CN104936923A - Method for manufacturing glass substrate with laminated film - Google Patents

Method for manufacturing glass substrate with laminated film Download PDF

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Publication number
CN104936923A
CN104936923A CN201480004902.0A CN201480004902A CN104936923A CN 104936923 A CN104936923 A CN 104936923A CN 201480004902 A CN201480004902 A CN 201480004902A CN 104936923 A CN104936923 A CN 104936923A
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CN
China
Prior art keywords
temperature
glass ribbon
glass
manufacture method
glass substrate
Prior art date
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Pending
Application number
CN201480004902.0A
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Chinese (zh)
Inventor
宫下纯一
白井正信
米道友广
远藤健朗
近藤裕己
广松邦明
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AGC Inc
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Asahi Glass Co Ltd
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Publication of CN104936923A publication Critical patent/CN104936923A/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B25/00—Annealing glass products
    • C03B25/04—Annealing glass products in a continuous way
    • C03B25/06—Annealing glass products in a continuous way with horizontal displacement of the glass products
    • C03B25/08—Annealing glass products in a continuous way with horizontal displacement of the glass products of glass sheets
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/001—General methods for coating; Devices therefor
    • C03C17/002—General methods for coating; Devices therefor for flat glass, e.g. float glass
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
    • C03C3/087—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal containing calcium oxide, e.g. common sheet or container glass
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40—Oxides

Abstract

A method for manufacturing a glass substrate with a laminated film, using a glass manufacturing apparatus which comprises a melting furnace that melts a starting material of glass, a float bath that molds a glass ribbon by floating molten glass on molten metal and an annealing furnace that anneals the glass ribbon, by forming a laminated film on the glass ribbon by the CVD method with multiple injectors provided in the annealing furnace and cutting the glass ribbon. This method is characterized in that the laminated film is composed of two or more layers, the glass substrate has a strain temperature Ts ( DEG C) of 550 DEG C or more, the laminated film is formed at Tg or less when the transition temperature of the glass substrate is Tg ( DEG C), and the drop temperature K1 per unit length of the glass ribbon in a temperature range in which all layers of the laminated film are formed is 0 DEG C/m<K1<10 DEG C/m.

Description

With the manufacture method of laminated film glass substrate
Technical field
The present invention relates to the manufacture method of band laminated film glass substrate, laminated film is formed in the manufacture method of the band laminated film glass substrate on glass ribbon especially by online CVD (chemical vapour deposition Chemical Vapor Deposition) method in annealing furnace.
As the method being formed film by online CVD on glass ribbon, the method recorded in known such as patent documentation 1 ~ 3.
Patent documentation 1 discloses on the glass ribbon in float tin groove and carries out film forming by CVD to the oxide compound containing silicon and oxygen.Now in order to prevent the oxidation caused due to oxygen of the molten metal of float tin groove, disclosing and using unsaturated hydrocarbon compound and carbonic acid gas as oxygen source.
Patent documentation 2 discloses the method forming silicon-dioxide tunicle, stannic oxide tunicle in the coating position (injector) being configured at float tin groove and the coating position that is configured at annealing furnace successively on glass ribbon.
Patent documentation 3 discloses and arrange nozzle (injector) in the scope between the outlet and annealing furnace entrance of float tin groove, and glass ribbon carries out the method for film forming.
Patent documentation 4 discloses the method forming the conducting film be made up of fluorine doped tin oxide or antimony doped tin oxide on the glass substrate that DEFORMATION POINTS is more than 525 DEG C.
Prior art document
Patent documentation
Patent documentation 1: Japanese Patent Laid-Open 1-201046 publication
Patent documentation 2: Japanese Patent Laid-Open 3-33036 publication
Patent documentation 3: Japanese Patent Laid-fair 4-35558 publication
Patent documentation 4: Japanese Patent Laid-Open 2010-28068 publication
Summary of the invention
Invent technical problem to be solved
In float tin groove, generally for and prevent the oxidation of molten metal and the surrounding of molten metal is set to nonoxidizing atmosphere.In addition, in float tin groove, glass ribbon is soft state, when carrying out film forming to the glass ribbon CVD of the softness in float tin groove, is difficult to warpage or cracking that the glass ribbon caused due to temperature head occurs.
Patent documentation 1 discloses the oxidation of the molten metal in order to prevent float tin groove, uses unsaturated hydrocarbon compound and carbonic acid gas as source of oxygen.This is owing to can not use oxygen when carrying out film forming to oxide compound in nonoxidizing atmosphere, and must use the cause of the reactant gases containing oxygen molecule.But when carrying out film forming by the method to the oxide compound containing silicon and oxygen, the carbon (C) deriving from hydrocarbon or carbonic acid gas can be mixed in oxide film.Consequently, the film that absorption increases, transmissivity has been deteriorated compared with the film not containing carbon of film has been made.
Therefore, there is the problem that when carrying out film forming by CVD to oxide compound in float tin groove, film quality is deteriorated, wish in the outer film forming of float tin groove.
In patent documentation 2, indicating when to possess coating position in annealing furnace due to different with temperature condition during for annealing to glass ribbon for the temperature condition of film forming and have problems, also there is more complicated problem when forming multilayer and being coated to.Therefore, in patent documentation 2, recommend the oxygen through being pre-mixed and coating precursor are contacted with glass ribbon in float tin groove.But owing to needing sealing to carry out airtight to oxygen in the method, therefore device is complicated.In addition, if possess coating position and form metal oxide coating in annealing furnace on glass ribbon, then compared with not possessing the situation of coating position, due to glass ribbon and injector heat exchange and occur from glass ribbon sharply desuperheating, glass ribbon likely deforms or damages and ftracture.Especially, what the quantity of coating position occurred to damage and ftracture more at most may be higher, and the glass ribbon due to warpage contacts with coating position and sometimes occurs and the damage of glass and cracking.
