CN102958855A - Glass plate and method for manufacturing glass plate - Google Patents

Glass plate and method for manufacturing glass plate Download PDF

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Publication number
CN102958855A
CN102958855A CN201080058710XA CN201080058710A CN102958855A CN 102958855 A CN102958855 A CN 102958855A CN 201080058710X A CN201080058710X A CN 201080058710XA CN 201080058710 A CN201080058710 A CN 201080058710A CN 102958855 A CN102958855 A CN 102958855A
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Prior art keywords
glass
sheet glass
sheet
ribbon
compressive stress
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CN201080058710XA
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CN102958855B (en
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君嶋哲郎
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Avanstrate Inc
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Avanstrate Inc
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B17/00—Forming molten glass by flowing-out, pushing-out, extruding or drawing downwardly or laterally from forming slits or by overflowing over lips
    • C03B17/06—Forming glass sheets
    • C03B17/064—Forming glass sheets by the overflow downdraw fusion process; Isopipes therefor
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B17/00—Forming molten glass by flowing-out, pushing-out, extruding or drawing downwardly or laterally from forming slits or by overflowing over lips
    • C03B17/06—Forming glass sheets
    • C03B17/067—Forming glass sheets combined with thermal conditioning of the sheets
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P40/00—Technologies relating to the processing of minerals
    • Y02P40/50—Glass production, e.g. reusing waste heat during processing or shaping
    • Y02P40/57—Improving the yield, e-g- reduction of reject rates

Abstract

Disclosed is a glass plate which has, at the time of being manufactured by a down-draw method, the glass surface strengthened to a certain extent that the processing efficiency after the glass formation is not affected and the glass surface is not easily scratched. The glass plate has a tensile stress layer formed inside of the glass plate, and compression stress layers formed on both the sides of the tensile stress layer. The compression stress layers are formed within a depth range of 10-50 [mu]m in the thickness direction of the glass plate from the surface of the glass plate, and the thickness of the compression stress layers is less than a thirteenth part of the thickness of the glass plate. The absolute value of the stress value of the compression stress layers is 4 MPa or less, and the absolute value of the stress value of the tensile stress layer is 0.4 MPa or less.

Description

The manufacture method of sheet glass and sheet glass
Technical field
The present invention relates to the method for sheet glass and manufacturing sheet glass.
Background technology
The flat-panel monitors such as liquid-crystal display and plasma display (below, be called " FPD ".) in, as glass substrate, used thickness for example to be the following thin glass plate of 1.0mm.In recent years, the maximization development of FPD glass substrate for example uses to be called as the sheet glass that the 8th generation was of a size of 2200mm * 2500mm.
In order to make such FPD glass substrate, the most often use glass tube down-drawing.In glass tube down-drawing, make melten glass overflow from the groove of shaped device, thus the glass ribbon of continuously moulding band shape.At this moment, glass ribbon is pulled to the below by roller etc.Adjusted the thickness of glass ribbon this moment by the drop-down speed of glass ribbon., with predetermined length cut off glass ribbon, make sheet glass thereafter.
For example, in the patent documentation 1 device for producing glass sheet shown in Figure 11 is disclosed.This device for producing glass sheet possesses shaped device 7 and surrounds the insulated structure 8 of shaped device 7.Insulated structure 8 is by keeping the air of high temperature around shaped device 7, thereby is used for keeping the temperature of the melten glass that overflows from shaped device 7, usually, is closed structure except the cast gate 81 that glass ribbon is passed through.
Specifically, in patent documentation 1 disclosed device for producing glass sheet, insulated structure 8 is consisted of by the container-like main body 8A of lower opening with the cast gate constituting body 8B that the mode of the opening of blocking main body 8A configures.The inside of cast gate constituting body 8B is the cavity, by the internal feed tempering air of cooling tube 82 to this cast gate constituting body 8B.Thus, in patent documentation 1 disclosed device for producing glass sheet, can be with glass ribbon 9 immediately cooling after it forms.
Under such situation, for example, can slimming, lightweight, physical strength and the transparency is high and glass substrate for display that can make at short notice is well-known (patent documentation 2).This glass substrate is formed by following glass material, and this glass material contains SiO 240～70 % by weight, Al 2O 30.1～20 % by weight, Na 2O 0～20 % by weight, Li 2O 0～15 % by weight, ZrO 20.1～9 % by weight, Li 2O and Na 2The total content of O is 3～20 % by weight.Formed the degree of depth on the surface of this glass substrate by chemical enhancement process and be the compressive stress layers more than the 50 μ m.
In addition, known a kind of glass, it carries out chemical enhancement process from the 1st temperature quenching that is higher than annealing point to the 2nd temperature that is lower than strain point by ion-exchange, has the ion-exchange surface layer (patent documentation 3) of the degree of depth that has 20 μ m from the surface at least.
In addition, the manufacture method of known a kind of reinforcing glass also, it can be optimized compression stress value and the thickness of the compressive stress layers in the glass, and can easily carry out hot-work (patent documentation 4) in order to obtain high mechanical strength.
In this manufacture method, the temperature province from annealing point to strain point with below 200 ℃/minute, the speed of cooling that is preferably below 50 ℃/minute cools off, and then carries out chemical enhancement process.
The prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Application Publication 2009-519884 communique
Patent documentation 2: TOHKEMY 2002-174810 communique
Patent documentation 3:US2009/0220761 A1
Patent documentation 4: TOHKEMY 2010-168252 communique
Summary of the invention
The problem that invention will solve
Yet, in the boundary surface that contacts with air, evaporate into branch and from melten glass, volatilize.The contriver of the present application considers, if effectively utilize this volatilization in glass tube down-drawing, perhaps can form desired compressive stress layers in the two sides in the table of sheet glass.
(the 1st problem)
But as patent documentation 1 disclosed manufacturing installation, insulated structure 8 is in the situation of closed structure, and therefore volatile component can't form the high compressive stress layers of stress value from suppressed by the volatilization in the melten glass that overflows the shaped device.
Need to prove, patent documentation 1 also discloses following content: cast gate constituting body 8B is provided with ejiction opening 83, this ejiction opening 83 will be ejected in the space that is covered by main body 8A from the cooling of cooling tube 82 with cold air, make tempering air flow to cast gate 81 from ejiction opening 83, the cooled glass band 9 thus.But even produce forced convections near making like this cast gate 81, the most air in the air of its upside, the space that namely covered by main body 8A still stays in herein, so the volatile component not change of repressed situation of volatilize from melten glass.
(the 2nd problem)
In patent documentation 2 disclosed glass substrates, carry out chemical enhancement process by carrying out ion-exchange, thereby form compressive stress layers on the surface of sheet glass.But, when coming that with the alkalimetal ion that is used for ion-exchange glass substrate carried out chemical enhancement process, for example, TFT (the Thin Film Transistor of meeting to forming on the liquid crystal indicator glass substrate, thin film transistor) characteristic impacts, and then the pollution liquid crystal material, consider not preferred from this respect.Therefore, the reinforcing glass that has carried out chemical enhancing by ion-exchange is difficult to use in the liquid crystal indicator glass substrate.Namely allow to utilize ion-exchange to carry out chemical enhancement process, in the front operation of chemical enhancement process, also can't avoid the surface of sheet glass to sustain damage.On the other hand, if after the moulding of sheet glass, carry out immediately above-mentioned chemical enhancement process, the cut-out of the glass surface that then carries out thereafter, the grinding of sheet glass and grinding, comprise the Efficiency Decreasing of the processing treatment of shape processing.
For patent documentation 3 disclosed sheet glass, owing in annealing operation, make the glass quenching, so glass surface forms little compressive stress layers sometimes.But, only in annealing operation, make the glass quenching and the stress value of the compressive stress layers that obtains is extremely low, therefore the surface of glass also can sustain damage sometimes in the front operation of chemical enhancement process.In addition, in the sheet glass of thin thickness, because through-thickness shows the internal stress distribution of parabolic shape, thereby the stress value of the tension stress layer that forms at inside of glass plate becomes large.When the stress value of tension stress layer is large, for example, in the situation that cut off sheet glass, the line of the predetermined depth that puts under in order to cut off is in the elongation of the thickness direction ahead of estimate ground of sheet glass, sometimes be difficult to sheet glass is divided into desired size, consider not preferred from this respect.
In the patent documentation 4, by to Slow cooling glass and the sheet glass of moulding carries out chemistry and strengthens, the stress value of compressive stress layers raises.But sheet glass is after moulding and carry out being truncated into predetermined size before chemistry strengthens, and carries out shape processing.In the transmission of such inter process or in the processing of cut-out, shape, the surface of sheet glass might sustain damage.If sheet glass strengthens the front glass surface and sustains damage carrying out chemistry, the acquisition high strength even then carry out thereafter chemistry to strengthen, glass surface also can residually have scar.
In light of this situation, the 1st purpose of the present invention be to provide the volatile component in the melten glass that can promote from shaped device, to overflow volatilization device for producing glass sheet and used the glass plate manufacturing method of this device for producing glass sheet, and provide the sheet glass that is obtained by above-mentioned glass plate manufacturing method.
In addition, the 2nd purpose of the present invention is to provide not cause the efficient of the processing treatment behind the glass ware forming when the manufacturing of sheet glass degree that detrimentally affect and glass surface be difficult to sustain damage that glass surface has been carried out the sheet glass that strengthens and the manufacture method of sheet glass.
For the scheme of dealing with problems
(the 1st scheme)
In order to reach above-mentioned the 1st purpose, a mode of the present invention provides a kind of device for producing glass sheet, it is the device of making sheet glass by glass tube down-drawing, this device possesses shaped device and insulated structure, in above-mentioned shaped device, make melten glass from the both sides overflow of the groove of above-mentioned shaped device, the melten glass of this overflow is guided and fuses by wall each other, thereby formation glass ribbon, above-mentioned insulated structure surrounds above-mentioned shaped device, and has the cast gate that the above-mentioned glass ribbon that formed by above-mentioned shaped device is passed through, above-mentioned insulated structure is provided with relief outlet, and this relief outlet is used for and will be fed in the above-mentioned insulated structure from above-mentioned heat insulating construction is external, and the melten glass that flows down along the wall at above-mentioned shaped device and the gas that rises to be discharged to above-mentioned heat insulating construction external.
In addition, a mode of the present invention provides a kind of glass plate manufacturing method, it is the method for making sheet glass by glass tube down-drawing, the method comprises following operation: Yi Bian make the both sides overflow of the groove of the shaped device that melten glass surrounds from insulated structure, make the melten glass rising that the gas in the above-mentioned insulated structure of the external importing of above-mentioned heat insulating construction flows down along the wall at above-mentioned shaped device on one side and will rise after gas to be discharged to above-mentioned heat insulating construction external.
In addition, a mode of the present invention provides a kind of sheet glass, its sheet glass for obtaining by above-mentioned glass plate manufacturing method, and it has compressive stress layers in the two sides in table.
(the 2nd scheme)
In order to reach above-mentioned the 2nd purpose, a mode of the present invention provides the sheet glass by the glass tube down-drawing moulding.
The Si area with high mercury is formed at from glass surface along thickness direction greater than 0 and be the scope of the degree of depth below the 30nm, and the atomic percent of the Si of described Si area with high mercury (atom %) is more than 105% with the concentration ratio of the atomic percent (atom %) of the Si of the central position of the thickness direction of above-mentioned sheet glass.
