality of thermal contraction.And then, the clarification of melten glass can be carried out efficiently, thereby damage or the melting loss of groove can be suppressed to melt.
Another aspect of the present invention is characterised in that, it is a kind of manufacturing installation of glass substrate, and comprises
Melt groove, it melts frit and cullet and making melten glass; And forming furnace, it is configured as plate glass by described melten glass;
And then comprising control part, it controls the allotment ratio with respect to the described cullet of the mixture of described frit and cullet so that β-OH value of described glass substrate becomes the mode of target beta-OH value.
According to this manufacturing installation, by so that β-OH value of glass substrate becomes target beta-OH value, and control is with respect to the allotment ratio of the cullet of the mixture of described frit and cullet, even if the variation of creating conditions that β-OH value of glass is impacted, β-OH value that also can suppress the glass substrate of manufacturing changes, thereby can reduce the inequality of β-OH value of each obtained glass substrate.Therefore, the inequality of the strain point of each glass substrate can be reduced, thereby the inequality of the percent thermal shrinkage of each glass substrate can be reduced.
Another aspect of the present invention is characterised in that, it is a kind of manufacture method of glass substrate, and comprises
Melt step, it makes melten glass; And forming step, it is configured as plate glass by described melten glass; And so that β-OH value of described glass substrate becomes target beta-OH value and controls.
According to this manufacture method, by so that β-OH value of glass substrate becomes target beta-OH value controls, even if the variation of creating conditions that β-OH value of glass is impacted, β-OH value that also can suppress the glass substrate of manufacturing changes, thereby can reduce the inequality of the percent thermal shrinkage of each glass substrate.
[effect of invention]
According to the present invention, by so that β-OH value of glass substrate becomes target beta-OH value, and control the allotment ratio with respect to the cullet of the mixture of frit and cullet, the inequality of β-OH value of each glass substrate obtaining diminishes.Therefore, the inequality of the strain point of each glass substrate diminishes, and the inequality of the percent thermal shrinkage of each glass substrate diminishes.In addition, according to this manufacture method, by controlling the allotment ratio of cullet, can easily carry out the adjustment of β-OH value of glass substrate.
And then by so that β-OH value of glass substrate becomes target beta-OH value controls, the inequality of β-OH value of each glass substrate obtaining diminishes.Therefore, the inequality of the strain point of each glass substrate diminishes, and the inequality of the percent thermal shrinkage of each glass substrate diminishes.
Accompanying drawing explanation
Fig. 1 means the figure of an example of step of the manufacture method of glass substrate of the present invention.
Fig. 2 be model utility represent to carry out the figure of an example of the device of the deciding step～determination step shown in Fig. 1.
Fig. 3 is the figure of melting groove of the manufacturing installation of explanation glass substrate of the present invention.
[explanation of symbol]
101 melt groove
116 control parts
201 forming furnaces
ST1 controls step
ST2 melts step
ST6 forming step
Embodiment
Below, the manufacturing installation of the manufacture method of glass substrate of the present invention and glass substrate is described.
(manufacture method of glass substrate)
First, the manufacture method of glass substrate is described.
Fig. 1 represents to illustrate the figure of an example of flow process of the manufacture method of glass substrate.
The manufacture method of glass substrate mainly comprises deciding step (ST1), melting step (ST2), clarification steps (ST3), homogenization step (ST4), supplying step (ST5), forming step (ST6), slow cooling step (ST7), cuts off step (ST8) and determination step (ST9).The control step of the manufacture method of glass substrate of the present invention comprises deciding step (ST1) and determination step (ST9).In addition, through grinding, cut step, grinding steps, cleaning step, inspection step, bale packing step etc., become the glass substrate of end article.
Control in step, amount of moisture as glass substrate, the caused absorbancy of OH base (β-OH value) in the glass substrate of use infrared spectrophotometry method, so that the β-OH value in glass substrate becomes target beta-OH value, and control allotment with respect to the cullet of the mixture of frit and cullet than (following, also referred to as cullet ratio).The situation of using cullet together with frit is because use the energy so that frit is melted to reduce.A melting of cullet and vitrifying, therefore compare when frit is melted, energy that can be less and melting.In addition, by use cullet together with frit, and by the glass recycling that does not become goods producing in the manufacturing step of glass substrate, suppress thus the generation of industrial waste, and can suppress raw materials cost.In addition, frit is for so that become the SiO that the composition of following glass substrate is prepared
2, Al
2o
3, B
2o
3deng each composition.Cullet is the glass that is called ear or the cullet producing in the manufacturing step of glass substrate.The part of the width both sides that ear is the sheet glass that cuts off from sheet glass in cutting off step (ST8).