Therefore, patent documentation 2 discloses and possesses more than one coating position when forming multilayer and being coated in annealing furnace, exist and must establish different temperature controlled problems.On the other hand, suitable method for managing temperature when not specifically being disclosed in the multiple coating position of configuration in annealing furnace why.
Patent Document 3 discloses, in the scope between the outlet and annealing furnace entrance of float tin groove, nozzle (injector) is set in the mode of cover glass overall width.But, when directly utilizing float glass process manufacturing installation in the past, between float tin groove and annealing furnace, there is no enough spaces to configure nozzle.In addition, the temperature of not carrying out glass ribbon in the space between float tin groove and annealing furnace controls, if carry out film forming in the space between float tin groove and annealing furnace, then there is heat exchange due to nozzle and glass ribbon and the problem of the glass ribbon caused sharply desuperheating.
In addition, Patent Document 4 discloses, by online CVD, film forming is carried out to conducting film, but only describe to manufacture in streamline at sheet glass about online CVD and utilize its heat to carry out film forming, do not disclose any concrete film.
The present invention is the invention being conceived to above problem and producing, and provides a kind of and in online CVD, the glass ribbon of the high DEFORMATION POINTS with more than 550 DEG C is carried out to suitable temperature treatment, uses the manufacture method of the multiple injectors band laminated film glass substrate of form layers integrated membrane on glass ribbon be arranged in annealing furnace.
The technical scheme that technical solution problem adopts
The invention provides a kind of manufacture method with laminated film glass substrate, it uses the melting furnace possessing molten raw, float tin groove melten glass being floated over molten metal forms glass ribbon and the glass manufacturing apparatus to the annealing furnace that described glass ribbon is annealed, by the CVD multiple injectors be arranged in described annealing furnace form layers integrated membrane on described glass ribbon, the manufacture method of the band laminated film glass substrate that described glass ribbon is cut off;
Above-mentioned laminated film is made up of the layer of more than 2 layers,
The deformation temperature Ts (DEG C) of above-mentioned glass substrate more than 550 DEG C,
When the second-order transition temperature of above-mentioned glass substrate is set to Tg (DEG C), above-mentioned laminated film is formed at below Tg,
The decline temperature K1 of the per unit length of the above-mentioned glass ribbon in the temperature range of whole layers forming above-mentioned laminated film is 0 DEG C/m < K1 <, 10 DEG C/m.
Here, in a form of manufacture method of the present invention, the linear expansivity of above-mentioned glass substrate at 50 DEG C ~ 350 DEG C can be 50 × 10 -7/ K ~ 105 × 10 -7/ K.This is because little with the common glassy phase specific thermic dilatation coefficient such as soda-lime glass, thus when there is identical temperature variation, distortion is also little, and the situation that glass ribbon warpage rises and falls tails off.
In addition, in a form of manufacture method of the present invention, the Young's modulus of above-mentioned glass substrate is at more than 75GPa.This is because high with the common glassy phase specific Young's modulus such as soda-lime glass, thus when there is identical temperature variation, distortion is also little, and the situation that glass ribbon warpage rises and falls tails off.
In addition, in a form of manufacture method of the present invention, above-mentioned glass substrate is when being set to η (dPas) by viscosity, the temperature meeting log η=2 can more than 1500 DEG C, and the temperature meeting log η=4 can be 1100 ~ 1260 DEG C.
In addition, in a form of manufacture method of the present invention, above-mentioned glass substrate represents to possess and contain in the quality % of oxide compound benchmark
In fact not containing B 2o 3composition.
In this case, especially, above-mentioned glass substrate represents in the quality % of oxide compound benchmark, can contain
ZrO 20.5～5。
In addition, above-mentioned glass substrate represents in the quality % of oxide compound benchmark, can contain
Na 2O+K 2O 1～19。
In addition, above-mentioned glass substrate represents in the quality % of oxide compound benchmark, can contain
MgO+CaO 5～15。
In addition, above-mentioned glass substrate represents in the quality % of oxide compound benchmark, can contain
SiO 2+Al 2O 364～82。
In addition, above-mentioned glass substrate represents in the quality % of oxide compound benchmark, can contain
Fe 2O 30.005～0.1。
In addition, in a form of manufacture method of the present invention, the layer of more than at least two layers of above-mentioned laminated film can be formed at the temperature more than 510 DEG C.
In addition, in a form of manufacture method of the present invention, at least two layers of above-mentioned laminated film can be formed at the temperature of more than Ts.
In addition, in a form of manufacture method of the present invention, at least one deck can be formed at lower than the temperature of Ts.
In addition, in a form of manufacture method of the present invention, the decline temperature of the per unit length in the temperature range from 510 DEG C to the temperature out of above-mentioned annealing furnace can be greater than falls temperature from the per unit length of the above-mentioned glass ribbon in the temperature range of Tg to 510 DEG C.
In addition, in a form of manufacture method of the present invention, well heater can be set between adjacent injectors in the carrying direction along above-mentioned glass ribbon.
In addition, in a form of manufacture method of the present invention, if the quantity of the above-mentioned multiple injector be arranged in above-mentioned annealing furnace is set to N iNJ, then along the spacing T at the center of above-mentioned carrying direction adjacent injectors iNJmeet 1.0m≤T iNJ≤ 25/N iNJm.
In addition, in a form of manufacture method of the present invention, the lower surface of above-mentioned injector and the distance of glass ribbon can be below 30mm.
The effect of invention
If adopt the manufacture method of band laminated film glass substrate of the present invention, then may be provided in online CVD and the glass ribbon of the DEFORMATION POINTS with more than 550 DEG C is carried out to suitable temperature treatment, uses the manufacture method of the multiple injectors band laminated film glass substrate of form layers integrated membrane on glass ribbon be arranged in annealing furnace.