Above-mentioned Si area with high mercury has the maximum peak of Si atomic percent, reduces continuously along surface and the above-mentioned central position of Si atomic percent from above-mentioned maximum peak position to above-mentioned sheet glass of the thickness direction of above-mentioned sheet glass.
Another way of the present invention provides the sheet glass by the glass tube down-drawing moulding.
This sheet glass has the tension stress layer that forms in the inside of above-mentioned sheet glass and the compressive stress layers that forms in the both sides of above-mentioned tension stress layer.
The absolute value of the stress value of above-mentioned compressive stress layers is below the 4MPa, above-mentioned compressive stress layers is formed at from the surface of above-mentioned sheet glass thickness direction along above-mentioned sheet glass greater than 10 μ m and is the scope of the degree of depth below the 50 μ m, and the thickness of above-mentioned compressive stress layers is less than 1/13rd of the thickness of above-mentioned sheet glass.
The absolute value of the stress value of above-mentioned tension stress layer is below the 0.4MPa, and the deviation of the stress value of above-mentioned tension stress layer is below the 0.2MPa.
Another way of the present invention provides the manufacture method of sheet glass.This manufacture method has following operation:
Operation with the frit melting;
Use glass tube down-drawing by the operation of the glass ware forming glass ribbon of melting; With
Cut off above-mentioned glass ribbon and form the operation of sheet glass.
At this moment, the in the following manner moulding of above-mentioned glass ribbon: the Si area with high mercury is formed at from glass surface along thickness direction greater than 0 and be the scope of the degree of depth below the 30nm, the atomic percent of the Si of described Si area with high mercury (atom %) is more than 105% with the concentration ratio of the atomic percent (atom %) of the Si of the central position of the thickness direction of above-mentioned sheet glass, above-mentioned Si area with high mercury has the maximum peak of Si atomic percent, reduces continuously along surface and the above-mentioned central position of Si atomic percent from above-mentioned maximum peak position to above-mentioned sheet glass of the thickness direction of above-mentioned sheet glass.
Another way of the present invention provides the manufacture method of sheet glass.This manufacture method has following operation:
Operation with the frit melting;
Use glass tube down-drawing by the operation of the glass ware forming glass ribbon of melting; With
Cut off above-mentioned glass ribbon and form the operation of sheet glass.
At this moment, above-mentioned glass ribbon is to have two compressive stress layers and by the mode moulding of the tension stress layer of above-mentioned two compressive stress layers clampings, above-mentioned compressive stress layers is formed at from the surface of above-mentioned glass ribbon thickness direction along above-mentioned glass ribbon greater than 10 μ m and is the scope of the degree of depth below the 50 μ m, have 1/13rd thickness less than the thickness of above-mentioned glass ribbon, and the absolute value of compression stress value is below the 4MPa; The absolute value of the tensile stress values of above-mentioned tension stress layer is below the 0.4MPa.
The invention effect
According to above-mentioned the 1st scheme, the gas by insulated structure is risen along the melten glass that the wall at shaped device flows down, can promote that thus volatile component volatilizees from melten glass.Thus, can access the sheet glass that in table two sides has formed the high compressive stress layers of stress value.
For the sheet glass of above-mentioned the 2nd scheme, can the efficient of the processing treatment behind the glass ware forming not being caused detrimentally affect when the manufacturing of sheet glass, and the degree that glass surface is difficult to sustain damage strengthens glass surface.Glass-making processes of the present invention can be made above-mentioned sheet glass efficiently.
Description of drawings
Fig. 1 is the figure of internal stress distribution that the sheet glass of present embodiment is shown.
Fig. 2 is the figure of the internal stress distribution of the existing sheet glass that obtains when being illustrated in the annealing operation the glass quenching.
Fig. 3 is the figure that the example to the flow process of the manufacture method of the sheet glass of present embodiment describes.
Fig. 4 is the figure that processing describes to the shape in the manufacture method of the sheet glass of present embodiment.
Fig. 5 is the sectional view of device for producing glass sheet of making the sheet glass of present embodiment.
Fig. 6 is the stereographic map of device for producing glass sheet shown in Figure 4.
Fig. 7 is the sectional view of the device for producing glass sheet of variation.
Fig. 8 is the sectional view of the device for producing glass sheet of other variation.
Fig. 9 is the figure of distribution of internal stress of actual measurement that the sheet glass of present embodiment is shown.
Figure 10 is the figure of distribution of Si atomic percent (%) of actual measurement that the sheet glass of present embodiment is shown.
Figure 11 is the sectional view of existing glass manufacturing apparatus.
Embodiment
Below, the manufacture method of sheet glass of the present invention and sheet glass is described.
(schematically illustrating of sheet glass)
Fig. 1 is the sectional view of internal stress distribution that the sheet glass 10 of present embodiment is shown.
Sheet glass 10 for example is used for the FPD glass substrate by the glass tube down-drawing manufacturing.Thickness and the size of sheet glass 10 are not particularly limited.The reinforcing glass that sheet glass 10 has been carried out strengthening for example is used for the cover glass of the display frame of electronics.
As shown in Figure 1, sheet glass 10 has the tension stress layer 12 that forms in the inside of sheet glass and the compressive stress layers 14 that forms in the both sides of tension stress layer 12.
Compressive stress layers 14 is formed at from the surface of sheet glass 10 thickness direction along sheet glass 10 greater than 10 μ m and is the scope of the degree of depth below the 50 μ m, and the thickness of compressive stress layers 14 is less than 1/13 of the thickness of sheet glass 10.The absolute value of the stress value of compressive stress layers 14 is below the 4MPa, and the absolute value of the stress value of tension stress layer 12 is below the 0.4MPa.
Specifically, the thickness with compressive stress layers 14 is made as W 1The time, thickness W 1Greater than 0 μ m and be below the 50 μ m, less than the thickness W of sheet glass 10 01/13.The maximum value S of the stress value of compressive stress layers 14 (absolute value) 1Below 4MPa, the maximum value S of the stress value of tension stress layer 12 (absolute value) 2Below 0.4MPa.
Heavy line among Fig. 1 represents along the internal stress distribution of the thickness direction of sheet glass 10, is the compressive/tensile stress profile.Fig. 2 is the figure of the internal stress distribution of the existing sheet glass that obtains when being illustrated in the annealing operation the glass quenching.
The compressive/tensile stress profile that obtains during with the glass quenching in annealing operation is to draw the such profile of para-curve.The compressive stress layers that is formed at sheet glass with the glass quenching time is to produce because of the difference of glass surface with the thermal expansion of inside.The difference of this coefficient of thermal expansion produces because of the thermal conductivity of glass.The thickness W ' of the compressive stress layers that in the past obtained in the annealing operation in addition, 1(with reference to Fig. 2) is the thickness W ' of sheet glass 0More than 1/10.
Relative therewith, in the sheet glass 10, because the caused thermal expansion of Si area with high mercury that glass surface forms is poor, form the compressive stress layers 14 of thin thickness at the near surface of sheet glass 10.As described later, in the molding procedure of glass ribbon, by volatilization or the increase volatile quantity of promotion volatile component from the surface of melten glass or glass ribbon, thereby form the Si area with high mercury.At this moment, tension stress layer 12 has roughly certain low stress values at the thickness direction of sheet glass 10, is different at the thickness direction of sheet glass with the situation that draws parabolical mode and distribute from the tensile stress values of existing tension stress layer.
In addition, the stretching that the compression and tension stressor layers 12 that compressive stress layers 14 produces in sheet glass 10 integral body produces offsets, if therefore compressive stress layers 14 attenuation, then in order to offset with tensile stress, the stress value of compressive stress layers 14 (absolute value) raises.Therefore, compressive stress layers 14 for example has than only in the situation that make the larger stress value of stress value of the compressive stress layers that the glass quenching obtains in the annealing operation.That is, sheet glass 10 has formed the compressive stress layers 14 with large stress value at glass surface, so the glass surface of sheet glass 10 is compared with the existing sheet glass that only by annealing operation glass surface has been carried out strengthening and is difficult to sustain damage.
Below, sheet glass 10 is described in detail.
(detailed description of sheet glass)
Be formed at the thickness W of the compressive stress layers 14 of sheet glass 10 1Greater than 0 μ m and be below the 50 μ m.Compressive stress layers 14 is formed at glass surface.That is, compressive stress layers 14 is formed at the scope of the degree of depth of maximum 50 μ m from glass surface.And then in other words, the degree of depth on compressive stress layers 14 distance surfaces is below the 50 μ m.The degree of depth of compressive stress layers can be by promoting melten glass from molding procedure or glass ribbon the volatilization on surface deepen, if but the degree of depth of compressive stress layers 14 surpasses 50 μ m, can produce thus the disengaging of moulding suitable condition or the reduction of productivity.Therefore, the degree of depth on compressive stress layers 14 distance surfaces is below the 50 μ m.Therefore, the degree of depth of compressive stress layers 14 be preferably that 45 μ m are following, 40 μ m following, below the 38 μ m.Such optimal way can comprise that volatilize in the surface that promotes the glass ribbon of volatile component from melten glass or moulding or creating conditions of the sheet glass of the condition of increase volatile quantity realized with the composition of sheet glass by adjustment.
Need to prove, the deep of the compressive stress layers that forms at face among in the table of the depth representing sheet glass 10 of the compressive stress layers 14 in this specification sheets is apart from the degree of depth of glass surface.That is, the surface has formed respectively the compressive stress layers 14 with above-mentioned degree of depth in the table of sheet glass 10.
In addition, the degree of depth of compressive stress layers 14 surpasses 10 μ m.Surpass 10 μ m by the degree of depth that makes compressive stress layers 14, can prevent that glass from easily breaking because processing caused fine scar.Even from having darker scar, sheet glass 10 also is difficult to damaged aspect to be considered, more preferably 15 μ m are above, 20 μ m are above, 25 μ m are above, 30 μ m are above for the degree of depth of compressive stress layers 14, more than the 35 μ m.
Be formed at the degree of depth of compressive stress layers 14 of glass surface less than the thickness W of sheet glass 10 01/13, but preferably less than 1/15, less than 1/17, less than 1/20, less than 1/22, less than 1/24.
Such optimal way can also comprise that volatilize in the surface that promotes the glass ribbon of volatile component from melten glass or moulding or creating conditions of the sheet glass of the condition of increase volatile quantity realized with the composition of sheet glass by adjustment.
The stress value (absolute value) of the compressive stress layers 14 that forms at the near surface of sheet glass 10 is 4MPa to the maximum.If the maximum value of above-mentioned stress value (absolute value) surpasses 4MPa, then the summation of the stress value of compressive stress layers 14 becomes large, the processing of sheet glass 10, for example shape processing difficult.Therefore, the maximum value of the stress value of compressive stress layers 14 (absolute value) be preferably that 3.7MPa is following, 3.5MPa following, 3.0MPa is following, below the 2.8MPa.In addition, the maximum value of the stress value of compressive stress layers 14 (absolute value) be preferably that 0.1MPa is above, 0.5MPa above, 1MPa is above, 1.5MPa is above, more than the 2MPa.Compressive stress layers 14 is layers that stress value (absolute value) surpasses 0MPa, therefore forms compressive stress layers 14 by the glass surface at sheet glass 10, and the physical strength of sheet glass 10 improves.