Moisture in glass substrate is because the moisture comprising in frit or cullet does not discharge and to remain in glass from melten glass, or near the environment liquid level of the melten glass in melting groove dissolves in melten glass and is included in glass substrate.In order to make amount of moisture in glass substrate keep fixing, can enumerate the amount of moisture making in frit or the glass melting temperature (Tm), the melten glass amount that melt in groove keep fixing.Yet, in order to realize thickness or the desired quality of the glass substrate of manufacture, must change melt the glass melting temperature (Tm) in groove, or change melts the melting amount of glass in groove.Thus, the amount of moisture in glass substrate changes, and is therefore difficult to make the amount of moisture in glass substrate to keep fixing.In addition, also have owing to causing that the amount of moisture in glass substrate changes outward thereby unconsciously.Therefore,, in the manufacture method of the glass substrate of present embodiment, by controlling the allotment ratio with respect to the cullet of the mixture of frit and cullet, and suppress the caused impact of change of the amount of moisture in glass substrate.By carrying out before the control of such cullet ratio in melting step (ST2), melt in step (ST2), according to controlled cullet, recently drop into frit and cullet.In addition, controlling step will be in below describing in detail.
Melt step (ST2) carries out in melting groove.Melt in groove, according to controlling the cullet ratio determining in step, frit and cullet are fed into the liquid level of accumulating in melting the melten glass of groove, make thus melten glass.Input side's rule of frit and cullet is as can be following mode: will take in the scraper bowl reversion of frit etc. and be fed into the mode that melts the melten glass in groove, the mode of using endless belt conveyor conveyance frit etc. and dropping into, utilizes feeding screw to drop into the mode of frit etc.In present embodiment, use scraper bowl to drop into frit etc.
The melten glass that melts groove for example both can be used to the flame radiation heat of spontaneous combustion burner and heat, also can be to circulating current between at least 1 pair of electrode (not shown) being formed by molybdenum, platinum or stannic oxide etc. and by melten glass energising heating, in addition, except energising heating, also can give the flame of burner complementaryly and frit is melted.In present embodiment, the flame radiation heat and the energising that are used to spontaneous combustion burner are heated and are heated.
In input frit and cullet, add finings.As finings, there is as everyone knows SnO
2, As
2o
3, Sb
2o
3deng, not restriction especially.Yet, with regard to the aspect of reduction carrying capacity of environment, preferably use SnO
2(stannic oxide) is as finings.
In addition, in present embodiment, in melting groove, use combustion heating in the gas phase of the combustion mechanism that utilizes burner etc., with the energising heating that utilizes 1 pair of electrode etc. to carry out melten glass circulating current, can make to become and comprise SnO
2, viscosity is 10
2.5temperature during pool is the mode of 1580 ℃ of above glass and frit is melted.Now, be preferably so that be more than 1.5 mode below 2.8 with respect to the ratio of the thermal value of the combustion heating of logical electrically heated thermal value, and carry out combustion heating, heat with energising.
If the ratio of the combustion heating that the burner of take is representative is too high, β-OH value of the glass substrate of manufacturing uprises so, and strain point diminishes, so the inequality of thermal contraction also becomes large.
In addition, it is large that the help of the thermal value of combustion heating becomes, and the temperature of gas-phase space uprises, so the SnO comprising in the state lower-glass raw material of the frit on the liquid level of melten glass
2deng finings in oxygen evolution to gas-phase space and oxygen diffusion.Therefore, rear step is in clarification steps during by melten glass deaeration, the finings comprising from melten glass is not supplied with sufficient oxygen, thereby cannot fully make the bubble comprising in melten glass absorb oxygen and grow up, and makes bubble float up to the liquid level of melten glass and discharges bubble.That is, deaeration is processed and is not fully carried out.This problem is not being used the As that clarifying effect is high
2o
3and use SnO
2obvious during as finings.