Accompanying drawing explanation
Fig. 1 is the sketch of the glass manufacturing apparatus of one embodiment of the present invention.
Fig. 2 is the sectional view of the injector of one embodiment of the present invention.
Fig. 3 is the sectional view of an embodiment of the transparent conductive substrate for solar cell manufactured by the manufacture method of band laminated film glass substrate of the present invention.
Fig. 4 controls to the temperature of the glass ribbon in the annealing furnace of one embodiment of the present invention the figure that is described.
Embodiment
First, an embodiment of the glass manufacturing apparatus used with reference to the manufacture method of Fig. 1 to band laminated film glass substrate of the present invention is described.In addition, in the following description, sometimes the situation forming integrated membrane at least is from level to level included, be called film forming.
As shown in Figure 1, glass manufacturing apparatus 50 possesses and is formed with lower part: the smelting furnace 51 of molten glass raw material and the melten glass of fusing is floated on molten tin is shaped the float tin groove 52 of smooth glass ribbon and carried out the annealing furnace 54 of annealing after being drawn from float tin groove 52 by glass ribbon by runner 53 by the temperature of the glass ribbon that slowly declines.
The glass ribbon carried by transport roller 55 such as to the heat that the needed position supply in stove is under control by combustion gases or its output of electric heater, is slowly cooled to the temperature province close to normal temperature by annealing furnace 54.By this, there is the effect eliminated the residual stress be present in glass ribbon, suppress glass ribbon occurs warpage or cracking.Multiple injector 60 is provided with, by CVD form layers integrated membrane on glass ribbon in annealing furnace 54.
Injector 60 is made up of 6 injector 60a ~ 60f, form layers integrated membrane on the glass ribbon be handled upside down.Electric heater 56 is provided with between each injector.In addition, the quantity of injector 60 is at this not circumscribed, and preferably within the scope of 2 ~ 9, electric heater also can increase and decrease as required.By these electric heaters, prevent from declining from the excessive temperature of the glass ribbon to outlet of the entrance in annealing furnace.On the other hand, the well heater be arranged between injector can heat the glass ribbon between injector, but owing to not heating the glass ribbon of injector lower surface, by the setting of this well heater, the temperature variation of the glass ribbon that the entrance from injector is cooled to outlet is not affected.
Injector 60 (60a ~ 60f) as shown in Figure 2, is configured at the top with the glass ribbon 70 of transport roller 55 opposition side in the mode clipping glass ribbon 70.In each injector, relative on the rectangular direction, carrying direction of glass ribbon, the substantially central portion in lower surface 65 arranges elongated slit-shaped blow-off outlet 61, and the fore-and-aft direction both sides of blow-off outlet 61 arrange the venting port 62 of expansion parallel with blow-off outlet 61 respectively.
Blow-off outlet 61 split shed has following hole: the 1st hole 61a being positioned at central authorities, and clips the 1st hole 61a, is positioned at fore-and-aft direction, respectively facing to the 2nd and the 3rd hole 61b, 61c that the 1st hole 61a is formed in the mode tilted from unstripped gas supply source stream.The width of these blow-off outlets 61 and venting port 62 is set as narrower than the width of glass ribbon 70, and more than the product width of the glass ribbon except the edge part of Separation and Recovery.In addition, symbol 66a, 66b are cooling duct, and it makes cooling gas or wet goods heat-eliminating medium circulate, and injector 60 are remained optimum temperuture, such as 100 DEG C ~ 220 DEG C (measuring at injector lower surface).The lower surface of injector 60 is the faces contacted with unstripped gas, if temperature is too high, the unstripped gas contacted with the lower surface of injector 60 reacts under heat, adheres to, and film forming is unwanted film.Therefore, the upper limit preferably less than 250 DEG C.In addition, if temperature is too low, many with the heat exchange quantitative change of glass ribbon, the dramatic temperature that glass ribbon occurs declines.Therefore lower limit it is desirable to more than 100 DEG C.
The interval of 3mm ~ 30mm left by injector 60 mode with sky is configured in above glass ribbon 70.Therefore, the lower surface 65 of injector 60 configures across the gap of 3mm ~ 30mm in opposite directions with the glass ribbon 70 be handled upside down in annealing furnace 54.Gap is less then more favourable to thickness during film forming, film quality, film forming speed, but when due to the warpage of glass ribbon or vibration and gap there occurs change, large on the impact of thickness, film quality.In addition, when gap is large, the decline of raw material efficiency when can produce film forming.Consider thickness, film quality, film forming speed, gap is 4 ~ 12mm preferably, more preferably 5 ~ 10mm.
The gas of the main raw material containing the compound forming oxide film is blown out from the 1st hole 61a.In addition, the reactant gases (gas as oxygen source) when forming oxide film from the 2nd and the 3rd hole 61b, 61c blowout.In addition, the reacted remaining gas of venting port 62 couples of CVD is exhausted.
As long as the composition that the composition of glass ribbon finally can obtain high DEFORMATION POINTS glass substrate is not particularly limited.
In addition, in the application, " high DEFORMATION POINTS glass (substrate) " refers to the glass of deformation temperature Ts more than 550 DEG C (substrate).
The composition of glass ribbon can be such as the composition finally manufacturing borosilicate glass or non-alkali glass.
Below, an example of the composition of glass ribbon is described.
Glass ribbon (or the final glass substrate manufactured.Identical below) such as represent with the quality % of oxide compound benchmark, can contain
In fact not containing B 2o 3.
Here, SiO 2(silicon oxide) is the main component of the skeleton forming glass.SiO 2weather resistance lower than 55 quality % then glass declines, and becomes difficulty more than the fusing of 72 quality % then glass.