Need to prove " stress value " expression in this specification sheets: cut respectively the sample that obtains the mean value of distance surface 0～10 μ m of this sample with predetermined depth at the glass surface from sheet glass 10.Therefore, as sheet glass 10, comprise that also compressive stress layers 14 has the sheet glass of the stress value of the scope that surpasses partly above-mentioned stress value.
As mentioned above, roughly certain at the thickness direction of sheet glass 10 at the stress value of the sheet glass 10 inner tension stress layer 12 that form.As mentioned above, the stress value of this tension stress layer 12 is below the 0.4MPa.If the maximum value of the stress value of tension stress layer 12 (absolute value) surpasses 0.4MPa, for example, in the situation that cut off sheet glass, the line of the predetermined depth that is used for cutting off and puts under is difficult to sheet glass 10 is divided into desired size in the elongation of the thickness direction ahead of estimate ground of sheet glass sometimes.Therefore, the maximum value of the stress value of tension stress layer 12 (absolute value) be preferably that 0.3MPa is following, 0.2MPa following, 0.15MPa, below the 0.10MPa.In the present embodiment, can make the maximum value of stress value (absolute value) of maximum value/tension stress layer 12 of stress value (absolute value) of the compressive stress layers 14 of glass surface is more than 6.
In addition, the thickness direction of sheet glass 10 remove tension stress layer 12 both sides each 1/10, obtain tension stress layer 12 centre portions 4/5 (below, referred to as " stretched center zone ".), in this centre portions 4/5, the change of the stress value in the tension stress layer 12 of sheet glass 10, be that the maximum value of stress value (absolute value) and the difference of minimum value are preferably below the 0.12MPa.Thus, can improve the cuttability of sheet glass.More preferably 0.10MPa is following, 0.05MPa following, below the 0.02MPa.Such optimal way also can comprise that volatilize in the surface that promotes the glass ribbon of volatile component from melten glass or moulding or creating conditions of the sheet glass of the condition of increase volatile quantity realized with the composition of sheet glass by adjustment.
The stress value of the tension stress layer 12 that forms in the inside of sheet glass 10 is roughly certain at the thickness direction of sheet glass 10, therefore compare with the situation that draws parabolical mode and form at the thickness direction of sheet glass with the stress value of tension stress layer, can keep tension stress layer 12 than unfertile land.
In more detail, the stress value of the tension stress layer 12 of sheet glass 10 is roughly certain at the thickness direction of sheet glass 10, compare with the maximum value (absolute value) of its stress value, the maximum value (absolute value) of the tensile stress values of the existing sheet glass that only obtains by annealing operation is larger.That is, in existing sheet glass, for the stress under compression with the compressive stress layers that is formed at glass surface offsets, with the profile formation tension stress layer of parabolic shape.Therefore, if the thickness attenuation of sheet glass, then be used for the also attenuation of thickness of the tension stress layer that the stress under compression with the compressive stress layers of glass surface offsets, therefore the stress value of tension stress layer extremely raises in existing sheet glass, for example, in the situation that cut off sheet glass, the line of the predetermined depth that puts under for cutting off is difficult to sheet glass 10 is divided into desired size in the elongation of the thickness direction ahead of estimate ground of sheet glass sometimes.But the stress value of the tension stress layer 12 of the sheet glass 10 of present embodiment is roughly certain at the thickness direction of sheet glass 10, so the maximum value of the stress value of tension stress layer is difficult to raise, and can carry out with good precision the processing of sheet glass.
If from the composition of glass sheet glass 10 is observed, then sheet glass 10 from glass surface along thickness direction greater than 0 and form Si area with high mercury (hereinafter being called the Si enriched layer) for the scope of the degree of depth below the 30nm.The Si enriched layer refers to, the concentration ratio of the atomic percent of Si (atom %) and the atomic percent (atom %) of the Si of the central position of the thickness direction of sheet glass 10 is the zone more than 105%.The scope that the Si enriched layer is positioned at is preferably and surpasses 0～25nm, 2～20nm, 5～16nm, 8～16nm.On the other hand, the volatilization on the surface that the degree of depth of Si enriched layer can be by promoting melten glass from molding procedure or glass ribbon is deepened, but can produce thus the disengaging of moulding suitable condition or the reduction of productivity.Perhaps, if the degree of depth of Si enriched layer surpasses 30nm, when then the glass surface of sheet glass 10 being implemented etch processes, be difficult to etching.In addition, if the degree of depth of Si enriched layer surpasses 30nm, the stress value (absolute value) of the compressive stress layers 14 that then forms at glass surface becomes large, produces the rough sledding that the cuttability of sheet glass reduces.Therefore, the degree of depth of Si enriched layer is preferably below the 30nm.
The Si enriched layer has the maximum peak of Si atomic percent, reduces to both sides from the position of above-mentioned maximum peak along the Si atomic percent of the thickness direction of sheet glass 10.Form by having such glass, formed above-mentioned compressive stress layers 14 and tension stress layer 12.The Si atomic percent refers to the atom % with respect to the Si of the whole glass ingredients except Sauerstoffatom (the whole glass ingredients except Sauerstoffatom such as Si, Al, B, Ca, Sr, Ba).
At this moment, from forming the aspect of above-mentioned Si enriched layer, preferably contain in the central position of the thickness direction of sheet glass more than the 30 quality % (for example, the viscosity of glass is 10 at the glass melting state 4.5～10 5Pool or temperature are 1100～1300 ℃) descend vapour pressure (saturation vapour pressure) to compare SiO 2High volatile component.
If above-mentioned concentration ratio less than 105%, then can't obtain the poor of sufficient coefficient of thermal expansion at glass surface and inside, can't effectively form compressive stress layers 14 herein.Perhaps, can't obtain sufficient Vickers' hardness and weather resistance.
On the other hand, if above-mentioned concentration ratio surpasses 130%, then the quality of sheet glass (physical property, thermal property, chemical property) changes, and for example, sometimes is difficult to carry out cut-out and the etch processes of sheet glass, can't be used for desired purposes.Consider from this aspect, the upper limit of above-mentioned concentration ratio is preferably 130%.
In addition, in the Si enriched layer, Si atom content or the highest peak position of Si atomic percent are positioned at the scope of the degree of depth of 0～5nm from glass surface.
By from glass surface along thickness direction greater than 0 and be that the scope of the degree of depth below the 30nm forms the Si enriched layer, can obtain the poor of sufficient coefficient of thermal expansion at glass surface and inside, can form compressive stress layers 14 at glass surface.In addition, can also improve Vickers' hardness and the weather resistance of glass surface, can prevent that sheet glass 10 from breaking.That is, Si is the composition that improves Vickers' hardness, and therefore by being formed at the Si enriched layer of glass surface, the Vickers' hardness of the glass surface of sheet glass 10 improves.In addition, the chemical proofing of Si is excellent, so the weather resistance that glass surface has formed the sheet glass 10 of Si enriched layer also improves.In addition, the Vickers' hardness of glass surface is compared raising with existing sheet glass, so the cracking frequency reduction, more is difficult to sustain damage, and can obtain being difficult to damaged effect.
The Vickers' hardness of the glass surface of sheet glass 10 for example is preferably that 4GPa is above, 5GPa above, more than the 5.3GPa.Perhaps, the Vickers' hardness of glass surface improves more than 0.01% in the ratio with the Vickers' hardness of inside glass, preferably improves more than 0.02%, more than 0.05%, more than 0.10%, more than 1%.
Like this, the aspect of stress is considered internally, and sheet glass 10 has tension stress layer 12 and compressive stress layers 14, considers to have the Si enriched layer near glass surface from the aspect that forms.In the molding procedure of glass ribbon described later, be 10 in the viscosity of glass for example by promotion 4.5～10 5Pool or temperature are saturated vapo(u)r pressure ratio SiO under 1100～1300 ℃ the glass melting state 2High volatile component can access sheet glass 10 thus from the surface volatilization of melten glass or glass ribbon.
Each mode of above-mentioned preferred value scope also can comprise that volatilize in the surface that promotes the glass ribbon of volatile component from melten glass or moulding or creating conditions of the sheet glass of the condition of increase volatile quantity realized with the composition of sheet glass by adjustment.
Such sheet glass 10 can also further utilize ion-exchange to carry out chemical enhancement process, thereby reinforcing glass is surperficial.Sheet glass 10 also can not utilize ion-exchange to carry out chemical enhancement process.Embodiments of the present invention also comprise the reinforcing glass that the glass surface of sheet glass 10 has been carried out chemical enhancing by ion-exchange.In this case, at glass surface and deposit and form above-mentioned Si enriched layer and based on the ion exchange treatment zone of ion-exchange.K plasma in the treatment solution that the ion exchange treatment zone refers to use as the Li of the composition in the glass surface, Na plasma exchange composition and ion-exchange is exchanged into and minute has carried out the zone that exchanges.At this moment, for the sheet glass 10 that strengthens through chemistry, with to result from the compressive stress layers 14 of Si enriched layer overlapping, form large compressive stress layers based on the compressive stress layers of chemical enhancement process.The thickness of the compressive stress layers that forms from glass surface to inside by ion-exchange is 20～100 μ m.
The maximum value of the stress value (absolute value) of the compressive stress layers that enlarges by ion-exchange be preferably 300MPa above, more preferably more than the 400MPa.Be more than the 300MPa by the maximum value that makes stress value (absolute value), the sheet glass 10 that strengthens through chemistry can access for sufficient intensity for protection indicating meter etc.Need to prove, the intensity of the higher then glass of above-mentioned stress value (absolute value) is higher, and the impact during glass breakage through strengthening also increases.For the accident that prevents that above-mentioned impact from causing, through the maximum value of the stress value (absolute value) of the compressive stress layers of the sheet glass 10 of chemical enhancement process be preferably below the 950MPa, more preferably below the 800MPa, more preferably below the 700MPa.On the other hand, compare with the existing sheet glass that has formed compressive stress layers at glass surface by making the glass quenching, it is large that the stress value of tension stress layer (absolute value) is difficult to become.
The thickness of the compressive stress layers of chemistry after the enhancement process is preferably that 20 μ m are above, 30 μ m are above, more than the 40 μ m.The thickness of compressive stress layers is larger, even the scar of reinforcing glass is dark, reinforcing glass also is difficult to break, and the deviation of physical strength reduces.On the other hand, the thickness of compressive stress layers is below the 100 μ m.Consider the easiness of the processing of reinforcing glass, the thickness of compressive stress layers is preferably below the 90 μ m, below the 80 μ m.
Need to prove, sheet glass 10, used the thickness of cover glass that sheet glass 10 has been carried out the reinforcing glass of chemical enhancing and be preferably below the 1.5mm.At this, be because: in the situation of the sheet glass that 1.5mm is above, it is large that the intensity of sheet glass self becomes, and near the compressive stress layers 14 that forms glass surface can't be given full play to function.That is, the sheet glass 10 that forms in the present embodiment and the thickness of cover glass is preferably that 1.0mm is following, 0.7mm following, 0.5mm is following, below the 0.3mm, and the thickness of sheet glass 10 is thinner, and then effect of the present invention is more remarkable.