On the other hand, if logical electrically heated ratio is too high, it is large that the help of so logical electrically heated thermal value becomes relatively, and in order to switch on heating, the electrorheological of circulation is many.Herein, make if strain point uprise and adjust glass and form, having so viscosity is 10
2.5the tendency that temperature during pool uprises, exists the ratio resistance of melten glass also to become large tendency.For example, contain SnO
2, viscosity is 10
2.5temperature during pool is 1580 ℃ of above glass, in the difference of ratio resistance of refractory brick storing at the temperature of melten glass that melts groove with melting the diapire of groove, diminishes.The containing ratio that this tendency does not substantially comprise alkalimetal oxide or alkalimetal oxide is obvious especially in the glass substrate that more than 0 quality % the active matric-type flat-panel monitor below 0.8 quality % is used.Therefore the part of electric current that, is supplied to 1 pair of electrode is not to melten glass but to melting the diapire circulation of groove body and by diapire energising heating.Therefore, while making the melten glass higher than resistance, high temperature viscosity is higher in melting groove, diapire a large amount of electric currents that also circulate due to electrode pair is supplied with to electric current in a large number, result, it is large that caused heating quantitative change is heated in the energising of diapire.Due to the increase of the thermal value of this diapire, and produce the phenomenon that heat is full of owing to melting the disconnected thermal property of bottom of groove.This heat is full of the mechanicalness intensity of the refractory brick that may weaken bottom and thermal creep is produced, and makes deformation of bottom.And then, also may be because heat be full of the temperature of refractory brick surpass heat resisting temperature and melting loss.Therefore, the help of the caused thermal value of energising heating becomes excessive, and not good enough.
In view of above aspect, being preferably the ratio making with respect to the thermal value of the combustion heating of logical electrically heated thermal value is 1.5～2.8.
Logical electrically heated thermal value for example can be measured power consumption by kilowatt meter, obtains power consumption amount.By power consumption amount (kW), be converted to logical electrically heated thermal value (kcal/ hour) (1kW=860kcal/ hour).In addition, power consumption also can be obtained by the electric current that applies circulation in voltage and electrode 114 of electrode 114.
Use the thermal value of the combustion heating of combustion gases to calculate by the thermal value of the per unit volume of the burning of combustion gases being multiplied by the feed rate (flows of combustion gases) of the combustion gases of unit time.
The ratio of the mean value of the thermal value that the ratio of the thermal value of using in present embodiment is per set time.Herein, the set time is all can for 1 hour or 1 day.
Clarification steps (ST3) is at least carried out in clarifying tank.In clarification steps (ST3), by the melten glass in clarifying tank is heated up, and in melten glass, comprise contain O
2, CO
2or SO
2bubble absorb the O produced by the reduction reaction of finings
2and grow up, thereby bubble floats up to the liquid level of melten glass and discharges.And then, in clarification steps, by the temperature of melten glass is reduced, and carry out oxidizing reaction by the reducing substance that the reduction reaction of finings obtains.Thus, remain in the O in the bubble in melten glass
2deng gaseous constituent be resorbed in melten glass, thereby bubble disappears.The oxidizing reaction of finings and reduction reaction are undertaken by controlling the temperature of melten glass.In addition, in clarification steps, also can use and in clarifying tank, make reduced pressure atmosphere, existing bubble in melten glass is grown up and the vacuum deaerator mode of deaeration under reduced pressure atmosphere.Now, do not use finings aspect comparatively effective.In addition, in following clarification steps, utilize and use stannic oxide as the defecation method of finings.
In homogenization step (ST4), by using agitator to stir the melten glass in the steel basin by supplying with from the pipe arrangement of clarifying tank extension, and carry out homogenizing of glass ingredient.The reason that thus, can reduce striped etc. is that the composition of glass is uneven.In addition, steel basin both can arrange 1, also can arrange more than 2.In supplying step (ST5), by the pipe arrangement extending from steel basin, melten glass is supplied to building mortion.
In building mortion, form step (ST6) and slow cooling step (ST7).In forming step (ST6), melten glass is configured as to sheet glass, makes the flow direction of sheet glass.Shaping can be used other the method such as overflow downdraw or floating method.
In present embodiment, use overflow downdraw.In slow cooling step (ST7), shaping mobile sheet glass so that diminishing, percent thermal shrinkage, internal strain and warpage are carried out to cooling (thermal contraction reduces processing).So, in the manufacture method of glass substrate of the present invention, be only preferably and carry out thermal contraction reduction processing by carrying out slow cooling online annealing (online anneal) but in the slow cooling step (ST7) after sheet glass is shaped.Only by online annealing, carrying out the preferred reason that thermal contraction reduce to process is, while carrying out thermal contraction processing by again implement heat treated off-line annealing (offline anneal) in cut-out step (ST8) after sheet glass cuts off, annealing furnace need to be set in addition.Annealing furnace is for example the stove beyond the slow cool furnace 202 of following building mortion.If anneal and carry out thermal contraction and reduce to process by off-line, even if the adjustment not forming by glass so make strain point for for example 680 ℃ also can reduce percent thermal shrinkage above.Yet, so obvious step-down of method production efficiency.