SiO 2content be preferably 57 ~ 72 quality %.
Al 2o 3(aluminum oxide) contains more than 5 quality % owing to being the composition of the weather resistance improving glass.But if more than 18 quality %, the fusing of glass is extremely difficult.
Al 2o 3content preferably 6 ~ 15 quality %, more preferably 7.5 ~ 14 quality %.
In addition, SiO 2and Al 2o 3resultant (SiO 2+ Al 2o 3) in order to improve the chemical durability of glass and preferred more than 64 quality %, stable in order to ensure glass melt, do not make its high temperature viscometrics too high and preferred below 82 quality %.
The oxide compound of alkaline-earth metal, namely, MgO (magnesium oxide), CaO (calcium oxide), SrO (strontium oxide) and BaO (barium oxide) improve glass weather resistance while, also for adjusting devitrification temperature, viscosity during shaping.
If MgO is more than 8 quality %, devitrification temperature rises.If CaO is more than 8 quality %, devitrification temperature rises.If SrO is more than 8 quality %, devitrification temperature rises.If BaO is more than 10 quality %, devitrification temperature rises.
In addition, the total amount (RO) of the oxide compound of alkaline-earth metal declines lower than the weather resistance of 3.5 quality % then glass, more than 27 quality % then devitrification temperature rise.
In addition, the total amount (RO) of the oxide compound of alkaline-earth metal is if be 3.5 ~ 27 quality %, then the Cl concentration step-down in film forming tin oxide film on the glass substrate, the mobility of this tin oxide film improves.Here, the generation source of the Cl in tin oxide film is when carrying out film forming by normal atmosphere CVD to tin oxide film, as the tin chloride compound (SnCl that Sn raw material uses 4, SnHCl 3, SnH 2cl 2, SnH 3these mineral-type tin chloride compounds of Cl, and monobutyl-tin-trichloride, these organic tin chloride compounds of dibutyltin dichloride).
RO, when above-mentioned scope, thinks that the reason of the Cl concentration step-down in film forming tin oxide film is on the glass substrate as follows.
Think when using normal atmosphere CVD to carry out film forming to tin oxide film on the glass substrate, when the RO of the glass forming glass substrate is the composition of above-mentioned scope, karyomorphism on glass substrate becomes site to increase, and the degree of crystallinity of the tin oxide film of institute's film forming improves.Think consequently, the Cl density loss in tin oxide film.
On the other hand, forming the RO of glass of glass substrate in above-mentioned extraneous situation, the karyomorphism on glass substrate becomes Wei Dian Minus few, and the degree of crystallinity of the tin oxide film of institute's film forming declines.Think consequently, the Cl concentration in tin oxide film increases, and the mobility of this tin oxide film declines.
Form RO preferably 5 ~ 27 quality % of the glass of glass substrate.
From the angle of the effect of the Cl density loss made above-mentioned film forming tin oxide film on the glass substrate, in the oxide compound of alkaline-earth metal, the impact that MgO and CaO produces is large.Therefore, total amount (MgO+CaO) preferably 2 ~ 16 quality % of MgO and CaO, more preferably 5 ~ 15 quality %.
Na 2o (sodium oxide) and K 2o (potassium oxide) uses as the fusing promotor of glass.But, if Na 2o more than 15 quality % then glass weather resistance decline.In addition, due to K 2o and Na 2it is high that O compares cost of material, therefore not preferably greater than 12 quality %.
In addition, in order to not make the weather resistance of glass decline, Na 2o and K 2total amount (the Na of O 2o+K 2o) preferred below 19 quality %, in order to the fusing promotor as glass is worked, Na 2o+K 2o is more than 1 quality % preferably.
ZrO 2(zirconium white) is identical with the oxide compound of alkaline-earth metal, owing to having the effect of the Cl density loss in the tin oxide film making film forming on the glass substrate, and therefore can containing the amount till 5 quality %.Think if ZrO 2content more than 5 quality %, then the karyomorphism on glass substrate becomes site to reduce, and the degree of crystallinity of the tin oxide film of institute's film forming declines.Think consequently, the Cl concentration in tin oxide film increases, and the mobility of this tin oxide film declines.
ZrO 2content more preferably 0.5 ~ 5 quality %.
TiO 2(titanium oxide), therefore can containing the amount till 5 quality % owing to having the effect of the high temperature viscometrics reducing glass.If TiO 2content more than 5 quality %, then the easy devitrification of glass.
Due to B 2o 3volatilization etc. can have problems when being shaped, therefore form the glass of glass substrate in fact not containing B 2o 3.
Form in the glass of glass substrate, Fe 2o 3(ferric oxide) can contain 0.005 ~ 0.1 quality %.
If Fe 2o 3content lower than 0.005 quality %, then because the thermal radiation transmissivity of glass uprises, during glass manufacture, to be difficult in melting channel formation temperature distribution, to be difficult to the convection current forming melten glass, to be thus difficult to the glass obtaining homogeneous.If Fe 2o 3content more than 0.1 quality %, then because the thermal radiation transmissivity of glass declines, use band transparent conductive film substrate make solar cell battery efficiency decline, thus not preferred.Fe 2o 3content more preferably 0.007 ~ 0.08 quality %.
The DEFORMATION POINTS of the glass substrate formed with the glass of above-mentioned composition is more than 550 DEG C.
As glass ribbon, by using the glass that such DEFORMATION POINTS is high, can film-forming temperature be improved when carrying out film forming to the tin oxide film as nesa coating on the glass substrate by normal atmosphere CVD, can at high temperature to carry out film forming at a high speed.
The DEFORMATION POINTS of glass substrate is preferably more than 565 DEG C.