In addition, the glass plate manufacturing method of present embodiment is suitable for large sheet glass.This be because, sheet glass is larger, then amount of flexibility is more, the easier fine scar that causes because of processing of sheet glass breaks, but by forming compressive stress layers 14 in glass pane surface, can reduce the generation of the problems referred to above.Therefore, be in the situation of the sheet glass more than the 1000mm, more than the 2000mm at the width of sheet glass 10, effect of the present invention is remarkable.
(kind of the glass of sheet glass)
Glass as being used for sheet glass 10 can use the kinds such as borosilicate glass, alumina silicate glass, aluminium borosilicate glass, soda-lime glass, alkaline silicate glass, alkaline alumina silicate glass, alkaline aluminum germanate glass.Need to prove, the glass that can be applicable to sheet glass of the present invention is not limited to mentioned kind, so long as comprise at least SiO 2With (viscosity of glass is 10 in the glass melting temperature 4.5～10 5The pool or temperature be 1100～1300 ℃) under saturation vapour pressure be higher than SiO 2The glass of kind of volatile component get final product.Need to prove Al 2O 3Being network forming oxide, is the lower composition of saturated steaming pressure ratio in the composition of glass.But, in the present embodiment, because its saturation vapour pressure is higher than SiO 2, so contain Al in the volatile component 2O 3
Need to prove, the content of the volatile component during glass forms more preferably 30 quality % above, more preferably 35 quality % above, more than the 40 quality %.Therefore, in the tension stress layer 12 of the nonvolatile sheet glass 10 of the volatile component of sheet glass 10, the content of volatile component is more than 30% quality.If the content of the volatile component during glass forms then can't promote the volatilization of volatile component less than 30 quality %, glass surface is difficult to form Si enriched layer and compressive stress layers.In addition, if contain a large amount of volatile components, then volatilization too increases the difficult that homogenizes of glass.The content of the volatile component during therefore, glass forms is preferably that 60 quality % are following, 50 quality % are following, more preferably below the 45 quality %.
(the composition example of each glass)
For example, aluminium borosilicate glass can example illustrate the glass that comprises following composition.Need to prove, the % of the composition of hereinafter putting down in writing is expressed as quality % and represents.Aluminium borosilicate glass for example is used for flat panel display glass substrate.The preferred content that is expressed as each composition in the following parantheses.
SiO 2：50～70%(55～65%、57～64%、58～62%)、
Al 2O 3：5～20%(10～20%、12～18%、15～18%)、
B 2O 3：0～15%(5～15%、6～13%、7～12%)、
At this moment, as optional component, can contain following composition.
MgO:0～10% (lower be limited to 0.01%, be limited to down 0.5%, on be limited to 5%, on be limited to 4%, on be limited to 2%),
CaO:0～10% (lower be limited to 1%, be limited to down 3%, be limited to down 4%, on be limited to 9%, on be limited to 8%, on be limited to 7%, on be limited to 6%),
SrO:0～10% (lower be limited to 0.5%, be limited to down 3%, on be limited to 9%, on be limited to 8%, on be limited to 7%, on be limited to 6%),
BaO:0～10% (on be limited to 8%, on be limited to 3%, on be limited to 1%, on be limited to 0.2%),
ZrO 2：0～10%(0～5%、0～4%、0～1%、0～0.1%)。
In addition, as aluminium borosilicate glass, can following composition be shown example.The preferred content that is expressed as each composition in the following parantheses.
SiO 2：50～70%(55～65%、58～62%)、
Al 2O 3：10～25%(15～20%、15～18%)、
B 2O 3：5～18%(8～14%、10～13%)、
MgO：0～10%(1～5%、1～2%)、
CaO：0～20%(1～7%、4～7%)、
SrO：0～20%(1～10%、1～3%)、
BaO：0～10%(0～2%、0～1%)、
K 2O：0～2%(0.1～2%、0.1～0.5%)、
SnO 2：0～1%(0.01～0.5%、0.01～0.3%)。
In addition, alkaline alumina silicate glass can example illustrate the glass that contains following composition.The alkalescence alumina silicate glass for example is used for the cover glass of the display frame of electronics.The preferred content that is expressed as each composition in the following parantheses.
SiO 2：50～70%(55～65%、57～64%、57～62%)、
Al 2O 3：5～20%(9～18%、12～17%)、
Na 2O：6～30%(7～20%、8～18%、10～15%)、
At this moment, as optional component, can contain following composition.
Li 2O：0～8%(0～6%、0～2%、0～0.6%、0～0.4%、0～0.2%)、
B 2O 3：0～5%(0～2%、0～1%、0～0.8%)、
K 2O:0～10% (lower be limited to 1%, be limited to down 2%, on be limited to 6%, on be limited to 5%, on be limited to 4%),
MgO:0～10% (lower be limited to 1%, be limited to down 2%, be limited to down 3%, be limited to down 4%, on be limited to 9%, on be limited to 8%, on be limited to 7%),
CaO:0～20% (lower be limited to 0.1%, be limited to down 1%, be limited to down 2%, on be limited to 10%, on be limited to 5%, on be limited to 4%, on be limited to 3%),
ZrO 2：0～10%(0～5%、0～4%、0～1%、0～0.1%)。
In addition, as alkaline alumina silicate glass, can following composition be shown example.
SiO 2：50～70%、
Al 2O 3：5～20%、
Na 2O：6～20%、
K 2O：0～10%、
MgO：0～10%、
CaO: surpass 2%～20%
ZrO 2：0～4.8%、
In addition, preferably,
SiO 2Content-1/2Al 2O 3Content: 46.5～59%,
CaO/RO (wherein, R is selected from least a among Mg, Ca, Sr and the Ba) content than surpass 0.3%,
SrO content+BaO content less than 10%,
(ZrO 2+ TiO 2)/SiO 2Content than 0～less than 0.07,
B 2O 3/R1 2O
(wherein, R1 is selected from least a among Li, Na and the K) content than 0～less than 0.1.
In addition, as other alkaline alumina silicate glass, can following composition be shown example.
SiO 2：58～68%、
Al 2O 3：8～15%、
Na 2O：10～20%、
Li 2O：0～1%、
K 2O：1～5%、
MgO：2～10%、
(each composition)
SiO 2Be the composition of skeleton that forms the glass of sheet glass 10, have the chemical durability and the stable on heating effect that improve glass.SiO 2Content is crossed when hanging down, and can't fully obtain chemical durability and stable on heating effect, if SiO 2Too high levels, then glass easily produces devitrification, the moulding difficult, viscosity rises simultaneously, the difficult that homogenizes of glass.
Al 2O 3Be the composition that forms the skeleton of glass, have the chemical durability and the stable on heating effect that improve glass.And, also have the effect that improves ion-exchange performance and etch-rate.Al 2O 3Content is crossed when hanging down, and can't fully obtain chemical durability and the stable on heating effect of glass.On the other hand, if Al 2O 3Too high levels, then the viscosity of glass rises, the melting difficult, acid resistance reduces simultaneously.
B 2O 3The viscosity that reduces glass, the melting that promotes glass and the composition of clarification.If B 2O 3Content is excessively low, and then the viscosity of glass raises, the difficult that homogenizes of glass.
MgO and CaO are the compositions that reduces the viscosity of glass and promote melting and the clarification of glass.And in alkaline-earth metal, the ratio that Mg and Ca rise the density of glass is little, so Mg and Ca are be used to making resulting glass lightweight and improving the effective composition of meltability.But if this MgO and CaO too high levels, then the chemical durability of glass reduces.
SrO and BaO are the compositions that reduces the viscosity of glass and promote melting and the clarification of glass.And, still improve the oxidisability of frit and the composition that property is clarified in raising.But if SrO and BaO too high levels, then the density of glass rises, and can't realize the lightweight of sheet glass, and the chemical durability of glass reduces simultaneously.
Li 2O is the composition that reduces the viscosity of glass and improve meltability and the formability of glass.And, Li 2O is the composition that improves the Young's modulus of glass.In addition, Li 2One of O or ion-exchange composition, the effect of the degree of depth of increase compressive stress layers 14 is high in alkalimetal oxide.But, if Li 2The too high levels of O, then liquid phase viscosity reduces, and therefore the easy devitrification of glass is difficult to utilize glass tube down-drawing to be stablized and carries out a large amount of productions of glass.And the thermal expansivity of glass becomes too high, and the resistance to sudden heating of glass reduces, and the periphery materials such as thermal expansivity and metal or organic system caking agent are difficult to coupling.In addition, following rough sledding can appear: carry out in the situation of ion exchange treatment the deteriorated quickening of the ion-exchange salt in the ion exchange treatment for the enhancing of carrying out sheet glass.And, if Li 2The too high levels of O, then the low temperature viscosity of glass excessively reduces, and stress occurs in the heating process after chemistry strengthens thus relax, and compression stress value is reduced, and therefore can't obtain sufficient intensity.
Na 2O is the neccessary composition that reduces the high temperature viscosity of glass and improve meltbility and the formability of glass.And, Na 2O still improves the composition of the devitrification resistance of glass.If Na 2O content is less than 6 quality %, and then the meltability of glass reduces, thereby is used for the cost up of melting.In addition, Na 2O is the ion-exchange composition, in the situation that carry out chemical enhancement process, if Na 2O content is less than 6 quality %, and then ion-exchange performance also reduces, thereby can't obtain sufficient intensity.And coefficient of thermal expansion excessively reduces, and causes thermal expansivity to be difficult to and the periphery material couplings such as metal or organic system caking agent.In addition, devitrification easily occurs in glass, and devitrification resistance also reduces, thereby can't use the glass tube down-drawing that makes the glass overflow, therefore is difficult to the stable a large amount of productions of glass of carrying out.On the other hand, if Na 2The O too high levels, then low temperature viscosity reduces, and coefficient of thermal expansion is superfluous, and shock-resistance reduces, and thermal expansivity is difficult to and the periphery material couplings such as metal or organic system caking agent.And, also can because the glass balance worsen the reduction that causes devitrification resistance, therefore be difficult to utilize glass tube down-drawing to be stablized and carry out a large amount of productions of glass.
K 2O is the high temperature viscosity that reduces glass, the meltability that improves glass and formability, improves the composition of devitrification resistance simultaneously.And, K 2O is the ion-exchange composition, by containing K 2O can improve the ion-exchange performance of glass.But, if K 2The too high levels of O, then low temperature viscosity reduces, and coefficient of thermal expansion is superfluous, and shock-resistance reduces, thereby in the situation that not preferred as cover glass.And, if K 2The too high levels of O, then thermal expansivity is difficult to and the periphery material couplings such as metal or organic system caking agent.In addition, also can because the glass balance worsen the reduction that causes devitrification resistance, therefore be difficult to utilize glass tube down-drawing to be stablized and carry out a large amount of productions of glass.
Li 2O, Na 2O and K 2O is stripping and make the TFT deterioration in characteristics and increase the thermal expansivity of glass and make the composition of substrate breakage when thermal treatment from glass, therefore in the situation that be applied to flat panel display glass substrate, does not preferably contain in a large number Li 2O, Na 2O and K 2O.But, by in glass, containing the mentioned component of specified quantitative, the thermal expansion of the deteriorated and glass of TFT characteristic can be suppressed within the specific limits, can improve simultaneously the meltability of glass and the basicity of raising glass, easily carry out the oxidation of the metal of valence state fluctuation, can also bring into play clarification.
