WO2017073580A1 - Substrat en verre pour afficheurs et procédé de production de substrat en verre pour afficheurs - Google Patents

Substrat en verre pour afficheurs et procédé de production de substrat en verre pour afficheurs Download PDF

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Publication number
WO2017073580A1
WO2017073580A1 PCT/JP2016/081637 JP2016081637W WO2017073580A1 WO 2017073580 A1 WO2017073580 A1 WO 2017073580A1 JP 2016081637 W JP2016081637 W JP 2016081637W WO 2017073580 A1 WO2017073580 A1 WO 2017073580A1
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WIPO (PCT)
Prior art keywords
glass
amount
glass substrate
depth
ratio
Prior art date
Application number
PCT/JP2016/081637
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English (en)
Japanese (ja)
Inventor
信彰 井川
興平 安田
泰夫 林
Original Assignee
旭硝子株式会社
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Application filed by 旭硝子株式会社 filed Critical 旭硝子株式会社
Priority to KR1020187011393A priority Critical patent/KR102594924B1/ko
Priority to JP2017547808A priority patent/JP6866848B2/ja
Priority to CN201680063213.6A priority patent/CN108349787B/zh
Publication of WO2017073580A1 publication Critical patent/WO2017073580A1/fr

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    • 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
    • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
    • C03C3/093—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium containing zinc or zirconium
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B18/00—Shaping glass in contact with the surface of a liquid
    • C03B18/02—Forming sheets
    • C03B18/14—Changing the surface of the glass ribbon, e.g. roughening
    • 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
    • C03C15/00—Surface treatment of glass, not in the form of fibres or filaments, by etching
    • 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
    • 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
    • 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
    • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P40/00—Technologies relating to the processing of minerals
    • Y02P40/50—Glass production, e.g. reusing waste heat during processing or shaping
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P40/00—Technologies relating to the processing of minerals
    • Y02P40/50—Glass production, e.g. reusing waste heat during processing or shaping
    • Y02P40/57—Improving the yield, e-g- reduction of reject rates

Definitions

  • the present invention relates to a glass substrate for display and a method for producing a glass substrate for display.
  • a substrate in which a transparent electrode, a semiconductor element, etc. are formed on a glass substrate is used.
  • a substrate in which a transparent electrode, a semiconductor element, etc. are formed on a glass substrate is used.
  • a substrate in which a transparent electrode, a TFT (Thin Film Transistor) and the like are formed on a glass substrate is used.
  • Formation of a transparent electrode, a semiconductor element, etc. on a glass substrate is performed in a state where the glass substrate is fixed on a suction stage by vacuum suction. However, when the glass substrate on which the transparent electrode, the semiconductor element and the like are formed is peeled from the adsorption stage, the glass substrate is charged, and electrostatic destruction of the semiconductor element such as a TFT occurs.
  • the surface of the glass substrate on the side in contact with the adsorption stage is roughened to reduce the contact area between the glass substrate and the adsorption stage.
  • a roughening treatment method for example, a method of chemically treating the surface of a glass substrate by an atmospheric pressure plasma process is known (Patent Document 1).
  • the conventional method does not consider the work function difference between the glass substrate and the adsorption stage, the occurrence of peeling electrification cannot be sufficiently suppressed, and the electrostatic breakdown of the semiconductor element may occur.
  • the present invention has been made in view of the above-described problems, and provides a glass substrate for display that hardly causes peeling charging when peeling from an adsorption stage, and a manufacturing method thereof.
  • the present invention includes SiO 2 and Al 2 O 3 and has a depth of 0 from the glass surface with respect to the Si amount (atomic%) at a depth of 40 ⁇ m from the glass surface opposite to the semiconductor element forming surface of the glass substrate.
  • the ratio of Si amount which is the ratio of the average value of Si amount (atomic%) at ⁇ 30 nm, is 0.9 or less, and from the glass surface to the Al amount (atomic%) at a depth of 40 ⁇ m from the glass surface.
  • a glass substrate for display wherein a ratio of Al amount, which is a ratio of average values of Al amount (atomic%) at a depth of 0 to 30 nm, is 1.0 to 7.4.