Cut off in step (ST8), in shut-off device, by the sheet glass of supplying with from building mortion is cut to specific length, and obtain tabular sheet glass.Now, from sheet glass, cut out ear, generate cullet.By cut off sheet glass and then be cut to specific size, make the glass substrate of target size.After this, carry out the grinding of end face of glass substrate and cut, grind, carry out the cleaning of glass substrate, and then, after checking the having or not of abnormal defect of bubble or striped etc., using the sheet glass of passed examination product as end article, carry out bale packing.
(control step)
Secondly, to controlling step, illustrate in greater detail.Control in step, in determination step (ST9), carry out the mensuration of β-OH value of glass substrate, in deciding step (ST1), β-OH value based on measured, determines that allotment with respect to the cullet of the mixture of frit and cullet is than (cullet ratio).
(determination step)
In determination step, according to the infrared absorption spectrum of the glass substrate that uses spectrophotometer to obtain, utilize following formula to obtain and cut off the β-OH value that is cut to the glass substrate of specific length in step.In addition, the frequency of β-OH value of mensuration glass substrate is not particularly limited.
The log10 (T1/T2) of β-OH value=(1/X)
X: thickness of glass (mm)
T1: the transmitance (%) during with reference to wavelength 2600nm
T2: the minimum transmitance (%) during hydroxyl absorbing wavelength 2800nm
β-OH value is by mm
-1represent.In addition, the value that β-OH value can be used the amount of moisture of take in glass substrate to measure with interior object as fixed amount, so that do not produce bubble in glass substrate.Determination step (ST9) in other embodiments, also can not cut off step (ST8) afterwards, and carry out before the deciding step of carrying out before in melting step (ST2).
(deciding step)
In deciding step (ST1), β-OH value of the glass substrate based on measured, determines that allotment with respect to the cullet of the mixture of frit and cullet is than (cullet ratio).Now, β-OH value of cullet is utilized the method same with the measuring method of β-OH value of described glass substrate and mensuration in advance.So, measure β-OH value of glass substrate, determine cullet ratio, and then, in melting step (ST2), by the cullet according to determined, than by frit and cullet, be fed into melting groove, carry out feedback control, precision is controlled β-OH value of glass substrate well.
Secondly, the reason that can control β-OH value of glass substrate by the control of cullet ratio is described.
In the moisture that β-OH value in glass substrate mainly comprises in (1) frit and cullet, in melting step, as gas foam, be not released into melten glass outer and dissolve in to the amount of moisture in melten glass, (2) melt the environment from contacting with molten glass level in step, via molten glass level, dissolve in to the amount of moisture in melten glass and determine.
For being that soda-lime glass etc. is compared with the glass that becomes manufacturing object, alkalimetal oxide amount is less, the higher LTPSTFT of melt temperature carries glass substrate for display or OLED display while use glass substrate, dissolves in to the amount of moisture increase in melten glass in described (2).This is because in the manufacture of the higher glass of melting temperature (Tm), as melting the gas burner using in step, not use air combustion gas burner, but use the very high oxygen burner of efficiency of combustion.In oxygen burner, owing to not comprising the nitrogen irrelevant with burning, thus replace obtaining the temperature of combustion of high temperature, and can comprise a large amount of water vapour in burning and gas-exhausting.That is, dissolve in to the amount of moisture in melten glass and increase.
Herein, because cullet once melts and vitrifying, so if by frit and cullet comparison, so generally speaking β-OH value of cullet uprises.Therefore, by improving the ratio of cullet, β-OH value of produced glass substrate can be improved, by the ratio of reduction cullet, the control of β-OH value etc. of produced glass substrate can be reduced.
The decision of cullet ratio is the β-OH value based on measured, so that β-OH value of glass substrate becomes the mode of target beta-OH value and carries out.For example, the decision of preferred glass bits ratio is the β-OH value based on measured, and the variation actual achievement of creating conditions and change that the β-OH value based on to glass substrate impacts are scheduled to and carry out.Target beta-OH value can adopt various values, and for example, also can pass by β-OH value of glass substrate of made is benchmark, take the amount of the hydrate in frit or the amount of moisture in liquid level environment as with reference to determining.In addition, from reducing the viewpoint of the absolute value of percent thermal shrinkage, target beta-OH value is more low more preferred.Target beta-OH value for example can be made as below 0.35/mm.In present embodiment, cullet than the mixture 100 quality % with respect to frit and cullet, for example, is 20～30 quality %.In addition, cullet ratio also can be used as with respect to the allotment of the mixture of frit and cullet and compares and determine, also can be used as with respect to the allotment of frit and compares and determine.Deciding step (ST1) in other embodiments, also can be melt step (ST2) before carry out, and carry out after the cut-out step (ST8) that produces this cullet determination step (ST9) afterwards.In addition, deciding step (ST1) also can be at determination step (ST9) afterwards, separates the time (for example, a couple of days) and carry out, also can be at determination step (ST9) then determination step (ST9) and carrying out afterwards.