ZrO 2To improve near the devitrification temperature of glass viscosity and the composition of strain point.And, ZrO 2Still improve the stable on heating composition of glass.In addition, ZrO 2It is the composition that significantly improves ion-exchange performance.But, if ZrO 2Too high levels, then devitrification temperature rises, devitrification resistance reduces.
TiO 2It is the composition that reduces the high temperature viscosity of glass.And, TiO 2It is the composition that improves ion-exchange performance.But, if TiO 2Too high levels, then devitrification resistance reduces.In addition, cause glass coloring, be not preferred in the cover glass etc. of display frame of FPD glass substrate, electronics.And because glass coloring, thereby ultraviolet ray transmissivity also reduces, and therefore when the processing of using ultraviolet curable resin, the rough sledding that ultraviolet curable resin is fully solidified can occur.
In the glass of sheet glass 10, can add finings as the composition of removing the bubble in the glass.As finings, so long as little and clarification excellence glass then is not particularly limited to the burden of environment, for example, can enumerate at least a in the metal oxides such as being selected from stannic oxide, ferric oxide, cerium oxide, terbium sesquioxide, molybdenum oxide and Tungsten oxide 99.999.
Need to prove As 2O 3And Sb 2O 3In melten glass, to produce the reaction of following the valence state fluctuation, the material with effect that glass is clarified, but because As 2O 3And Sb 2O 3Be the large material of burden that environment is caused, therefore, in the sheet glass 10 of present embodiment, do not contain in fact As in the glass 2O 3And Sb 2O 3Need to prove, in this specification sheets, do not contain in fact As 2O 3And Sb 2O 3Refer to remove do not add outside the impurity deliberately and content less than 0.01% quality.
(manufacture method of sheet glass)
Use the such sheet glass 10 of glass tube down-drawing manufacturing.Fig. 3 is the figure that the example to the flow process of the manufacture method of the sheet glass of present embodiment describes.The manufacture method of sheet glass mainly has melting operation (step S10), clarification operation (step S20), agitating procedure (step S30), molding procedure (step S40), annealing operation (step S50), cuts out plate operation (step S60), shape manufacturing procedure (step S70) and chemical enhancement process operation (step S80).
Melt in the operation (step S10), in not shown calciner, by heating frit based on the indirect heating of the burning of fossil oil with based on the direct heating of energising, make melten glass.The melting of glass also can be undertaken by the method beyond this.
Next, clarify operation (step S20).In the clarification operation, melten glass uses above-mentioned finings to remove bubble in the melten glass to be stored in state in the not shown liquid bath.Specifically, undertaken by the redox reaction of the metal oxide of valence state change in the melten glass.In the melten glass when high temperature, metal oxide is emitted oxygen by reduction reaction, and this oxygen becomes gas, makes the bubble growth in the melten glass and floats to liquid level.Thus, remove bubble in the melten glass.Perhaps, the bubble of oxygen absorbs the gas in other bubbles in the melten glass and grows up, and floats the liquid level to melten glass.Thus, remove bubble in the melten glass.In addition, after the deaeration, if the drop in temperature of glass, metal oxide generation oxidizing reaction then absorbs and does not float and residue in oxygen in the vesicle in the glass.Oxygen is absorbed, and vesicle further diminishes, and is absorbed in the glass again.
Next, carry out agitating procedure (step S30).In the agitating procedure, for chemical uniformity and the thermal uniformity that keeps glass, melten glass passes through towards vertical and not shown steel basin.Utilize the agitator that is arranged at steel basin to stir melten glass on one side, to vertical lower to bottom move on one side, be imported into rear operation.The ununiformity that can suppress thus, the glass such as brush line.
Next, carry out molding procedure (step S40).In the molding procedure, use glass tube down-drawing.Comprise that overflow down draw and discharge orifice drop-down etc. glass tube down-drawing is to have used the known method of TOHKEMY 2010-189220 communique for example, No. 3586142 communique of Japanese Patent or device shown in Figure 5.About the molding procedure in the glass tube down-drawing, as described later.Thus, mold the glass ribbon of the sheet with predetermined thickness, width.As forming method, overflow down draw most preferably in glass tube down-drawing also can be drop-down for discharge orifice.But, for the volatilization that promotes volatile component or increase volatile quantity and improve the stress value (absolute value) of compressive stress layers 14, the many overflow down draw of preferred volatile quantity.
Next, carry out annealing operation (step S50).Specifically, for the glass ribbon that is shaped to sheet, not control speed of cooling in order not deforming, to utilize not shown annealing furnace to be cooled to below the annealing point.Thus, glass ribbon with similarly have compressive stress layers 14 and tension stress layer 12 aspect the stress as the sheet glass 10 of end article, have the Si enriched layer aspect forming.
Next, cut out plate operation (step S60).Specifically, the glass ribbon that generates is continuously cut out plate every certain length, obtain sheet glass.
Carry out shape manufacturing procedure (step S70) thereafter.In the shape manufacturing procedure, except the size and dimension that cuts into predetermined sheet glass, carry out grinding and the grinding of glass surface and end face.Shape processing can utilize sandblast, use the physical means of cutting unit or laser apparatus, also can utilize the chemical means such as etching.Need to prove, when glass sheet shape being processed into complicated shape, preferably before chemical enhancement process, implement above-mentioned etch processes.
As the example that the shape of sheet glass 10 is processed, can enumerate following etch processes: perforate 11 on sheet glass shown in Figure 4 10, are processed into the outer shape that comprises curve and straight line.The sheet glass 10 that is processed into such outer shape is used for the cover glass of the display frame of electronics.
In this situation, at first, painting erosion resistant agent material on two major surfacess of sheet glass.Then, the photomask across the pattern with desired outer shape exposes anticorrosive additive material.Above-mentioned outer shape is not particularly limited, for example, for comprising the outer shape of part with negative curvature (when the intra-zone of observing to the left outer shape along the end of outer shape on one side advances, along with front and then crooked part to the right) on one side.Then, the anticorrosive additive material after the exposure is developed, and the zone beyond the etched zone of sheet glass forms corrosion-resisting pattern, and the etched zone of sheet glass is etched.At this moment, use in the situation of wet etchant as etching reagent, sheet glass is by isotropically etching.Thus, the central part of the end face of sheet glass is the most outstanding to foreign side, has formed from its central part to two main surface side crooked lentamente scarp.Need to prove the suitable circular shape of band that forms in the border of scarp and major surfaces and scarp border each other.
The anticorrosive additive material that uses in the etching work procedure is not particularly limited, and can be suitable for for the indefatigable material of etching reagent tool, and above-mentioned etching reagent uses when sheltering corrosion-resisting pattern after etching glass.For example, because glass is contained the wet etching of the aqueous solution of hydrofluoric acid usually and the dry etching that fluorine is gas is corroded, therefore be suitably the anticorrosive additive material of hydrofluoric acid patience excellence etc.In addition, as above-mentioned etching reagent, can be suitable for the mixing acid that comprises at least a acid among hydrofluoric acid, sulfuric acid, nitric acid, hydrochloric acid, the silicofluoric acid.By using hydrofluoric acid or above-mentioned mixed acid aqueous solution as etching reagent, can access the cover glass of desired shape.
In addition, add man-hour utilizing etching to carry out shape, can only easily realize complicated outer shape by adjusting mask pattern.In addition, carry out shape processing by utilizing etching, can also further boost productivity, can cut down finished cost.Need to prove, the stripping liquid as being used for anticorrosive additive material is peeled off from sheet glass can use the alkaline solutions such as KOH or NaOH.The kind of above-mentioned anticorrosive additive material, etching reagent, stripping liquid can be selected according to the material of sheet glass is suitable.
Need to prove, as etching method, not only can use the method that only impregnated in the etching solution, can also use the spraying etching method of spraying etching solution etc.Has the cover glass that surfaceness is the end face of high smoothness by utilizing such etching that sheet glass is carried out shape processing, can accessing.That is, can prevent from further to improve the physical strength of cover glass utilizing mechanical workout to carry out the generation that shape adds the tiny crack that must produce man-hour.
At last, utilize ion-exchange to carry out chemical enhancement process (step S80).Need to prove that difference is not according to circumstances carried out chemical enhancement process sometimes.For example, the sheet glass such as aluminium borosilicate glass that are used for flat-panel monitor do not carry out chemical enhancement process.On the other hand, the sheet glass for the cover glass of the such display frame that is suitable for electronics of alkaline alumina silicate glass carries out chemical enhancement process.
Strengthen by near the sheet glass 10 that has formed Si enriched layer and compressive stress layers 14 glass surface further being carried out chemistry, can further improve the intensity of sheet glass 10.In addition, and compare by the existing sheet glass that the glass quenching is formed compressive stress layers on the surface, it is large that the stress value of the tension stress layer of the sheet glass of present embodiment (absolute value) is difficult to become.
Need to prove, in order to carry out ion exchange treatment, preferably in glass ingredient, contain the Na as the ion-exchange composition 2O, Li 2O.Present embodiment through reinforcing glass that chemistry strengthens except the cover glass of the display frame that goes for electronics, can also be applicable to the housing of mobile communication terminal, the cover glass of solar cell, the glass substrate that indicating meter is used, the cover glass of contact panel indicating meter, the glass substrate of contact panel indicating meter etc.
For example, chemical enhancement process can use following method to carry out.
In the chemistry enhancement process, sheet glass 10 be impregnated in remain for example KNO about 350～550 ℃ 3During 100% processing is bathed approximately 1～25 hour.At this moment, the Na of surface layer of glass +Ion or Li +Ion and the K that processes in bathing +Ion or Li +Ion carries out ion-exchange, and sheet glass is strengthened by chemistry thus.Need to prove, the temperature during ion exchange treatment, time, ion exchanged soln etc. can suit to change.For example, ion exchanged soln can be two or more mixing solutionss.
In addition, the manufacture method of sheet glass has matting and inspection Check operation, and the explanation of these operations is omitted.Need to prove, the shape manufacturing procedure was carried out before chemical enhancement process operation, but also can carry out after chemical enhancement process operation.
In the molding procedure of the manufacturing of the sheet glass 10 of present embodiment, promote volatile component from the volatilization of glass ribbon or increased volatile quantity, formed thus the Si enriched layer, because this Si enriched layer, after annealing, cut out the plate operation before, form compressive stress layers 14 and tension stress layer 12.Volatile component represents to compare SiO 2Hold volatile composition, in other words, (for example, the viscosity of glass is 10 in the expression melten glass 4.5～10 5Pool or temperature are 1100～1300 ℃) saturation vapour pressure is higher than SiO 2Composition.As volatile component, can enumerate for example Al 2O 3, B 2O 3, Li 2O, Na 2O, K 2O, MgO, CaO, SrO, BaO, ZrO 2, SnO 2Deng, but be not limited to this.Need to prove B 2O 3, alkalimetal oxide (Li 2O, Na 2O, K 2O), the volatility of alkaline earth metal oxide (MgO, CaO, SrO, BaO) is high, therefore, as glass ingredient, preferably contains at least a.SnO 2Form volatilization with SnO.
If volatilization excessively then can't suitably be carried out the moulding of sheet glass, therefore, for example, B 2O 3The upper limit 14 quality % more preferably of content, be particularly preferably 13 quality %.In addition, if SnO 2Content high, then devitrification may occur in glass.Therefore, consider SnO from the aspect of the devitrification that prevents glass 2The upper limit 0.5 quality % more preferably of content, be particularly preferably 0.3 quality %.In addition, if a large amount of K that uses as the melting promotor of glass that adds 2O, then it is from the sheet glass stripping.Therefore, in the situation that be used for liquid crystal indicator with the flat panel display glass substrates such as glass substrate, K 2The upper limit of the content of O is 0.5 quality % more preferably.