  • the present invention is formed by a melting apparatus that melts a glass raw material to form molten glass, a molding apparatus that forms the molten glass supplied from the melting apparatus into a strip shape to form a glass ribbon, and the molding apparatus.
  • a method for producing a glass substrate for display comprising SiO 2 and Al 2 O 3 using a float glass production apparatus comprising a slow cooling apparatus for gradually cooling the glass ribbon, the glass ribbon being installed above the glass ribbon
  • a gas containing 3.0 vol% or more of hydrogen fluoride (HF) to the top surface of the glass ribbon, the glass substrate is separated from the surface of the glass substrate opposite to the semiconductor element formation surface.
  • Si which is the ratio of the average value of the Si amount (atomic%) at a depth of 0 to 30 nm from the glass surface to the Si amount (atomic%) at a depth of 40 ⁇ m
  • the ratio of the average value of the Al amount (atomic%) at a depth of 0 to 30 nm from the glass surface to the Al amount (atomic%) at a depth of 40 ⁇ m from the glass surface is controlled to 0.9 or less.
  • a method for producing a glass substrate for display wherein the ratio of the amount of Al is controlled to 1.0 to 7.4.
  • the glass substrate for display of the present invention when the glass substrate is peeled from the adsorption stage on the glass surface, it is possible to suppress the occurrence of peeling electrification.
  • Glass substrate for display Hereinafter, the glass substrate for display which concerns on embodiment of this invention is demonstrated.
  • the aluminosilicate glass is used for the display glass substrate of the present embodiment.
  • the aluminosilicate glass may be a glass containing a boron component or a glass containing an alkaline earth metal component.
  • the work function is the minimum amount of energy required to take electrons in a solid out of the solid, precisely into a vacuum. Charges are generated by electrons moving from a material having a low work function to a material having a high work function.
  • the glass substrate is charged due to a work function difference from the adsorption stage.
  • the inventors of the present application paid attention to the work function of the glass substrate in order to reduce the charge amount of the glass substrate.
  • a method for measuring the work function of the glass substrate has not been established.
  • the work function of the atoms constituting the glass substrate has a correlation with the Pauling electronegativity for each atom, so the charging of the glass substrate is based on the electronegativity of the atoms constituting the glass substrate. I decided to consider it.
  • the electronegativity of the atoms constituting the glass substrate is as follows: Si 1.90, Al 1.61, B 2.04, Mg 1.31, Ca 1.00, Sr 0.95, Ba 0.89.
  • a glass substrate containing many atoms having a high electronegativity has a high work function.
  • the Si amount and B amount of the glass substrate are reduced, and the Al amount, Mg amount, Ca amount, Sr amount, and Ba amount are increased, the work function of the glass substrate is reduced, and the work function of the glass substrate and the adsorption stage is reduced. Since the difference is reduced, the charge amount of the glass substrate is reduced.
  • the glass substrate for display of this embodiment contains SiO 2 and Al 2 O 3 , and the glass surface with respect to the Si amount (atomic%) at a depth of 40 ⁇ m from the glass surface opposite to the semiconductor element forming surface of the glass substrate.
  • the ratio of the amount of Si which is the ratio of the average value of the amount of Si (atomic%) at a depth of 0 to 30 nm from the glass, is 0.9 or less, and the glass with respect to the amount of Al (atomic%) at a depth of 40 ⁇ m from the glass surface
  • the ratio of the Al amount that is the ratio of the average value of the Al amount (atomic%) at a depth of 0 to 30 nm from the surface is 1.0 to 7.4.
  • the display glass substrate of this embodiment contains B 2 O 3 , and the B amount (atomic%) at a depth of 0 to 30 nm from the glass surface with respect to the B amount (atomic%) at a depth of 40 ⁇ m from the glass surface. It is preferable that the ratio of the B amount, which is the ratio of the average values of ()), is 0.7 or less.
  • the display glass substrate of this embodiment contains MgO, and the average amount of Mg (atomic%) at a depth of 0 to 30 nm from the glass surface with respect to the Mg quantity (atomic%) at a depth of 40 ⁇ m from the glass surface.