In addition, the variation of creating conditions or the change that as β-OH value of the glass substrate to described, impact, for example, can enumerate the change of frit, the keeping method of frit, melten glass are trapped in time, the melten glass temperature in melting step melting in groove, the change that melts the gas of the gas burner using in step, the change of the ratio of gas burner and electric melting etc.In addition, as the gas using in gas burner, for example, for example, by changing to the longer gas of carbochain number (, replacing the propane gas of methane gas), can make β-OH value of glass substrate diminish.
The manufacture method of above glass substrate for example can be used the manufacturing installation of following glass substrate and carry out.Now, also only the step of a part for the manufacture method of glass substrate is used the manufacturing installation of this glass substrate and is carried out.
According to the manufacture method of the glass substrate of present embodiment, so that β-OH value of glass substrate becomes target beta-OH value, and control is with respect to the allotment ratio of the cullet of the mixture of frit and cullet.Thus, for example, even if the change of having created conditions that β-OH value is impacted, the inequality of β-OH value of each glass substrate also diminishes.Therefore, the inequality of the strain point of each glass substrate diminishes, and the inequality of the percent thermal shrinkage of each glass substrate diminishes.In addition, by controlling the allotment ratio of cullet, can easily adjust β-OH value of glass substrate.
In the manufacture method of the glass substrate of other embodiments, replace overflow downdraw, also can use under discharge orifice additive methods such as drawing (slot downdraw) method, floating method, roll extrusion (roll out) method.In addition, in frit, may not allocate cullet, also can only use frit to make melten glass.
(manufacturing installation of glass substrate)
Secondly, the manufacturing installation of glass substrate is described.
Fig. 2 be model utility represent to carry out the figure of an example of the device of deciding step (the ST1)～determination step (ST9) in present embodiment.This device as shown in Figure 2, mainly has fusing device 100, building mortion 200 and shut-off device 300.Fusing device 100 has the groove 101 of melting, clarifying tank 102, steel basin 103, glass supply-pipe 104,105,106 and determination section 116.Shut-off device 300 has determination part 117.In addition, the control part of the manufacturing installation of glass substrate of the present invention comprises determination section 116 and determination part 117.Control part is so that β-OH value of glass substrate becomes target beta-OH value, and control is with respect to the allotment ratio of the cullet of the mixture of frit and cullet.Particularly, by determination section 116 and determination part 117, carry out the decision of cullet ratio, the mensuration of the β-OH value before it.
In routine melting groove 101 shown in Fig. 2, the scraper bowl 101d that comes into operation of frit and cullet carries out.Melt in groove 101 and connecting determination section 116.β-OH value of the glass substrate that determination section 116 is measured based on determination part 117, determines cullet ratio.In clarifying tank 102, adjust the temperature of melten glass MG, utilize the redox reaction of finings to carry out the clarification of melten glass MG.And then, in steel basin 103, by agitator 103a, melten glass MG stirred and homogenize.
Building mortion 200 has forming furnace 201 and slow cool furnace 202, utilizes and uses the overflow downdraw that is configured in the molding 210 in forming furnace 201, from melten glass MG matrix band glass SG.
Shut-off device 300 is cut to specific size by the sheet glass SG supplying with from building mortion 200, makes the glass substrate of target size.Now, generate cullet.In shut-off device 300, connecting determination part 117.Determination part 117 is measured β-OH value of glass substrate.
According to the manufacturing installation of the glass substrate of present embodiment, by so that β-OH value of glass substrate becomes target beta-OH value, and control is with respect to the allotment ratio of the cullet of the mixture of frit and cullet, for example, even if the change of having created conditions that β-OH value is impacted, the inequality of β-OH value of each glass substrate obtaining also diminishes.Therefore, the inequality of the strain point of each glass substrate diminishes, and the inequality of the percent thermal shrinkage of each glass substrate diminishes.
In addition, by controlling the allotment ratio of cullet, can easily adjust β-OH value of glass substrate.
(glass substrate)
Herein, illustrate by the manufacture method of glass substrate of the present invention and manufacturing installation and the summary of the glass substrate of manufacturing.
The thickness of glass substrate is for example 0.1～1.5mm.
The size of glass substrate is for example 300～2500mm * 400～3500mm (short side direction length * long side direction length).