In addition, in the present invention, DEFORMATION POINTS refers to the DEFORMATION POINTS (deformation point) measured according to " JIS R3103-2 ".
In addition, be 50 × 10 by the mean thermal expansion coefficients of glass substrate at 50 ~ 300 DEG C of the above-mentioned glass ribbon manufacture formed -7~ 105 × 10 -7/ DEG C.
The mean thermal expansion coefficients of glass substrate at 50 ~ 300 DEG C preferably 54 × 10 -7~ 100 × 10 -7/ DEG C.
In addition, the glass substrate formed with the glass of above-mentioned composition is when being set to η (dPas) by viscosity, the temperature meeting log η=2 is more than 1500 DEG C, and the temperature meeting log η=4 is 1100 ~ 1260 DEG C.Here, the temperature meeting log η=2 is the temperature of the index as melting, and the temperature meeting log η=4 is the temperature of the index of plasticity as glass.If meet the temperature of log η=4 in above-mentioned scope, be applicable to float forming.
The thickness of glass ribbon can suitably be selected, and thickness of glass is 0.1 ~ 6.0mm preferably.Owing to being difficult to cause the temperature head on surface and the back side in thin glass, the generation therefore to the warpage of injector side is few, but due to glass itself gently, glass is once to injector side warpage, and owing to conducting oneself with dignity, warpage can not be replied.In addition, heavy sheet glass easily causes the temperature head at surface and the back side, but due to deadweight, the power reducing warpage works.Therefore, even if the thickness of glass changes between 0.1 ~ 6.0mm, amount of warpage itself also can not great changes have taken place.
In addition, in the scope not damaging effect of the present invention, the film of more than 1 layer can be formed in the operation before annealing furnace in advance to the surface of glass ribbon.Such as, in float tin groove, stratum basale can be formed on the surface of glass ribbon.
The kind, formation etc. of the laminated film of institute's film forming are not particularly limited, can suitably select, but in the following description, use the example forming nesa coating used for solar batteries to be described.As the purposes beyond nesa coating used for solar batteries, such as antireflection film, hot line reflectance coating etc. can be exemplified.
Fig. 3 is the sectional view of an embodiment of the transparent conductive substrate for solar cell manufactured by the manufacture method of band laminated film glass substrate of the present invention.Illustrate in the mode making the incident light side of transparent conductive substrate for solar cell be positioned at the downside of Fig. 3.
As shown in Figure 3, transparent conductive substrate for solar cell 10 from glass substrate 12 side, has titanium oxide layer 14, silicon oxide layer 16, the 1st stannic oxide layer 18, the 2nd stannic oxide layer 20 successively as laminated film 13 on glass substrate 12.
Such as, as long as the high DEFORMATION POINTS glass of glass substrate 12, be then not particularly limited its material, can be pyrex or non-alkali glass.
The thickness preferably 0.1 ~ 6.0mm of glass substrate 12.If in above-mentioned scope, then the balance of physical strength and light transmission is excellent.
In Fig. 3, glass substrate 12 is formed with titanium oxide layer 14.In the present invention, the form between glass substrate 12 and silicon oxide layer 16 with titanium oxide layer 14 is one of suitable forms in order to suppress the reflection produced at the interface of glass substrate 12 and stannic oxide layer 18,20 due to the difference of the specific refractory power of glass substrate 12 and stannic oxide layer 18,20.
In order to be formed the laminated film 13 of this transparent conductive substrate for solar cell 10 in the annealing furnace 54 of the glass manufacturing apparatus 50 shown in Fig. 1 by CVD, such as on glass ribbon, form titanium oxide layer 14 with the 1st injector 60a, silicon oxide layer 16 is formed with the 2nd injector 60b, form the 1st stannic oxide layer 18 with the 3rd injector 60c, form the 2nd stannic oxide layer 20 with the 4th ~ 6th injector 60d ~ 60f.
In this case, in the blow-off outlet 61 of the 1st injector 60a, the tetraisopropoxy titanium after the 1st hole 61a carburation by spraying, sprays nitrogen from the 2nd and the 3rd hole 61b, 61c.By this, there is pyrolysis in tetraisopropoxy titanium on glass ribbon, and the surface of the glass ribbon of the state be handled upside down forms titanium oxide layer 14.
In the blow-off outlet 61 of the 2nd injector 60b, spray silane gas from the 1st hole 61a, spray oxygen from the 2nd and the 3rd hole 61b, 61c.By this, the raw reaction of silane gas and oxygen hybrid concurrency on the titanium oxide 14 layers of glass ribbon, the surface of the titanium oxide layer 14 of the glass ribbon of the state be handled upside down forms silicon oxide layer 16.
In the blow-off outlet 61 of the 3rd injector 60c, spray tin tetrachloride, from the 2nd and the 3rd hole 61b, 61c injection water steam from the 1st hole 61a.By this, the raw reaction of tin tetrachloride and water hybrid concurrency on the silicon oxide layer 16 of glass ribbon, the surface of the silicon oxide layer 16 of the glass ribbon of the state be handled upside down is formed the 1st stannic oxide layer 18 of the fluorine that undopes.
In the blow-off outlet 61 of the 4th ~ 6th injector 60d ~ 60f, spray tin tetrachloride from the 1st hole 61a, the hydrogen fluoride after the 2nd and the 3rd hole 61b, 61c injection water steam and gasification.By this, the raw reaction of tin tetrachloride, water and hydrogen fluoride hybrid concurrency on the 1st stannic oxide layer 18 of glass ribbon, the surface of the 1st stannic oxide layer 18 of the glass ribbon of the state be handled upside down is formed the 2nd stannic oxide layer 20 of doped with fluorine.
The glass ribbon being formed with the 2nd stannic oxide layer 20 is handled upside down while discharge from annealing furnace 54, be cooled near room temperature, is cut to desired size, becomes transparent conductive substrate for solar cell 10 and is transported.