  • the ratio of the amount of Mg which is the ratio of the values, is preferably 1.0 to 7.4.
  • the display glass substrate of this embodiment contains CaO, and the average of the Ca content (atomic%) at a depth of 0 to 30 nm from the glass surface with respect to the Ca content (atomic%) at a depth of 40 ⁇ m from the glass surface.
  • the ratio of Ca which is the ratio of the values, is preferably 1.0 to 7.4.
  • the glass substrate for display of this embodiment contains the alkaline-earth metal oxide,
  • the said glass surface with respect to the total amount (atomic%) of Mg, Ca, Sr, and Ba in the depth of 40 micrometers from the said glass surface.
  • the ratio of the total amount which is the ratio of the average value of the total amount (atomic%) of Mg, Ca, Sr, and Ba at a depth of 0 to 30 nm from 1.0 to 7.4.
  • the movement of electrons in contact charging mainly occurs in a region having a depth of 0 to 30 nm from the glass surface, so the amount of atoms in the region affects the work function of the glass substrate.
  • the amount of atoms at a depth of 0 to 30 nm from the glass surface substantially represents the amount of atoms in the surface layer of the glass substrate.
  • the amount of atoms at a depth of 40 ⁇ m from the glass surface substantially represents the amount of atoms in the glass substrate.
  • the glass surface is processed with hydrogen fluoride (HF) gas in the glass forming step or the slow cooling step, Si and B on the glass surface are SiF 4 , respectively. It becomes BF 3 and evaporates from the glass surface. Therefore, the Si amount and B amount (atomic%) of the glass substrate surface layer are less than the Si amount and B amount (atomic%) inside the glass substrate, and the Al amount, Mg amount, Ca amount, Sr amount of the glass substrate surface layer, The Ba content (atomic%) is larger than the Al content, Mg content, Ca content, Sr content, and Ba content (atomic%) inside the glass substrate.
  • HF hydrogen fluoride
  • the number of atoms having a large electronegativity decreases and the number of atoms having a low electronegativity increases, so that the work function of the glass substrate decreases. Therefore, by using the glass substrate of the present embodiment, the difference in work function between the glass substrate and the suction stage is reduced, so that peeling charging of the glass substrate can be suppressed.
  • the ratio of Si amount is preferably 0.8 or less.
  • the ratio of Al amount is preferably 1.2 or more.
  • the ratio of Al amount is more preferably 3.0 or less.
  • the ratio of the B amount is more preferably 0.3 or less.
  • the ratio of Mg amount is more preferably 1.2 or more.
  • the ratio of the amount of Mg is more preferably 3.0 or less.
  • the ratio of Ca amount is more preferably 1.2 or more. Moreover, the ratio of the Ca amount is more preferably 2.0 or less.
  • the ratio of the total amount of Mg, Ca, Sr and Ba is more preferably 3.0 or less.
  • the upper limit of the Al amount ratio, the Mg amount ratio, the Ca amount ratio, and the total amount ratio is a value calculated when the Si amount and B amount of the glass substrate surface layer are assumed to be zero.
  • the glass substrate for display of the present embodiment may be a glass containing an alkali metal component in an aluminosilicate glass, or may be an alkali-free glass substantially not containing an alkali metal component.
  • substantially not containing an alkali metal component means that the total content of alkali metal oxides is 0.1% by mass or less.
  • the alkali-free glass is, for example, SiO 2 : 50 to 73% (preferably 50 to 66%), Al 2 O 3 : 10.5 to 24%, B 2 O 3 : 0 in terms of mass% based on oxide. ⁇ 12%, MgO: 0 ⁇ 8%, CaO: 0 ⁇ 14.5%, SrO: 0 ⁇ 24%, BaO: 0 ⁇ 13.5%, ZrO 2: 0 contains ⁇ 5%, MgO + CaO + SrO + BaO: 8 To 29.5% (preferably 9 to 29.5%).
  • the alkali-free glass has both a high strain point and high solubility, it is preferably expressed in terms of mass% on the basis of oxide, SiO 2 : 58 to 66%, Al 2 O 3 : 15 to 22%, B 2 O 3 : 5 to 12%, MgO: 0 to 8%, CaO: 0 to 9%, SrO: 3 to 12.5%, BaO: 0 to 2%, MgO + CaO + SrO + BaO: 9 to 18%.