These volatile components saturated vapour pressure in melten glass is higher than SiO 2, therefore (under the state of glass melting) volatilizees from melten glass or glass ribbon when moulding.That is, formed in the molding procedure of glass ribbon SiO by melten glass 2Composition in addition volatilizees on the glass ribbon surface, therefore, its result, the glass surface after moulding forms the Si enriched layer that the Si atomic percent is higher than the Si atomic percent of inside glass.In addition, if the glass surface of sheet glass forms the Si enriched layer, then owing to forming compressive stress layers 14 with the difference of the coefficient of thermal expansion of inside glass at glass surface.
(shaped device)
Fig. 5 is the figure that an example of implementing based on the shaped device of the forming method of glass tube down-drawing is described.The cross-sectional shape of shaped device 101 is the downward pentagon wedge-like (the home base shape that width is narrow) of point.Shaped device 101 have be provided with linearly extended groove 111 top, be arranged at groove 111 and downwards a pair of wall 112 from parallel both ends above this.Need to prove, in this specification sheets, for convenience of explanation, the bearing of trend (the paper vertical direction of Fig. 5) of groove on the horizontal plane 111 is also referred to as directions X, with being also referred to as Y-direction with the direction of directions X quadrature on the horizontal plane, vertical direction is also referred to as Z direction (referring to Fig. 6).
Illustrated supply-pipe supplies to the melten glass 103 of an end in the equably overflow of total length of groove 111 in order to make never, and the groove 111 from one end to the other side degree of depth shoals gradually.A pair of wall 112 has respectively from the end of top Y-direction vertical sagging vertical surface and the intilted scarp close to each other from the bottom of this vertical surface.The bottom on these scarp intersects each other and is formed on the crest line that directions X extends.
Shaped device 101 makes melten glass 103 from the both sides overflow of groove 111, and the melten glass of this overflow is directed and fuses in the bottom on scarp at wall 12 each other, thereby forms banded glass ribbon 104 continuously.
Insulated structure 102 has formed the molding space (chamber) that holds shaped device 101.Specifically, insulated structure 102 is made of the material of heat insulating ability excellence, have at above-below direction clip shaped device 101 and mutual opposed diapire 121 and roof 123, with the perisporium 122 of the peripheral rectangular drum like connected to one another of diapire 121 and roof 123.Be provided with the cast gate 125 that the glass ribbon 104 that formed by shaped device 101 is passed through in the central authorities of diapire 121.Need to prove, insulated structure 102 forms hollow structure, can use or cool off to the internal feed heating air of usefulness.
In the present embodiment, as shown in Figure 5,112 opposed with the wall of shaped device 101, be provided with the relief outlet more than 2 126 that connects perisporium 122 on the top towards the longwell section of Y-direction of perisporium 122.And, be provided with the introducing port more than 2 127 that connects perisporium 122 in the bottom towards the longwell section of Y-direction of perisporium 122.Therefore, by natural convection, form among Fig. 5 flowing of air such shown in arrow a, b, the c.That is, insulated structure 102 outer air are fed in the insulated structure 102 by introducing port 127.The air that imports rises along the melten glass 103 that the wall 112 at shaped device 101 flows down, and is discharged to outside the insulated structure 102 by relief outlet 126 thereafter.Like this, by making the fresh air that enters from the outside in insulated structure 102 interior risings, can promote volatile component (for example, Al 2O 3, B 2O 3, Li 2O, Na 2O, K 2O, MgO, CaO, SrO, BaO, ZrO 2, SnO 2Deng) volatilization from melten glass 103.The surface of the part of this volatile component volatilization, the melten glass 103 that namely contacts with the air that rises forms the Si enriched layer when glass ribbon 104 is cooled.By the generation of this Si enriched layer, form compressive stress layers 14.For the stress value (absolute value) that improves compressive stress layers 14, melten glass 103 preferably contains more volatile component.
Need to prove, relief outlet 126 and introducing port 127 also can be arranged at the shortwall section towards directions X in the perisporium 122.Perhaps, also can be only in the shortwall section towards directions X of perisporium 122 relief outlet 126 and introducing port 127 be set.But, in order to make volatile component equably volatilization on the total width of melten glass 103, preferred only with certain spacing relief outlet 126 and introducing port 127 are set in the longwell section towards Y-direction of perisporium 122.
And as long as can keep the required intensity of perisporium 122, then the shape of relief outlet 126 and introducing port 127 and quantity can suit to select.For example, can make as shown in Figure 6 the circle that is shaped as of relief outlet 126 and introducing port 127, also can form the slit-shaped of extending at directions X and reduce quantity.Need to prove, for Exhaust Gas from insulated structure 102 evenly and effectively, use that the width that spreads all over glass ribbon is whole and slit that extend is more effective.But the port area of slit is wider, and then airshed degree of crossing increases, and can produce following problem: the surface imperfection of sheet glass increases, the concave-convex surface of sheet glass worsens, be difficult to guarantee mold temperature.But this problem can solve in the following manner: the flow of adjusting gas, so that the temperature that is directed into air in the insulated structure 102 or rare gas element from introducing port 127 can be the target temperature in the insulated structure 102, and the pressure in the insulated structure 102 can be maintained predetermined pressure.
In addition, be directed into air preference in the insulated structure 102 such as the temperature of the degree that reduces for the temperature that does not make melten glass 103 and glass ribbon 104 by introducing port 127.Herein, if the amount of the air that imports is few, even then import the air of normal temperature, the temperature of melten glass 103 and glass ribbon 104 can not reduce like that yet.Therefore, can import the air of normal temperature.On the other hand, if it is many to import the amount of the air in the insulated structure 102, if then import the air of normal temperature, the temperature of melten glass 103 and glass ribbon 104 can significantly reduce.In this situation, preferably in the outside of insulated structure 102 or the inboard air heating that will import by introducing port 127 of arranging to the not shown heating unit of preset temperature.
In shaped device 101 described above, melten glass 103 is from the both sides overflow of the groove 111 of the shaped device 101 of insulated structure 102 encirclements, on the other hand, air rises along the melten glass 103 that the wall 112 at shaped device 101 flows down, and is discharged to afterwards outside the insulated structure 102.Herein, above-mentioned air is imported in the insulated structure 102 outside insulated structure 102.Like this, flow along the melten glass that the wall 112 at shaped device 101 flows down by making the air in the insulated structure 102, can promote volatile component from melten glass 103, to volatilize.Thus, can access the sheet glass 10 that in the table of the glass of sheet glass 10 two sides has formed the high compressive stress layers 14 of stress value.
Need to prove, in the present embodiment, relief outlet 126 is arranged at the top of perisporium 122, but the position of relief outlet 126 is not particularly limited.For example, as shown in Figure 7, relief outlet 126 can be arranged at shaped device 101 in the roof 123 directly over part.Even like this, utilize natural convection, also can make the air that outside insulated structure 102, is directed in the insulated structure 102 after the melten glass 103 that flows down along the wall 112 in shaped device 101 rises, be discharged to outside the insulated structure 102 by relief outlet 126.And in this situation, even on the top of shaped device 101, melten glass 103 also contacts with air by insulated structure 102, compares during therefore with the top that relief outlet 126 is arranged at perisporium 122, can further promote the volatilization of volatile component.
But, when relief outlet 126 is arranged at roof 123, might drop on the melten glass 103 by relief outlet 126 from the droppings such as dust of the top of insulated structure 102.Consider from this respect, preferably the embodiment shown in Fig. 5,6 is arranged at relief outlet 126 top of perisporium 122 like that.
And in the embodiment shown in Fig. 5,6, although introducing port 127 is arranged at the bottom of perisporium 122, the position of introducing port 127 is not particularly limited.For example, also can as shown in Figure 8, introducing port 127 be arranged at diapire 121.In this case, if introducing port 127 be positioned at shaped device 101 under regional R, then might the shape stability of glass ribbon 104 be impacted from flowing of the air of introducing port 127.Therefore, introducing port 127 is preferably disposed on the outside of regional R.
In addition, as shown in Figure 7, also introducing port 127 can be set.Even like this, insulated structure 102 outer air also import in the insulated structure 102 by cast gate 125.But in this situation, by cast gate 125, the shape stability of glass ribbon 104 might be impaired towards the direction opposite with glass ribbon 104 for air, and therefore preferred and cast gate 125 differently arranges introducing port 127.
And, in the embodiment shown in Fig. 5～8, carry out importing and air the discharge to insulated structure 102 outside of air in the insulated structure 102 by natural convection, but also can carry out by forced convection importing and the discharge of air.For example, when the bottom of insulated structure 102 connects supply-pipe, connect vent pipe on the top of insulated structure 102, supply-pipe or vent pipe connection gas blower are got final product.In this case, the end of the supply-pipe of the space opening in insulated structure 102 and vent pipe consists of respectively introducing port and relief outlet.Need to prove, in addition, the introduction method of air is such as having by strainer methods such as pressurized air decompression and importings.Need to prove, the introduction method of air is not limited to aforesaid method, can take other air introduction method.
In addition, the gas that is directed in the insulated structure 102 by introducing port 127 or cast gate 125 may not be air, also can be rare gas element.As rare gas element, consider from the aspect of the corrosion that prevents shaped device 101 and insulated structure 102, particularly preferably use nitrogen.
In the embodiment shown in Fig. 5～8, gas is imported in the insulated structure 102, gas is flowed along the flow direction of melten glass 103 or glass ribbon 104, can reduce thus the concentration of the volatile component of the gasification in the insulated structure 102.In the situation that flowing gas not, therefore the volatile component state that reaches capacity in insulated structure 102 can't further promote the volatilization of volatile component.That is, import insulated structure 102 interior gases and brought into play the function that the concentration of the volatile component that makes the gasification in the insulated structure 102 reduces.Therefore, flowing of the gas that imports from the outside is not only to be limited to rising, can be for descending yet.
In addition, the additive method as the volatilization of the volatile component that promotes melten glass 103 or glass ribbon 104 can also make to be reduced atmosphere in the molding space in the insulated structure 102.If the molding space in the insulated structure 102 is depressurized, then the volatilization of volatile component is promoted.
For example, by at relief outlet shown in Figure 5 126 suction device being set, can be with insulated structure 102 interior decompressions.Need to prove, be arranged at the relief outlet 126 of insulated structure 102 and the quantity of set suction device and be not particularly limited, arrange more than 1 and get final product.
Need to prove, if the molding spaces in the insulated structure 102 are excessively reduced pressure, then be imported into from cast gate 125 than the low gas of insulated structure 102 interior temperature, glass ribbon 104 can't homogenizing, and the thickness of sheet glass 10 produces deviation, and then also can deform.
Therefore, and compare in the insulated structure 102 before the decompression, preferably with the scope 1/10th below the interior molding spaces of insulated structure 102 are reduced pressure.That is, the air pressure of the molding space in the insulated structure 102 is in 1 atmospheric situation, preferably upper limit of pressure is made as 0.9 normal atmosphere and reduces pressure.
Atmosphere by the molding space in such adjustment insulated structure 102 forms glass ribbon 104.