As mentioned above preferably in annealing furnace, film forming is carried out to the operation that the oxide material that titanium oxide, silicon oxide, stannic oxide are such carries out film forming.Atmosphere in annealing furnace is air, the oxygen molecule such as easy oxygen gas-supplying when this is to manufacture oxide compound.
Here, also with reference to Fig. 4, control to be described to the temperature of glass ribbon during film forming.
The surface temperature of glass ribbon during entrance by annealing furnace 54 is set to Tin, and the surface temperature of glass ribbon during outlet by annealing furnace 54 is set to Tout.In addition, the second-order transition temperature of glass ribbon is set to Tg, glass deformation temperature is set to Ts.
In present embodiment, the surface temperature of the glass ribbon of film forming is at below Tg.If the surface temperature of glass ribbon is higher than Tg, then on glass ribbon, easily there is " marking flaw " or planar disfigurement.In addition, if the surface temperature of glass ribbon is the high-temperature scope far above Tg, then the vapor phase growth of film forming raw material increases, the increase etc. of the film defect decline of film forming speed easily occurs, causing owing to producing powder.
In addition, as long as the lower limit of the surface temperature of the glass ribbon of film forming is then not particularly limited higher than the temperature of Tout, the surface temperature of glass ribbon preferably more than 510 DEG C.If the surface temperature of glass ribbon is lower than 510 DEG C, then significantly declined by the film forming speed of the laminated film of CVD.Therefore, preferably in scope more than 510 DEG C of the surface temperature of glass ribbon, whole film forming is completed.
In addition, in present embodiment, at least two layers can be formed at the temperature of more than Ts.If at more than Ts, then can relax the deformation be imported between laminated film and glass ribbon.
Here, in present embodiment, at least 1 layer of laminated film can be carried out film forming at the temperature of below Ts.
In the glass ribbon used when manufacturing the glass of the usual composition beyond high DEFORMATION POINTS glass, deformation temperature roughly below 510 DEG C (in such as soda-lime glass, being 510 DEG C).Therefore, when carrying out film forming under the state that the temperature of glass ribbon is below deformation temperature Ts, the film forming speed of laminated film significantly declines, and is difficult to carry out film forming with the film forming speed of practicality.
On the other hand, the glass ribbon used in present embodiment is the glass ribbon of high DEFORMATION POINTS glass, has the deformation temperature Ts of more than 550 DEG C.Therefore, even if under having the state being below deformation temperature Ts in the temperature of glass ribbon, as long as the advantage that the temperature of glass ribbon can be then layer with suitable film forming speed film forming more than 510 DEG C.
As known from the above, the laminated film 13 be made up of above-mentioned titanium oxide layer 14, silicon oxide layer 16, the 1st stannic oxide layer 18 and the 2nd stannic oxide layer 20 is formed at the temperature of below Tg.Preferably layer integrated membrane 13 is formed in below Tg, the temperature range of more than 510 DEG C.
Because injector 60 maintains the temperature lower than glass ribbon, therefore in film forming and between injector 60, carry out heat exchange, the temperature of glass ribbon is declined.
Therefore, in the present invention, " the decline temperature of the per unit length of the glass ribbon in the temperature range of whole laminated film will be formed " as K1 (hreinafter referred to as decline temperature K1.) time, K1 is set as 0 DEG C/m < K1 <, 10 DEG C/m.K1 is preferably set to 1 DEG C/m≤K1≤5 DEG C/m, is more preferably set as 2 DEG C/m≤K1≤3 DEG C/m.
In addition, decline temperature K1 be form layers integrated membrane temperature range in " temperature head of the glass ribbon temperature of the glass ribbon temperature of the entrance of initial injector during form layers integrated membrane and the outlet of last injector " obtain divided by " range difference of the entry position of the initial injector of form layers integrated membrane and the outlet position of last injector ".If decline temperature K1 is at 10 DEG C/more than m, glass ribbon generation moderate finite deformation, has because injector causes the damage of glass ribbon and the anxiety of cracking with contacting of glass ribbon; If decline temperature K1 is 0 DEG C/m, when film forming because glass ribbon in annealing furnace 54 is not annealed, but anneals after film forming, cause the length of annealing furnace 54.
Can be heated the glass ribbon that the temperature by injector 60 declines by electric heater 56 grade be arranged on along the carrying direction of glass ribbon between adjacent injectors 60, relax decline temperature K1.In addition, the desuperheating amount caused due to injector 60 depends on the area of the lower surface 65 of the injector 60 relative with glass ribbon, therefore in order to reduce desuperheating amount, can reduce the area of lower surface 65 in advance.
The temperature of the glass ribbon used for calculating decline temperature K1 is the temperature of the upper surface (film forming side) of glass ribbon.The temperature head of the upper surface of the glass ribbon in film forming and the lower surface of this position is preferably within 10 DEG C.By the temperature head of the lower surface of the upper surface He this position that make glass ribbon within 10 DEG C, the warpage of the glass ribbon of the below of injector can be suppressed further, reliably suppress contacting of injector and glass ribbon further.
Here, the total length that it is desirable to annealing furnace is short as much as possible.More specifically, in the quantity of the injector that will be arranged in annealing furnace as N iNJtime, the spacing T at the center of the injector adjacent along the carrying direction of glass ribbon iNJpreferably be set to 1.0m≤T iNJ≤ 25/N iNJm.The spacing T at the center of adjacent injectors iNJif be the spacing T that more than 1.0m is due to center iNJbe shorter than the anxiety that 1.0m then has the impact being subject to adjacent injector.In above-described embodiment, because the quantity being located at the injector in annealing furnace is 6, the therefore spacing T at the center of injector iNJbe set to 1.0m≤T iNJ≤ 4.17m.In addition, the length in the carrying direction using injector is as L iNJtime, the gap between adjacent injectors, the length L of well heater can be configured in other words hfor 1.0-L iNJm≤L h≤ 4.17-L iNJm.