  • the alkali-free glass is preferably expressed in terms of mass% based on oxide, SiO 2 : 54 to 73%, Al 2 O 3 : 10.5 to 22.5%, B 2 O 3 : 0 to 5.5%, MgO: 0 to 8%, CaO: 0 to 9%, SrO: 0 to 16%, BaO: 0 to 2.5%, MgO + CaO + SrO + BaO: 8 to 26%.
  • the glass substrate for display of the present embodiment preferably has an average surface roughness Ra of the glass surface of 0.2 to 1.0 nm.
  • the glass substrate for display of the present embodiment preferably has an average surface roughness Ra of the semiconductor element formation surface of 0.15 to 0.25 nm.
  • FIG. 1 is an explanatory view of a method for manufacturing a glass substrate for display according to an embodiment of the present invention, and is a cross-sectional view schematically showing a float glass manufacturing apparatus.
  • FIG. 2 is an explanatory view of a method for manufacturing a glass substrate for display according to another embodiment of the present invention, and is a cross-sectional view schematically showing a float glass manufacturing apparatus.
  • the float glass manufacturing apparatus 100 includes a melting apparatus 200 that melts the glass raw material 10 to form a molten glass 12, a molding apparatus 300 that forms the molten glass 12 supplied from the melting apparatus 200 into a strip shape, and forms a glass ribbon 14. And a slow cooling device 400 that slowly cools the glass ribbon 14 formed by the device 300.
  • the melting apparatus 200 includes a melting tank 210 that stores the molten glass 12 and a burner 220 that forms a flame above the molten glass 12 stored in the melting tank 210.
  • the glass raw material 10 thrown into the melting tank 210 is gradually melted into the molten glass 12 by the radiant heat from the flame formed by the burner 220.
  • the molten glass 12 is continuously supplied from the melting tank 210 to the molding apparatus 300.
  • the molding apparatus 300 includes a bathtub 320 that stores molten tin 310.
  • the forming apparatus 300 forms the glass ribbon 14 by forming the molten glass 12 continuously supplied onto the molten tin 310 into a strip shape by causing the molten glass 12 to flow in a predetermined direction on the molten tin 310.
  • the atmosphere temperature in the molding apparatus 300 becomes lower as it goes from the inlet to the outlet of the molding apparatus 300.
  • the atmospheric temperature in the molding apparatus 300 is adjusted by a heater (not shown) provided in the molding apparatus 300.
  • the glass ribbon 14 is cooled while flowing in a predetermined direction, and is pulled up from the molten tin 310 in the downstream area of the bathtub 320.
  • the glass ribbon 14 pulled up from the molten tin 310 is conveyed to the slow cooling device 400 by the lift-out roll 510.
  • the slow cooling device 400 gradually cools the glass ribbon 14 formed by the forming device 300.
  • the slow cooling device 400 includes, for example, a slow cooling furnace (rare) 410 having a heat insulating structure and a plurality of transport rolls 420 disposed in the slow cooling furnace 410 and transporting the glass ribbon 14 in a predetermined direction.
  • the atmospheric temperature in the slow cooling furnace 410 becomes lower as it goes from the inlet to the outlet of the slow cooling furnace 410.
  • the atmospheric temperature in the slow cooling furnace 410 is adjusted by a heater 440 or the like provided in the slow cooling furnace 410.
  • the glass ribbon 14 carried out from the outlet of the slow cooling furnace 410 is cut into a predetermined size by a cutting machine and shipped as a product.
  • both surfaces of the glass substrate may be polished to clean the glass substrate. Even if the surface of the glass substrate is polished once, if the quality requirement such as flatness is not satisfied, the surface of the glass substrate may be polished again.
  • the glass surface opposite to the semiconductor element formation surface of the glass substrate corresponds to the top surface of the glass ribbon 14, and the semiconductor element formation surface corresponds to the bottom surface of the glass ribbon 14. In the present embodiment, it is preferable to polish only the bottom surface of the glass ribbon 14 so that the effect of suppressing the charging of the glass substrate can be obtained by changing the composition of the glass surface layer.