In addition, as the additive method of the volatilization of the volatile component that promotes melten glass 103 or glass ribbon 104, can also improve the atmosphere temperature of the molding space in the insulated structure 102.If the atmosphere temperature of the molding space in the insulated structure 102 rises, then the saturation vapour pressure of volatile component also rises, and therefore promotes the volatilization of volatile component.
Need to prove, if the atmosphere temperature of the molding space in the insulated structure 102 excessively rises, the then moulding difficult of glass ribbon 104, and then energy consumption increases.Therefore, the scope of the rising of the atmosphere temperature of the molding space in the insulated structure 102 of rising is preferably and surpasses 0～100 ℃, more preferably surpasses 0～50 ℃, more preferably above 0～10 ℃.
Adjust like this atmosphere of the molding space in the insulated structure 102, increase saturation vapour pressure poor of the dividing potential drop of the volatile component in the atmosphere of the surface of melten glass 103 in the insulated structure 102 or glass ribbon 104 facing and volatile component.Thus, in the volatilization that promotes volatile component, form glass ribbon 104.Such promotion volatile component not only goes for two surfaces of glass and the glass ribbon of melting from the method for the surface volatilization of the glass of melting and glass ribbon, can also be applicable to only surface.
In addition, as the method for the volatile quantity of the volatile component that increases melten glass 103 or glass ribbon 104, the distance that can prolong the bottom of the shaped device 101 from molding procedure to the upper end of cast gate 125.By prolonging this distance, can prolong glass ribbon 104 by passing through the time in the molding space.Its result, it is elongated that the space glass ribbon 104 in insulated structure 102 is exposed to time of high temperature, and the volatilization time increases.Therefore, the volatile quantity of the volatile component of glass ribbon 104 increases.
If excessively prolong above-mentioned distance, then the thickness of the glass ribbon 104 of institute's moulding changes.Therefore, the increase of above-mentioned distance part more preferably surpasses 0～20mm, surpasses 0～10mm, surpasses 0～5mm, surpasses 0～1mm, surpasses 0～0.1mm.
In addition, can also increase the size of moulding body device 101 self, increase the length of flow of the wall 112 that melten glass 103 flows.Thus, it is elongated that the space melten glass 103 in insulated structure 102 is exposed to time of high temperature, and the volatilization time increases.Therefore, the volatile quantity of the volatile component of melten glass 103 increases.
For promoting volatile component from having carried out various explanations by the method for volatilization the melten glass in the insulated structure 102 or increase volatile quantity, these methods can be used alone or in combination.
The sheet glass 10 of making has like this formed compressive stress layers 14 at glass surface than unfertile land, therefore can in the processibility that keeps sheet glass, prevent that glass surface is injured.
Particularly, in the situation that sheet glass 10 is used for liquid crystal indicator with FDP glass substrates such as glass substrates, can't more contain the alkalimetal ion as the ion-exchange composition.Therefore, never carry out ion-exchange and set out in the aspect that obtains compressive stress layers 14, sheet glass 10 is effective.In addition, obtain than the compressive stress layers 14 that compressive stress layers is thinner and stress value (absolute value) is larger by existing sheet glass that the glass quenching is obtained in annealing operation, so sheet glass 10 can be effectively as the thin glass plate before the shape processing.
Existing sheet glass may be in the transmission of inter process, the surface is injured in cut-out and the shape processing.But sheet glass 10 can prevent that to strengthen the front glass surface injured carrying out chemistry, therefore can prevent the scar on cover glass surface, can improve surface quality.
(embodiment)
Fig. 9 is the figure of distribution that the atomic percent (%) of the Si that the sheet glass 10 of aluminium borosilicate glass is surveyed is shown.The atomic percent of Si (%) uses x-ray photoelectron light-dividing device (ULVAC-PHI company makes QuanteraSXM) to measure the Si atomic percent of near surface.Specifically, by sputter the surface of sheet glass is deep-cut to the various degree of depth, measured the atomic percent of each degree of depth.As measuring element, specifying Si and the relatively high volatile component of content is Al, B, Ca, Sr, Ba, obtains Si shared ratio in measuring element.These compositions are the volatile components that volatilize from the surface of glass ribbon in the molding procedure of glass ribbon.Need to prove, the content of K and Sn is little among volatile component, think that their amount is few on the impact that the Si atomic percent produces, so they is not included in the mensuration element.Sheet glass A shown in Figure 9, sheet glass B are the sheet glass that uses device shown in Figure 5 and change the condition made of flowing air.
As shown in Figure 9, among sheet glass A, the sheet glass B, compare the high zone more than 5% of Si atomic percent with the center of glass position and all be formed at from glass surface along thickness direction greater than 0 and be the scope of the degree of depth below the 30nm.Think that this is because in sheet glass A, sheet glass B, the amount of volatile component is lacked than inner near glass surface.
Need to prove, the content (quality %) of each composition of above-mentioned sheet glass A and sheet glass B is as described below.
SiO 260.9%
Al 2O 316.9%
B 2O 311.6%
MgO 1.7%
CaO 5.1%
SrO 2.6%
BaO 0.7%
K 2O 0.25%
SnO 20.13%
Figure 10 is the figure that the distribution of the internal stress that the sheet glass 10 of above-mentioned sheet glass A is surveyed is shown.About internal stress, use small area double refraction instrument (prince's instrumentation machine society makes KOBRA-CCD/X), the cross section that forms at thickness direction cut-out sheet glass 10 is measured respectively the light path rate (path difference/optical length) of 1cm every predetermined depth from the surface, it divided by photoelastic constant, is calculated internal stress.Need to prove, " internal stress " expression is along the mean value of the thickness of 0～10 μ m of the thickness direction of sheet glass.Therefore, sometimes also can form partly the stress value that surpasses result shown in Figure 10.
As shown in figure 10, the two sides has formed compressive stress layers 14 in the table of sheet glass 10 as can be known, and section has formed the tension stress layer 14 with roughly certain tensile stress values within it.In addition, the stress value that also is formed at as can be known the tension stress layer 14 of inside of glass plate roughly forms definitely in the sheet thickness direction.This is because volatile component is tailing off near the two sides in the glass table of sheet glass 10.
In addition, take out the sheet glass 10 that polylith uses device shown in Figure 5 to make, as embodiment 1～5.In addition, the compressive stress layers 14 of the sheet glass that utilizes the method making identical with embodiment 1 is carried out surface grinding and is removed, obtain thus compressing the sheet glass different with tensile stress profile shape and embodiment 1～5, with its as a comparative example 1.When the manufacturing of sheet glass, use possesses the continuous fusion device of the melting groove of refractory brick system and the picture frame groove of platinum system etc., with the frit of aluminium borosilicate glass with 1580 ℃ of meltings, and with 1650 ℃ of clarifications, after 1500 ℃ of stirrings, mold thickness by the glass tube down-drawing of having used device shown in Figure 5 and be the laminal sheet glass of 0.7mm.Utilize the method identical with above-mentioned sheet glass A, B to carry out the actual measurement of Si atomic percent of sheet glass of embodiment 1～5 and comparative example 1 and the actual measurement of internal stress.
In addition, loading at cut is that 2N, cut length are under the condition of 30mm, believe that in instrument power the front end of 318 types (manufacturing of instrument power letter company) scratch hardness tester arranges the ball point that diameter is 0.7mm (Bosch standard), with the sheet glass scratch of embodiment 1～5, comparative example 1.After this, utilize laser microscope that the glass surface of the sheet glass of embodiment 1～5, comparative example 1 is observed, the crack growth that scar is caused sheet glass be evaluated as badly, the sheet glass that crackle is not developed is evaluated as well.
Measured result and evaluation result have been shown in the following table 1.
[table 1]
Figure BDA00001796763500271
By above-mentioned table 1 as can be known, all to have formed thickness be the following compressive stress layers 14 of 50 μ m to embodiment 1～5.Therefore, be difficult for the efficient of the processing treatment behind the glass ware forming is caused detrimentally affect.In addition, the evaluation of scar all is evaluated as well among the embodiment 1～5.Hence one can see that, and sheet glass 10 strengthens glass surface can the efficient of the processing treatment behind the glass ware forming not caused detrimentally affect, glass surface to be difficult to injured degree.
In addition, the change of the stress value in " stretched center zone " of the tension stress layer 12 of embodiment 1～5, be that the maximum value of stress value (absolute value) and the difference of minimum value are below the 0.12MPa.
In addition, with following condition the embodiment 6～8 of the composition shown in the following table 2 and the sheet glass of comparative example 2 are carried out the chemistry enhancing.Comparative example 2 is to carry out the resulting reinforcing glass of chemistry enhancing after the part of compressive stress layers 14 that the surface at the sheet glass that utilizes the method manufacturing identical with embodiment 6～8 is formed is ground.
Sheet glass about embodiment 6～8 and comparative example 2, use possesses the continuous fusion device of the melting groove of refractory brick system and the picture frame groove of platinum system etc., to be mixed into the frit of the composition shown in the following table 2 with 1520 ℃ of meltings, and with 1550 ℃ of clarifications, after 1350 ℃ of stirrings, mold thickness by the glass tube down-drawing of having used device shown in Figure 5 and be the laminal sheet glass of 0.7mm, obtain chemistry enhancing sheet glass.For the sheet glass of comparative example 2, similarly the part of the compressive stress layers 14 of sheet glass 10 is carried out surface grinding with comparative example 1 and remove.
Next, by the glass surface scratch of aforesaid method with the sheet glass of embodiment 6～8 and comparative example 2.
With the sheet glass after cleaning at the KNO that remains 400 ℃ 3Dipping was approximately 2.5 hours during 100% processing was bathed, the Na that surface layer of glass is existed +Ion and the K that processes in bathing +Ion carries out ion-exchange, sheet glass is carried out chemistry strengthen.Sheet glass after chemistry strengthens impregnated in the rinse bath successively and cleans, and obtains dry reinforcing glass.
Utilize laser microscope that the embodiment 6～8 that so obtains and the glass surface of comparative example 2 are observed.At this moment, the crack growth that scar is caused sheet glass be evaluated as badly, the sheet glass that crackle is not developed is evaluated as well.
Composition and evaluation result have been shown in the following table 2.
[table 2]
Embodiment 6 Embodiment 7 Embodiment 8 Comparative example 2
SiO 2 65.2 65.5 66.0 65.5
Al 2O 3 8.3 8.0 10.0 8.0
B 2O 3 - - 1.0 -
MgO 4.0 8.0 5.0 8.0
CaO 3.5 - 0.8 -
Li 2O - 0.5 - 0.5
Na 2O 15.3 15.8 14.4 15.8
K 2O 2.0 1.5 2.8 1.5
ZrO 2 1.7 0.7 - 0.7
The evaluation of scar Well Well Well Bad
By above-mentioned table 2 as can be known, being evaluated as of the scar of embodiment 6～8 is good, but being evaluated as of comparative example 2 is bad.Hence one can see that, considers from the aspect that the scar that can prevent the reinforcing glass surface occurs, and it is effective that the sheet glass 10 with compressive stress layers 14 and tension stress layer 12 is carried out the chemistry enhancing.
Above, the manufacture method of sheet glass of the present invention and sheet glass is had been described in detail, but the present invention is not limited to above-mentioned embodiment, certainly can carry out various improvement and change in the scope that does not break away from purport of the present invention.