When film forming, the lower surface 65 of injector 60 and the gap of glass ribbon must be stablized, if but glass ribbon warpage, the lower surface 65 of injector 60 and the gap of glass ribbon change, and thickness during film forming, film quality are easily uneven.Especially when the film of film forming is thicker (such as more than 600nm), owing to producing the stress of film, the warpage of the glass ribbon after film forming easily becomes large.Therefore, especially when carrying out film forming to thicker film, preferably all layer is formed in the temperature range of Tg to Ts.
In addition, due to lower than little on the impact of the warpage of glass in the temperature range of 510 DEG C, therefore, after whole layers of film forming of laminated film 13, can cool glass ribbon with the cooling rate be greater than laminated film 13 carries out the decline temperature of the glass ribbon in the temperature range of film forming.
Embodiment
Below, embodiments of the invention are described.
In embodiment illustrated below, temperature measuring is by K type thermopair (sensor, An Li gauge Co., Ltd. (An Limeterqi society) system: 213K-TC1-ASP) measure of contact.
< embodiment 1>
In the present embodiment, when manufacturing high DEFORMATION POINTS glass, as shown in Figure 1, in annealing furnace, configure 6 injector 60a ~ 60f, between each injector, configure electric heater 56, glass ribbon forms titanium oxide layer 14 with the 1st injector 60a, silicon oxide layer 16 is formed with the 2nd injector 60b, the 1st stannic oxide layer 18 is formed with the 3rd injector 60c, the 2nd stannic oxide layer 20 is formed with the 4th ~ 6th injector 60d ~ 60f, be cut to desired size afterwards, form the nesa coating used for solar batteries 10 shown in Fig. 3.The gas sprayed from each injector 60a ~ 60f is described above.6 injectors configure at equal intervals in the mode of interval 2m between injector center.The flow P of glass ribbon is 300 tons/day, and the area S of the lower surface of injector is 0.36m 2.Especially, due to can oxygen be used when making silicon oxide, therefore formed without film quality deterioration, absorb few film.In addition, 7mm ± 1mm is set to from the gap of lower surface to glass ribbon of injector.
As glass ribbon, use and represent with the quality % of oxide compound benchmark, SiO 2be 57.6, Al 2o 3be 7.0, SiO 2+ Al 2o 3be 64.6, MgO be 2.0, CaO is 5.0, SrO is 7.0, BaO is 8.0, RO (MgO+CaO+SrO+BaO) is 22.0, MgO+CaO is 7.0, Na 2o is 4.1, K 2o is 6.3, Na 2o+K 2o is 10.4, ZrO 2it is the glass ribbon of the composition of 3.0.
The temperature of glass ribbon measures in the front and back of injector.Be 2m between measuring point.The temperature of the glass ribbon of the lower surface at injector center is obtained by calculating.Principal element due to the decline of the temperature of glass ribbon cools the radiation of injector, therefore using the temperature of the mean value of the temperature before and after injector as the glass ribbon of the lower surface at injector center.The temperature of temperature measuring position when using 6 injectors to carry out film forming to nesa coating and the glass ribbon at injector center is shown in table 1.
[table 1]
The glass ribbon temperature of the entrance of annealing furnace is set to 620 DEG C, the glass ribbon temperature of the outlet of annealing furnace is set to 250 DEG C, second-order transition temperature Tg be 625 DEG C, glass deformation temperature Ts is in the high DEFORMATION POINTS glass of 570 DEG C, configuration 3 injectors in the temperature range of the temperature range from Tg to Tg-35 DEG C, namely 625 DEG C to 590 DEG C, formation 3 layers in the temperature range of Tg to Tg-35 DEG C.In addition, in the temperature range of 590 DEG C to 550 DEG C, configure 3 injectors, in the temperature range of Tg-35 DEG C to Ts-10 DEG C, form 3 layers.
Now, by heating glass ribbon with electric heater, the decline temperature of the per unit length in the temperature range of Tg to Tg-35 DEG C is maintained 5 DEG C/m ~ 7 DEG C/m, and average out to 6 DEG C/m.Tg-35 DEG C of decline temperature to the per unit length in the temperature range of Ts is also set to 2 DEG C/m ~ 3.5 DEG C/m.The decline temperature K1 forming the per unit length of the glass ribbon in the temperature range of whole laminated film is 4.3 DEG C/m.Now, from the temperature of glass ribbon cooled the entrance Iin of each injector to outlet Iout be 4 DEG C ~ 14 DEG C.In addition, from glass deformation temperature Ts to temperature out 250 DEG C, with 14 DEG C/m ~ 18 DEG C/m and the decline temperature of the per unit length of average out to 16 DEG C/m glass ribbon is annealed.
In the film forming of the laminated film of CVD, think the cracking or warpage that there is no glass ribbon.After glass ribbon cools, be cut to desired size, obtain band transparent conductive film substrate used for solar batteries.
When measuring the warpage of the transparent conductive substrate for solar cell made like this, warpage is 0.3mm, in allowed band (1mm).In addition, there are not damage and cracking etc.In addition, the mensuration of warpage is carried out by the following method: by product size be 1100mm × 1400mm transparent conductive substrate for solar cell both ends horizontal supporting, measure from sensor to transparent conductive substrate for solar cell surface till distance while, by the distance till the back side that is contrary in transparent conductive substrate for solar cell table, that measure from sensor to transparent conductive substrate for solar cell, get rid of the bending impact caused due to deadweight.