As glass for liquid crystal display plate or sheet glass for organic EL (Electro-Luminescence), the preferred applicable alkali micro glass substrate that does not contain in fact the alkali-free glass substrate of alkalimetal oxide or only contain the alkalimetal oxide below 2%.
In addition, about forming the characteristic of the glass of glass substrate, viscosity is 10
2.5the temperature of melten glass during pool can be more than 1580 ℃, for example 1590～1700 ℃.In addition, the ratio resistance of the melten glass of 1550 ℃ of the glass of formation glass substrate can be made as 100～350 Ω cm more than can be 100 Ω cm, and then, can be made as 150～350 Ω cm.Described higher than resistance, the problem of the melting loss of described melting groove is more obvious.In addition, if want to improve the strain point of glass substrate, existing so described is 10 than resistance and viscosity
2.5the tendency that the temperature of melten glass during pool uprises.
Glass substrate for example comprises the composition shown in following.The % demonstration of following composition ratio all represents quality %.
SiO
2：50～70％，
Al
2O
3：5～25％，
B
2O
3：0～15％。
In addition, also can comprise arbitrarily the composition shown in following.
MgO：0～10％，
CaO：0～20％，
SrO：0～20％，
BaO：0～10％，
ZrO
2：0～10％。
In addition, in described composition, especially, preferably contain SiO
2: 50～70%, B
2o
3: 5～18%, Al
2o
3: 10～25%, MgO:0～10%, CaO:0～20%, SrO:0～20%, BaO:0～10%, RO:5～20% (wherein, R is selected from all the components containing in the glass substrate of Mg, Ca, Sr and Ba).
And then, can comprise R '
2o: surpass (wherein, R ' is for being selected from all the components containing in the glass substrate of Li, Na and K) below 0% and 2.0%.Thus, even if reduce β-OH value, also can prevent that melting temperature (Tm) from uprising superfluously.If β-OH value of glass substrate diminishes, strain point uprises so, therefore can reduce the absolute value of the percent thermal shrinkage of glass substrate.Thus, also can reduce the inequality of the percent thermal shrinkage of glass substrate.
And then, preferably comprise finings and add up to 0.05～1.5%, do not comprise in fact As
2o
3, Sb
2o
3and PbO.Because As
2o
3, Sb
2o
3although and PbO is for having the material of the effect of fining glass, is the material that carrying capacity of environment is larger.Herein, what is called does not comprise in fact, refers to that quality % does not reach 0.01%, and the removal of impurity does not contain to intention outward.As finings, preferably comprise SnO
2.
In addition, the content of the ferric oxide in preferred glass is 0.01～0.2%.
As the glass that is forming the glass substrate of LTPSTFT, form, can enumerate following glass and form.The % demonstration of following composition ratio all represents quality %.
Contain SiO
2: 52～78%, Al
2o
3: 3～25%, B
2o
3: 0～15%, RO (wherein, R is all the components comprising in the glass substrate in Mg, Ca, Sr and Ba): 3～20%, R '
2o (wherein, R is all the components comprising in the glass substrate in Li, Na and K): 0.01～0.8%, Sb
2o
3: 0～0.3 quality %, does not contain in fact As
2o
3, mass ratio CaO/RO is more than 0.65, mass ratio (SiO
2+ Al
2o
3)/B
2o
3be 7～30 scope, and mass ratio (SiO
2+ Al
2o
3)/RO is more than 5.Now, preferably strain point is more than 688 ℃.
β-OH value of glass substrate is preferably below 0.45/mm, more preferably below 0.35/mm, and then is preferably below 0.30/mm, most preferably is below 0.25/mm.This is because the more little strain point (viscosity rising) that more can improve of β-OH value, more can reduce percent thermal shrinkage.On the other hand, if reduce obstinately β-OH value so cost of material or manufacturing cost surging.Therefore, β-OH value of glass substrate is preferably 0～0.35/mm, both can be 0.05～0.35/mm, also can be 0.05～0.30/mm.
In addition, according to the present invention, the inequality of β-OH value of glass substrate for example can maintain ± below 0.015/mm, also can maintain ± below 0.01/mm.So, by reducing the inequality of β-OH value, can reduce the inequality of the percent thermal shrinkage of each glass substrate.
From reducing the aspect of percent thermal shrinkage, the strain point of glass substrate is preferably more than 680 ℃, more preferably more than 690 ℃.By making strain point, be more than 680 ℃, can reduce the absolute value of the percent thermal shrinkage of glass substrate.Thus, also can reduce the inequality of the percent thermal shrinkage of glass substrate.Strain point for example utilizes camber beam method to use viscometric viscometer to measure.