  • the semiconductor element forming surface of the glass substrate is polished by a polishing tool while supplying a cerium oxide aqueous solution. At the time of polishing, a part of the aqueous cerium oxide solution wraps around the glass surface opposite to the semiconductor element formation surface of the glass substrate and becomes a slurry residue.
  • the glass substrate is cleaned by, for example, shower cleaning, slurry cleaning using a disk brush, or shower rinsing.
  • Slurry cleaning is performed by polishing with a disk brush while supplying slurry (for example, cerium oxide aqueous solution or calcium carbonate aqueous solution) to the glass surface opposite to the semiconductor element forming surface of the glass substrate.
  • slurry for example, cerium oxide aqueous solution or calcium carbonate aqueous solution
  • the top surface of the glass ribbon 14 is used by using injectors 70 and 80 installed above the glass ribbon 14 in the molding apparatus 300.
  • the top surface of the glass ribbon 14 is etched to roughen the surface of the glass ribbon.
  • the injectors 70, 80 installed above the glass ribbon 14 in the slow cooling device 400 are used, and the glass ribbon 14 By supplying a gas containing hydrogen fluoride (HF) to the top surface of the glass ribbon, the top surface of the glass ribbon 14 is etched to roughen the glass ribbon surface.
  • HF hydrogen fluoride
  • the manufacturing method of the glass substrate for display of this invention is not limited to the said embodiment etc., Using the injectors 70 and 80 installed above the glass ribbon 14 in the shaping
  • FIG. 3 is a diagram schematically showing a double-flow type injector 70 according to the embodiment of the present invention.
  • FIG. 4 is a diagram schematically showing a single-flow injector 80 according to the embodiment of the present invention.
  • the gas blown from the supply ports 71 and 81 of the injectors 70 and 80 to the top surface of the glass ribbon 14 moves through the flow paths 74 and 84 in the forward direction or the reverse direction with respect to the moving direction of the glass ribbon 14, and the exhaust port. It flows out to 75,85.
  • the injectors 70 and 80 may be used in any form, and two or more injectors may be arranged in series in the moving direction of the glass ribbon 14 to treat the glass ribbon surface. Although not shown, the injectors 70 and 80 have a water cooling structure in order to be installed in the molding apparatus 300 or the slow cooling apparatus 400.
  • the double-flow injector 70 is an injector in which the gas flow from the supply port 71 to the exhaust port 75 is equally divided in the forward direction and the reverse direction with respect to the moving direction of the glass ribbon 14.
  • the single-flow injector 80 is an injector in which the gas flow from the supply port 81 to the exhaust port 85 is fixed in either the forward direction or the reverse direction with respect to the moving direction of the glass ribbon 14. In the embodiment of FIG. 4, the gas flow from the supply port 81 to the exhaust port 85 is forward with respect to the moving direction of the glass ribbon 14.
  • the distance D between the supply ports 71 and 81 of the injectors 70 and 80 and the top surface of the glass ribbon 14 is preferably 5 to 50 mm.
  • the distance D is more preferably 8 mm or more.
  • the distance D is more preferably 30 mm or less, and still more preferably 20 mm or less.
  • the distance L in the moving direction of the glass ribbon 14 of the injectors 70 and 80 is preferably 100 to 500 mm.
  • the distance L is more preferably 150 mm or more, and further preferably 200 mm or more.
  • the distance L is more preferably 450 mm or less, and still more preferably 400 mm or less.
  • the distance L of the injector 70 is preferably 150 mm or more
  • the distance L of the injector 80 is preferably 100 mm or more.
  • the amount of heat removal of the glass ribbon 14 by the injectors 70 and 80 installed in the molding apparatus 300 or the slow cooling apparatus 400 can be suppressed by setting the distance L to 500 mm or less, the output of a plurality of heaters can be suppressed.
  • the distance in the width direction of the glass ribbon 14 of the injectors 70 and 80 is preferably equal to or greater than the product area of the glass ribbon 14 in that direction. Preferably it is 3000 mm or more, More preferably, it is 4000 mm or more.