Industrial applicibility
Sheet glass 10 of the present invention is suitable for flat panel display glass substrate.In addition, sheet glass of the present invention is carried out that chemistry strengthens and the reinforcing glass that obtains is suitable for the cover glass of mobile telephone, digital camera, PDA (mobile communication terminal), solar cell, flat-panel monitor.In addition, sheet glass of the present invention can also be expected using with in the cover glass etc. such as the substrate of contact panel indicating meter, window glass, substrate for magnetic disc, solid photographic device.
Nomenclature
10 sheet glass
11 holes
12 tension stress layer
14 compressive stress layers
101 shaped devices
102 insulated structures
103 melten glass
104 glass ribbons
111 grooves
112 walls
121 diapires
122 perisporiums
123 roofs
125 cast gates
126 relief outlets
127 introducing ports

Claims (23)

1. sheet glass, it is characterized in that for the sheet glass by the glass tube down-drawing moulding,
The Si area with high mercury is formed at from glass surface along thickness direction greater than 0 and be the scope of the degree of depth below the 30nm, the atomic percent of the Si of described Si area with high mercury (atom %) is more than 105% with respect to the concentration ratio of the atomic percent (atom %) of the Si of the central position of the thickness direction of described sheet glass
Described Si area with high mercury has the maximum peak of Si atomic percent, reduces continuously from position to surface and the described central position of described sheet glass of described maximum peak along the Si atomic percent of the thickness direction of described sheet glass.
2. sheet glass as claimed in claim 1, wherein, the material of described sheet glass contained, under the glass melting state saturated vapo(u)r pressure ratio SiO 2High volatile component contains more than the 30 quality % in the central position of the thickness direction of described sheet glass.
3. sheet glass as claimed in claim 1 or 2, wherein,
Described sheet glass has the tension stress layer that forms in the inside of described sheet glass and the compressive stress layers that forms in the both sides of described tension stress layer,
The absolute value of the stress value of described compressive stress layers is below the 4MPa,
Described compressive stress layers is formed at from the surface of described sheet glass thickness direction along described sheet glass greater than 10 μ m and is the scope of the degree of depth below the 50 μ m, and the thickness of described compressive stress layers is less than 1/13rd of the thickness of described sheet glass,
The absolute value of the stress value of described tension stress layer is below the 0.4MPa, and the deviation of the stress value of described tension stress layer is below the 0.2MPa.
4. sheet glass as claimed in claim 1 or 2, wherein,
The glass surface of described sheet glass is formed with the ion exchange treatment zone of having carried out chemical enhancing by ion-exchange,
This sheet glass has the tension stress layer that forms in the inside of described sheet glass and the compressive stress layers that forms in the both sides of described tension stress layer,
Described compressive stress layers is formed at from glass surface the scope of the degree of depth of thickness direction 20 μ m along described sheet glass～100 μ m.
5. such as each described sheet glass of claim 1～4, wherein, this sheet glass is used for flat panel display glass substrate.
6. sheet glass, it is characterized in that for the sheet glass by the glass tube down-drawing moulding,
It has the tension stress layer that forms in the inside of described sheet glass and the compressive stress layers that forms in the both sides of described tension stress layer,
The absolute value of the stress value of described compressive stress layers is below the 4MPa,
Described compressive stress layers is formed at from the surface of described sheet glass thickness direction along described sheet glass greater than 10 μ m and is the scope of the degree of depth below the 50 μ m, and the thickness of described compressive stress layers is less than 1/13rd of the thickness of described sheet glass,
The absolute value of the stress value of described tension stress layer is below the 0.4MPa, and the deviation of the stress value of described tension stress layer is below the 0.2MPa.
7. sheet glass as claimed in claim 6, wherein, the described tension stress layer of described sheet glass contains the above saturated vapo(u)r pressure ratio SiO under the molten state of described sheet glass of 30 quality % 2High volatile component.
8. such as claim 6 or 7 described sheet glass, wherein, this sheet glass is used for flat panel display glass substrate.
9. the manufacture method of a sheet glass is characterized in that, the method has following operation:
Operation with the frit melting;
Use glass tube down-drawing by the operation of the glass ware forming glass ribbon of melting; With
Cut off described glass ribbon and form the operation of sheet glass,
The in the following manner moulding of described glass ribbon: the Si area with high mercury is formed at from glass surface along thickness direction greater than 0 and be the scope of the degree of depth below the 30nm, the atomic percent of the Si of described Si area with high mercury (atom %) is more than 105% with respect to the concentration ratio of the atomic percent (atom %) of the Si of the central position of the thickness direction of described sheet glass, described Si area with high mercury has the maximum peak of Si atomic percent, reduces continuously from position to surface and the described central position of described sheet glass of described maximum peak along the Si atomic percent of the thickness direction of described sheet glass.
10. the manufacture method of sheet glass as claimed in claim 9, wherein, when the described glass ribbon of moulding, increase with the right atmosphere of at least one surface of the glass of described melting and described glass ribbon in the dividing potential drop of described volatile component and the saturation vapour pressure of described volatile component poor, promote thus volatile component from least one surface volatilization of the glass of described melting and described glass ribbon, form described glass ribbon.
11. the manufacture method of sheet glass as claimed in claim 10 wherein, when the described glass ribbon of moulding, is adjusted at least one of the pressure and temperature in the space of the described glass ribbon of moulding, thereby promotes saturated steaming pressure ratio SiO in the glass of described melting 2The volatilization of high volatile component.
12. the manufacture method of sheet glass as claimed in claim 10 wherein, when the described glass ribbon of moulding, in the space of the described glass ribbon of moulding, forms flowing of gas along described glass ribbon.
13. the manufacture method of sheet glass as claimed in claim 9 wherein, when the described glass ribbon of moulding, is adjusted the time of passing through of the glass ribbon in the space of the described glass ribbon of moulding, thereby increases saturated steaming pressure ratio SiO in the glass of described melting 2The volatile quantity of high volatile component.
14. the manufacture method of a cover glass, the method have 3 operations of manufacture method of each described sheet glass of claim 9～13, and further have following operation:
Strengthen carrying out chemistry by the surface of the described sheet glass of the manufacture method manufacturing of described sheet glass by ion-exchange.
15. the manufacture method of a sheet glass is characterized in that, it has following operation:
Operation with the frit melting;
Use glass tube down-drawing by the operation of the glass ware forming glass ribbon of melting; With
Cut off described glass ribbon and form the operation of sheet glass,
Described glass ribbon is to have two compressive stress layers and by the mode moulding of the tension stress layer of described two compressive stress layers clampings, described compressive stress layers is formed at from the surface of described glass ribbon thickness direction along described glass ribbon greater than 10 μ m and is the scope of the degree of depth below the 50 μ m, have 1/13rd thickness less than the thickness of described glass ribbon, and the absolute value of compression stress value is below the 4MPa; The absolute value of the tensile stress values of described tension stress layer is below the 0.4MPa.
16. the manufacture method of sheet glass as claimed in claim 15, wherein, by the described glass ribbon of described glass ware forming of melting the time, increase with the right atmosphere of at least one surface of the glass of described melting and described glass ribbon in the dividing potential drop of described volatile component and the saturation vapour pressure of described volatile component poor, promote thus volatile component from least one surface volatilization of the glass of described melting and described glass ribbon, form described glass ribbon.
17. the manufacture method of sheet glass as claimed in claim 16 wherein, when the described glass ribbon of moulding, is adjusted at least one of the pressure and temperature in the described space, thereby promotes saturated steaming pressure ratio SiO in the glass of described melting 2The volatilization of high volatile component.
18. the manufacture method of sheet glass as claimed in claim 16 wherein, when the described glass ribbon of moulding, in the space of the described glass ribbon of moulding, forms flowing of gas along described glass ribbon.
19. the manufacture method of sheet glass as claimed in claim 15 wherein, when the described glass ribbon of moulding, is adjusted the time of passing through of the glass ribbon in the space of the described glass ribbon of moulding, thereby increases saturated steaming pressure ratio SiO in the glass of described melting 2The volatile quantity of high volatile component.
20. the manufacture method of a cover glass, the method have 3 operations of manufacture method of each described sheet glass of claim 9～13, and further have following operation:
Strengthen carrying out chemistry by the surface of the described sheet glass of the manufacture method manufacturing of described sheet glass by ion-exchange.
21. a device for producing glass sheet, it is the device of making sheet glass by glass tube down-drawing, wherein,
This device possesses shaped device and insulated structure,
Described shaped device makes melten glass from the both sides overflow of groove, and the melten glass of this overflow is guided and fuses by wall each other, thereby forms glass ribbon,
Described insulated structure surrounds described shaped device, and has the cast gate that the described glass ribbon that formed by described shaped device is passed through,
Described insulated structure is provided with relief outlet, and it is external that the gas that this relief outlet is used for rising from the external melten glass that is directed in the described insulated structure and flows down along the wall at described shaped device of described heat insulating construction is discharged to described heat insulating construction.
22. a glass plate manufacturing method, it is the method for making sheet glass by glass tube down-drawing, wherein,
The method comprises following operation: Yi Bian make the both sides overflow of the groove of the shaped device that melten glass surrounds from insulated structure, make the melten glass rising that flows down along the wall at described shaped device from the external gas that is directed in the described insulated structure of described heat insulating construction on one side and will rise after gas to be discharged to described heat insulating construction external.
23. a sheet glass, its sheet glass for obtaining by the described glass plate manufacturing method of claim 22, wherein, this sheet glass has compressive stress layers in the two sides in table.
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US11079309B2 (en) 2013-07-26 2021-08-03 Corning Incorporated Strengthened glass articles having improved survivability
CN103395985A (en) * 2013-08-15 2013-11-20 蚌埠玻璃工业设计研究院 Amber alumina silicate glass
CN103395985B (en) * 2013-08-15 2015-09-16 蚌埠玻璃工业设计研究院 A kind of amber alumina silicate glass
US11634359B2 (en) 2014-02-24 2023-04-25 Corning Incorporated Strengthened glass with deep depth of compression
US11878941B2 (en) 2014-06-19 2024-01-23 Corning Incorporated Glasses having non-frangible stress profiles
US10364182B2 (en) 2014-10-08 2019-07-30 Corning Incorporated Glasses and glass ceramics including a metal oxide concentration gradient
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US11084756B2 (en) 2014-10-31 2021-08-10 Corning Incorporated Strengthened glass with ultra deep depth of compression
US11746046B2 (en) 2014-10-31 2023-09-05 Corning Incorporated Strengthened glass with ultra deep depth of compression
US11021393B2 (en) 2014-11-04 2021-06-01 Corning Incorporated Deep non-frangible stress profiles and methods of making
US11377388B2 (en) 2014-11-04 2022-07-05 Corning Incorporated Deep non-frangible stress profiles and methods of making
US11267228B2 (en) 2015-07-21 2022-03-08 Corning Incorporated Glass articles exhibiting improved fracture performance
US11613103B2 (en) 2015-07-21 2023-03-28 Corning Incorporated Glass articles exhibiting improved fracture performance
US10579106B2 (en) 2015-07-21 2020-03-03 Corning Incorporated Glass articles exhibiting improved fracture performance
US11472734B2 (en) 2015-12-11 2022-10-18 Corning Incorporated Fusion-formable glass-based articles including a metal oxide concentration gradient
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