The percent thermal shrinkage of glass substrate is for example below 70ppm.The glass substrate thermostability with lower percent thermal shrinkage is like this higher, especially, preferred as the glass substrate that is forming LTPSTFT.In addition, when only carrying out thermal contraction reduction processing by online annealing, in order to suppress gigantism and the cost of producing apparatus, be preferably 10～70ppm.
Glass substrate is glass substrate for plane display device.As flat-panel monitor, can enumerate liquid-crystal display, plasma display, OLED display etc.Wherein, from reducing the uneven aspect of thermal contraction, preferably use liquid-crystal display or OLED display.
(experimental example)
Below, represent experimental example, confirm effect of the present invention.
According to the manufacture method of described glass substrate of the present invention, control cullet ratio, utilize overflow downdraw, manufacture glass substrate.Particularly, to comprising SiO with glass substrate
2: 61.3 quality %, Al
2o
3: 19.5 quality %, B
2o
3: 9 quality %, CaO:9.8 quality %, K
2o:0.15 quality %, Fe
2o
3: 0.05 quality %, SnO
2: the frit that the mode of 0.2 quality % is concocted, the cullet that is 0.24/mm by β-OH value is fed into melting groove with cullet than the ratio of 30 quality %.The composition of cullet is identical with described glass substrate.In addition, β-OH value of glass substrate is 0.24/mm, and target beta-OH value is also 0.24/mm.In addition, the strain point of glass is now 700 ℃, and viscosity is 10
2.5temperature during pool is 1595 ℃.
Secondly, the melten glass temperature that makes to melt in step rises 20 ℃, and after the week as a result, β-OH value of glass substrate becomes 0.26/mm, and percent thermal shrinkage also large 2%.Therefore, calculate with so that β-OH value of glass substrate reduces the cullet ratio of 0.02/mm, change and be fed into the cullet ratio that melts step.Herein, the mixture 100 quality % with respect to frit and cullet, make cullet than being reduced to 21 quality % from 30 quality %.Its result, β-OH value that can make glass substrate is 0.24/mm.In addition, the percent thermal shrinkage of each glass substrate also with make the melten glass temperature glass substrate of manufacturings that rises before approximately 20 ℃ equal.
In addition, infer in advance β-OH value rate of rise that the glass melting temperature that makes to melt in step rises 20 ℃ time, correspondence makes melt temperature rise 20 ℃ and while making cullet be reduced to 21 quality % than from 30 quality %, also β-OH value of glass substrate can be maintained to 0.24/mm, also can maintenance heat shrinking percentage.
In addition, β-OH value, the percent thermal shrinkage of described glass substrate and cullet are obtained according to following main points respectively.
In order to calculate, use so that β-OH value reduces the cullet ratio of particular value, be preferably the help rate measured in advance with respect to glass substrate β-OH value of frit (in the moisture comprising in frit and cullet, in melting step, as gas foam, be not released into melten glass outer and dissolve in to the amount of moisture in melten glass).For example, the help rate of the frit using in this experimental example is 0.023 o'clock, by the temperature operation of described melten glass, can calculate and melt in step the caused help rate X to β-OH value of moisture dissolving in to glass from the environment of high water vapor concentration according to following formula (1)." raw material ratio " is the allotment ratio with respect to the frit of the mixture of frit and cullet.
β-OH value=(the help rate * raw material ratio of frit)+(cullet β-OH value * cullet ratio)+help rate X (1)
That is, in described embodiment, the help rate X1 before melten glass temperature operation is 0.152, and the help rate X2 after melten glass temperature operation is 0.172, has increased by 0.20.Therefore, in order to make β-OH value be back to the 0.24/mm before the temperature operation of melten glass, as to as described in as shown in the following formula (2) that obtained of formula (1) substitution numerical value, make cullet ratio
.
0.24＝(0.023×(1-C))+(0.24×C)+0.172 (2)
(β-OH value of glass substrate and cullet)
To obtained glass substrate and cullet, use fourier transform infrared spectrophotometer, according to the infrared absorption spectrum of glass substrate, according to above-mentioned formula, obtain respectively β-OH value.Cullet is used while manufacturing glass substrate in the past and cuts off and the cullet of acquisition from sheet glass.
(percent thermal shrinkage)
Percent thermal shrinkage is with 10 ℃/min of intensifications from normal temperature, at 550 ℃, keep 1 hour, afterwards, till being cooled to normal temperature with 10 ℃/min, again with 10 ℃/min of intensifications, at 550 ℃, keep 1 hour, use the shrinkage of the glass substrate after being cooled to till normal temperature with 10 ℃/min, according to obtaining with following formula.