  • the supply ports 71 and 81 for supplying a gas containing hydrogen fluoride (HF) and the exhaust ports 75 and 85 face the top surface of the glass ribbon 14.
  • the supply ports 71 and 81 and the exhaust ports 75 and 85 have a slit shape over the entire width direction of the glass ribbon 14 of the injectors 70 and 80.
  • the temperature of the glass ribbon 14 when supplying a gas containing hydrogen fluoride (HF) to the top surface of the glass ribbon 14 being conveyed is preferably 700 to 1100 ° C. in the molding apparatus 300. Yes, more preferably 800 to 1000 ° C.
  • the temperature of the glass ribbon 14 is 700 ° C. or higher, the etching of the glass ribbon surface proceeds rapidly.
  • the amount of heat removal of the glass ribbon 14 by the injectors 70 and 80 installed in the molding apparatus 300 can be suppressed when the temperature of the glass ribbon 14 is 1100 ° C. or less, the output of a plurality of heaters can be suppressed.
  • the temperature of the glass ribbon 14 is preferably 300 to 700 ° C. in the slow cooling device 400.
  • the temperature of the glass ribbon 14 is 300 ° C. or higher, the effect of the etching of the glass ribbon surface can be maintained.
  • the amount of heat removal of the glass ribbon 14 by the injectors 70 and 80 installed in the slow cooling device 400 can be suppressed when the temperature of the glass ribbon 14 is 700 ° C. or less, the output of a plurality of heaters can be suppressed.
  • the hydrogen fluoride (HF) concentration c of the gas containing hydrogen fluoride (HF) is preferably 3.0 to 30 vol%.
  • the hydrogen fluoride (HF) concentration c is more preferably 4.0 vol% or more. Further, the hydrogen fluoride (HF) concentration c is more preferably 26 vol% or less, and further preferably 22 vol% or less.
  • the flow velocity (linear velocity) u of the gas containing hydrogen fluoride (HF) is preferably 20 to 300 cm / s.
  • the flow velocity (linear velocity) u is more preferably 50 cm / s or more, and still more preferably 80 cm / s or more.
  • the flow velocity (linear velocity) u is more preferably 250 cm / s or less, and further preferably 200 cm / s or less.
  • the flow rate (linear velocity) u of the gas containing hydrogen fluoride (HF) within the above preferred range, the ratio of Si amount, Al ratio, B amount, Mg amount, Ca amount
  • the ratio and the ratio of the total amount of Mg, Ca, Sr and Ba can be controlled.
  • hydrogen chloride (HCl) gas may be added to the gas containing hydrogen fluoride (HF).
  • HCl hydrogen chloride
  • HF hydrogen fluoride
  • Hydrogen chloride (HCl) gas removes metallic tin by the following reaction mechanism. Sn + 2HCl ⁇ SnCl 2 + H 2 SnCl 2 produced by the reaction is volatilized from the glass ribbon surface.
  • the gas containing hydrogen fluoride (HF) is a carrier of inert gas such as nitrogen (N 2 ) or rare gas from the viewpoint of preventing corrosion of equipment such as an injector that supplies the gas to the glass ribbon surface. It is preferable to use it as a gas and supply it to the glass ribbon surface as a mixed gas with these carrier gases.
  • FIG. 5 is a diagram showing the relationship between the hydrogen fluoride (HF) concentration of the gas supplied by the injector and the characteristics of the glass surface layer of the obtained glass substrate. As shown in FIG. 5, Examples 4 and 5 are examples, and Examples 1 to 3 are comparative examples.
  • HF hydrogen fluoride
  • Example 1 The composition of the obtained glass substrate is expressed in terms of mass percentage based on oxide, SiO 2 : 59.5%, Al 2 O 3 : 17%, B 2 O 3 : 8%, MgO: 3.3%, CaO: 4%, SrO: 7.6%, BaO: 0.1%, ZrO 2 : 0.1%, MgO + CaO + SrO + BaO: 15%, the balance being inevitable impurities, containing alkali metal oxide
  • the glass raw material 10 was adjusted so that the total amount was 0.1% or less, and the glass raw material 10 was put into the melting apparatus 200.