As shown in Table 1, in each injector, from the entrance of injector to outlet, the temperature of cooled glass ribbon is below 14 DEG C.
According to table 1, obtain the temperature head of initial injector temperature in and last injector temperature out, the decline temperature K1 of the per unit length of the temperature range of whole for the formation obtained thus layer, divided by the range difference 10.5m of initial injector entry position and last injector outlet position, is shown in table 2 by this temperature gap.
[table 2]
Form the decline temperature K1 of the per unit length of the temperature range of whole layer 5.0℃/m
According to table 2, the decline temperature K1 forming the per unit length in the temperature range of whole layer is 5.0 DEG C/m.
As mentioned above, the manufacture method of glass substrate according to the present embodiment, by online CVD on the inherent high DEFORMATION POINTS glass ribbon of annealing furnace during form layers integrated membrane, at the temperature of below Tg while form layers integrated membrane, by the decline temperature of the glass ribbon in the temperature range of whole layers of form layers integrated membrane being set to 0 DEG C/m < K1 <, 10 DEG C/m, contacting of injector and glass ribbon can be avoided, suppress glass ribbon occurs for damage and cracking.
In addition, the invention is not restricted to above-mentioned embodiment, in the scope not departing from its technological thought, may be used for various embodiment.
Such as, as well heater exemplified with electric heater, but be not limited by this, any type of heating can be used.
In addition, the application advocates the right of priority of No. 2013-005029, the Japanese patent application proposed based on January 16th, 2013, and quotes the reference of full content as the application of identical application.
Nomenclature
10 transparent conductive substrate for solar cell (band laminated film glass substrate)
13 laminated films
50 glass manufacturing apparatus
51 smelting furnace
52 float tin grooves
54 annealing furnaces
56 electric heaters
60 injectors
70 glass ribbons

Claims (17)

1. the manufacture method with laminated film glass substrate, it uses the melting furnace possessing molten raw, float tin groove melten glass being floated over molten metal forms glass ribbon and the glass manufacturing apparatus to the annealing furnace that described glass ribbon is annealed, by the CVD multiple injectors be arranged in described annealing furnace form layers integrated membrane on described glass ribbon, the manufacture method of the band laminated film glass substrate that described glass ribbon is cut off;
It is characterized in that,
Described laminated film is made up of the layer of more than 2 layers,
The deformation temperature Ts(DEG C of described glass substrate) more than 550 DEG C,
The second-order transition temperature of described glass substrate is set to Tg(DEG C) time, described laminated film is formed at below Tg,
The decline temperature K1 of the per unit length of the described glass ribbon in the temperature range of whole layers forming described laminated film is 0 DEG C/m < K1 <, 10 DEG C/m.
2. manufacture method as claimed in claim 1, it is characterized in that, the linear expansivity of described glass substrate at 50 DEG C ~ 350 DEG C is 50 × 10 -7/ K ~ 105 × 10 -7/ K.
3. manufacture method as described in claim 1 or 2, it is characterized in that, the Young's modulus of described glass substrate is more than 75GPa.
4. manufacture method as claimed any one in claims 1 to 3, it is characterized in that, when viscosity being set to η (dPas), described glass substrate meets the temperature of log η=2 more than 1500 DEG C, and the temperature meeting log η=4 is 1100 ~ 1260 DEG C.
5. the manufacture method according to any one of Claims 1-4, is characterized in that,
Described glass substrate represents in the quality % of oxide compound benchmark, contains
In fact not containing B 2o 3.
6. manufacture method as claimed in claim 5, is characterized in that,
Described glass substrate represents in the quality % of oxide compound benchmark, contains
ZrO 20.5～5。
7. the manufacture method as described in claim 5 or 6, is characterized in that,
Described glass substrate represents in the quality % of oxide compound benchmark, contains
Na 2O+K 2O 1～19。
8. the manufacture method according to any one of claim 5 to 7, is characterized in that,
Described glass substrate represents in the quality % of oxide compound benchmark, contains
MgO+CaO 5～15。
9. the manufacture method according to any one of claim 5 to 8, is characterized in that,
Described glass substrate represents in the quality % of oxide compound benchmark, contains
SiO 2+Al 2O 364～82。
10. the manufacture method according to any one of claim 5 to 9, is characterized in that,
Described glass substrate represents in the quality % of oxide compound benchmark, contains
Fe 2O 30.005～0.1。
11. manufacture method according to any one of claim 1 to 10, is characterized in that, form the layer of more than at least two layers of described laminated film at the temperature more than 510 DEG C.
12. manufacture method according to any one of claim 1 to 11, is characterized in that, form at least two layers of described laminated film at the temperature of more than Ts.
13. manufacture method according to any one of claim 1 to 12, is characterized in that, at lower than the temperature of Ts, form at least one deck.
14. manufacture method according to any one of claim 1 to 13, it is characterized in that, the decline temperature of the per unit length in the temperature range from 510 DEG C to the temperature out of described annealing furnace is greater than the decline temperature of the per unit length from the described glass ribbon in the temperature range of Tg to 510 DEG C.
15. manufacture method according to any one of claim 1 to 14, it is characterized in that, the carrying direction along described glass ribbon arranges well heater between adjacent injectors.
16. manufacture method according to any one of claim 1 to 15, is characterized in that, the quantity of the described multiple injector be arranged in described annealing furnace is set to N iNJ, then along the spacing T at the center of described carrying direction adjacent injectors iNJmeet 1.0m≤T iNJ≤ 25/N iNJm.
17. manufacture method according to any one of claim 1 to 16, it is characterized in that, the distance between the lower surface of described injector and glass ribbon is below 30mm.
CN201480004902.0A 2013-01-16 2014-01-08 Method for manufacturing glass substrate with laminated film Pending CN104936923A (en)

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Application publication date: 20150923