Percent thermal shrinkage (ppm)={ length of the glass before the shrinkage/thermal treatment of the glass before and after thermal treatment } * 10
6
Above, the manufacture method of glass substrate of the present invention and manufacturing installation are explained, but the present invention is not defined in described embodiment, in not departing from the scope of purport of the present invention, can carries out various improvement or change is natural.
Claims (6)
1. a manufacture method for glass substrate, is characterized in that comprising:
Melt step, it melts frit and cullet and making melten glass; And forming step, it is configured as plate glass by described melten glass; And
So that becoming the mode of target beta-OH value, β-OH value of described glass substrate controls the allotment ratio with respect to the described cullet of the mixture of described frit and cullet.
2. the manufacture method of glass substrate according to claim 1, it is characterized in that, in described melting step, the allotment ratio of the described cullet of the mixture with respect to described frit and cullet determining according to β-OH value of the glass substrate based on manufacturing, is fed into melting groove by described frit and cullet.
3. the manufacture method of glass substrate according to claim 1 and 2, is characterized in that, described glass substrate is that low-temperature polysilicon film transistor carries glass substrate for display.
4. according to the manufacture method of the glass substrate described in any one in claims 1 to 3, it is characterized in that, described glass substrate is liquid crystal display glass substrate or display of organic electroluminescence glass substrate.
5. a manufacturing installation for glass substrate, is characterized in that comprising:
Melt groove, it melts frit and cullet and making melten glass; And forming furnace, it is configured as plate glass by described melten glass;
And then comprising control part, it controls the allotment ratio with respect to the described cullet of the mixture of described frit and cullet so that β-OH value of described glass substrate becomes the mode of target beta-OH value.
6. a manufacture method for glass substrate, is characterized in that comprising:
Melt step, it makes melten glass; And forming step, it is configured as plate glass by described melten glass; And
So that β-OH value of described glass substrate becomes target beta-OH value and controls.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012220297 | 2012-10-02 | ||
| JP2012-220297 | 2012-10-02 | ||
| JP2013087988A JP5797222B2 (en) | 2012-10-02 | 2013-04-19 | Glass substrate manufacturing method and manufacturing apparatus |
| JP2013-087988 | 2013-04-19 |
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| Publication Number | Publication Date |
|---|---|
| CN103708706A true CN103708706A (en) | 2014-04-09 |
| CN103708706B CN103708706B (en) | 2016-11-30 |
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| CN110114318A (en) * | 2016-12-26 | 2019-08-09 | 日本电气硝子株式会社 | The manufacturing method of alkali-free glass substrate |
| CN111183120A (en) * | 2017-12-20 | 2020-05-19 | 日本电气硝子株式会社 | Method for manufacturing glass plate |
| CN111943507A (en) * | 2020-07-22 | 2020-11-17 | 杨国秀 | Preparation process of high-permeability glass product |
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| WO2009054314A1 (en) * | 2007-10-25 | 2009-04-30 | Asahi Glass Company, Limited | Method for production of non-alkali glass |
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| WO2009054314A1 (en) * | 2007-10-25 | 2009-04-30 | Asahi Glass Company, Limited | Method for production of non-alkali glass |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109715572A (en) * | 2016-09-16 | 2019-05-03 | Ａｇｃ株式会社 | Glass substrate and multilayer board |
| CN109715572B (en) * | 2016-09-16 | 2022-06-14 | Ａｇｃ株式会社 | Glass substrate and laminated substrate |
| CN110114318A (en) * | 2016-12-26 | 2019-08-09 | 日本电气硝子株式会社 | The manufacturing method of alkali-free glass substrate |
| TWI830984B (en) * | 2016-12-26 | 2024-02-01 | 日商日本電氣硝子股份有限公司 | Manufacturing method of alkali-free glass substrate |
| CN111183120A (en) * | 2017-12-20 | 2020-05-19 | 日本电气硝子株式会社 | Method for manufacturing glass plate |
| CN111183120B (en) * | 2017-12-20 | 2022-07-26 | 日本电气硝子株式会社 | Method for manufacturing glass plate |
| CN115043576A (en) * | 2017-12-20 | 2022-09-13 | 日本电气硝子株式会社 | Method for manufacturing glass plate |
| CN111943507A (en) * | 2020-07-22 | 2020-11-17 | 杨国秀 | Preparation process of high-permeability glass product |
| CN111943507B (en) * | 2020-07-22 | 2022-06-17 | 淄博金田轻工制品有限公司 | Preparation process of high-permeability glass product |
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| KR20140043657A (en) | 2014-04-10 |
| KR101583114B1 (en) | 2016-01-07 |
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