  • the molten glass 12 was supplied to the molding apparatus 300, and the molten glass 12 was formed into a strip shape to obtain a glass ribbon 14.
  • An injector 70 having a distance L in the moving direction of the glass ribbon 14 of 300 mm was installed at a position where the temperature of the glass ribbon 14 in the molding apparatus 300 was 900 ° C.
  • the distance D between the supply port 71 of the injector 70 and the top surface of the glass ribbon 14 was set to 10 mm.
  • Nitrogen (N 2 ) gas was sprayed from the supply port 71 of the injector 70 onto the top surface of the glass ribbon 14 at a flow velocity (linear velocity) u of 100 cm / s. After pulling out the glass ribbon 14 from the outlet of the molding apparatus 300, the glass ribbon 14 was gradually cooled in the slow cooling apparatus 400 and cut to obtain a glass substrate having a width of 410 mm ⁇ a length of 510 mm.
  • Example 2 Except that nitrogen (N 2 ) having a hydrogen fluoride (HF) concentration c of 1.0 vol% was blown onto the top surface of the glass ribbon 14 instead of the nitrogen (N 2 ) gas of Example 1 A glass substrate was obtained under the same conditions as in Example 1.
  • nitrogen (N 2 ) having a hydrogen fluoride (HF) concentration c of 1.0 vol% was blown onto the top surface of the glass ribbon 14 instead of the nitrogen (N 2 ) gas of Example 1
  • a glass substrate was obtained under the same conditions as in Example 1.
  • Example 3 Instead of Example 1 of nitrogen (N 2) gas, except that hydrogen fluoride (HF) concentration c was blown gas was 2.0 vol% of nitrogen (N 2) carrier gas in the top surface of the glass ribbon 14 A glass substrate was obtained under the same conditions as in Example 1.
  • HF hydrogen fluoride
  • Example 4 Except that nitrogen (N 2 ) having a hydrogen fluoride (HF) concentration c of 5.0 vol% was blown onto the top surface of the glass ribbon 14 instead of the nitrogen (N 2 ) gas of Example 1 A glass substrate was obtained under the same conditions as in Example 1.
  • nitrogen (N 2 ) having a hydrogen fluoride (HF) concentration c of 5.0 vol% was blown onto the top surface of the glass ribbon 14 instead of the nitrogen (N 2 ) gas of Example 1
  • a glass substrate was obtained under the same conditions as in Example 1.
  • Example 5 After polishing the semiconductor element formation surface of the glass substrate obtained in Example 4, the glass substrate was cleaned by shower cleaning, slurry cleaning, and shower rinsing.
  • the measured values of the amount of each atom at the depth of 0, 4, 8, 12, 16, 20, 24, and 28 nm were averaged, and the average value of the amount of each atom at the depth of 0 to 30 nm was calculated.
  • Grinding to a depth 28nm from the glass substrate surface was sputter etched by C 60 ion beam. Grinding from the surface of the glass substrate to a depth of 40 ⁇ m was performed with a cerium oxide aqueous solution to a depth of 39 ⁇ m, and then sputter-etched with a C 60 ion beam.
  • the work function W k (eV) of each atom k constituting the glass substrate can be calculated using the following formula based on the electronegativity X k of each atom k.
  • W k 2.27 ⁇ X k +0.34 Therefore, a pseudo work function was calculated as an alternative index of the work function of the glass substrate surface layer.
  • the pseudo work function (eV) is the average value of the amount of each atom k (Si amount, B amount, O amount, Al amount, Mg amount, Ca amount, and Sr amount (atomic%)) at a depth of 0 to 30 nm. based on the electronegativity X k of each atom k, was calculated using the following equation.
  • Pseudo work function 2.27 ⁇ ⁇ ⁇ (amount of atom k ⁇ X k ) / (amount of atom k) ⁇ + 0.34
  • each of the glass substrates obtained in Examples 1 to 5 was cut into a width of 5 mm and a length of 5 mm, and the average surface roughness Ra (arithmetic average surface roughness Ra (JIS B0601-2013)) of the glass surface of the glass substrate was It measured by the method of.
  • the glass surface of the glass substrate was observed using an atomic force microscope (product name: SPI-3800N, manufactured by Seiko Instruments Inc.).
  • SI-DF40P2 was used as the cantilever. Observation was performed on a scan area of 5 ⁇ m ⁇ 5 ⁇ m using a dynamic force mode at a scan rate of 1 Hz (number of data in area: 256 ⁇ 256). Based on this observation, the average surface roughness Ra at each measurement point was calculated.
  • the software (software name: SPA-400) attached to the atomic force microscope was used.
  • the peel charge amount of each glass substrate obtained in Examples 1 to 5 was measured by the following method. A glass substrate having a width of 410 mm and a length of 510 mm was placed on a vacuum suction stage made of SUS310 for a certain time, and then the glass substrate was peeled off from the vacuum suction stage using lift pins. The charge amount of the glass substrate immediately after peeling was measured with a surface potentiometer (product name: MODEL 341B, manufactured by Trek Japan). The charge amounts of Examples 1 to 5 shown in FIG. 5 are relative values when the charge amount of Example 1 is 1.
  • FIG. 6 is a diagram showing the relationship between the pseudo work function of the glass substrate surface layer and the charge amount (relative value). As shown in FIG. 6, when the hydrogen fluoride (HF) concentration c is 5.0 vol%, the pseudo work function becomes small and the charge amount becomes low.
  • HF hydrogen fluoride
  • Example 4 Comparing Example 4 and Example 5, the average surface roughness Ra of the glass surface of Example 4 is 0.28 nm, and the average surface roughness Ra of the glass surface of Example 5 is 0.71 nm.
  • the charge amount of Example 4 is 0.55, and the charge amount of Example 5 is 0.51. Even if the surface of the glass is roughened by slurry cleaning, the amount of charge on the glass substrate was about the same, so it is better to reduce the pseudo work function of the glass surface layer than to roughen the surface of the glass. It turns out that there is an effect.

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Abstract

La présente invention concerne un substrat en verre pour afficheurs qui contient du SiO2 et de l'Al2O3. Le rapport des quantités de Si, qui est le rapport de la valeur moyenne de quantités de Si (en % atomique) dans une partie d'une surface de verre du substrat en verre, ladite surface de verre étant sur le côté inverse de la surface de formation d'élément semi-conducteurs, à la profondeur de 0 à 30 nm, rapportée à la quantité de Si (en % atomique) à la profondeur de 40 µm de la surface de verre, est inférieur ou égal à 0,9 ; et le rapport des quantités d'Al, qui est le rapport de la valeur moyenne de quantités d'Al (en % atomique) dans une partie de la surface de verre à une profondeur allant de 0 à 30 nm, rapportée à la quantité d'Al (en % atomique) à la profondeur de 40 µm de la surface de verre, va de 1,0 à 7,4.
PCT/JP2016/081637 2015-10-29 2016-10-25 Substrat en verre pour afficheurs et procédé de production de substrat en verre pour afficheurs WO2017073580A1 (fr)

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JP2017547808A JP6866848B2 (ja) 2015-10-29 2016-10-25 ディスプレイ用ガラス基板、及びディスプレイ用ガラス基板の製造方法
CN201680063213.6A CN108349787B (zh) 2015-10-29 2016-10-25 显示器用玻璃基板、以及显示器用玻璃基板的制造方法

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CN110395903A (zh) * 2018-04-25 2019-11-01 Ａｇｃ株式会社 玻璃基板
KR20190124151A (ko) * 2018-04-25 2019-11-04 에이지씨 가부시키가이샤 유리 기판
JP2020040864A (ja) * 2018-09-13 2020-03-19 日本電気硝子株式会社 ガラス板の製造方法
JP2021155320A (ja) * 2020-03-27 2021-10-07 Ａｇｃ株式会社 ガラス板及びその製造方法

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JP7024373B2 (ja) 2017-12-18 2022-02-24 Ａｇｃ株式会社 ディスプレイ用ガラス基板
CN110395903A (zh) * 2018-04-25 2019-11-01 Ａｇｃ株式会社 玻璃基板
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TW201728544A (zh) 2017-08-16
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