WO2022130831A1 - Procédé servant à produire un substrat de verre exempt d'alcali - Google Patents

Procédé servant à produire un substrat de verre exempt d'alcali Download PDF

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WO2022130831A1
WO2022130831A1 PCT/JP2021/041181 JP2021041181W WO2022130831A1 WO 2022130831 A1 WO2022130831 A1 WO 2022130831A1 JP 2021041181 W JP2021041181 W JP 2021041181W WO 2022130831 A1 WO2022130831 A1 WO 2022130831A1
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glass
glass substrate
alkali
raw material
producing
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PCT/JP2021/041181
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English (en)
Japanese (ja)
Inventor
陸朗 愛
達 櫻林
晃朗 福西
康志 紀井
洋大 増田
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日本電気硝子株式会社
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Priority to KR1020237019314A priority Critical patent/KR20230122005A/ko
Priority to CN202180084882.2A priority patent/CN116648438A/zh
Publication of WO2022130831A1 publication Critical patent/WO2022130831A1/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
    • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B1/00—Preparing the batches
    • C03B1/02—Compacting the glass batches, e.g. pelletising
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B17/00—Forming molten glass by flowing-out, pushing-out, extruding or drawing downwardly or laterally from forming slits or by overflowing over lips
    • C03B17/06—Forming glass sheets
    • C03B17/064—Forming glass sheets by the overflow downdraw fusion process; Isopipes therefor
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B3/00—Charging the melting furnaces
    • C03B3/02—Charging the melting furnaces combined with preheating, premelting or pretreating the glass-making ingredients, pellets or cullet
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
    • C03B5/02—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture in electric furnaces, e.g. by dielectric heating
    • C03B5/027—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture in electric furnaces, e.g. by dielectric heating by passing an electric current between electrodes immersed in the glass bath, i.e. by direct resistance heating
    • 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
    • C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
    • 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
    • C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
    • C03C1/02—Pretreated ingredients
    • C03C1/024—Chemical treatment of cullet or glass fibres
    • 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
    • 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 method for manufacturing a non-alkali glass substrate, and more specifically, is a non-alkali glass substrate suitable for a display provided with a thin film transistor (TFT: Thin Film Transistor) having an oxide film such as Indium Gallium Zinc Oxide (IGZO). Regarding the manufacturing method of.
  • TFT Thin Film Transistor
  • IGZO Indium Gallium Zinc Oxide
  • a glass substrate is generally used as a support substrate in a flat panel display.
  • An electric circuit pattern such as a TFT is formed on the surface of this glass substrate.
  • a non-alkali glass substrate that does not substantially contain an alkali metal component is adopted for this type of glass substrate so as not to adversely affect the TFT or the like.
  • the down draw method is a method in which molten glass is stretched downward to form a plate.
  • the overflow downdraw method which is a kind of downdraw method, is a method of forming a glass ribbon by stretching the molten glass overflowing from both sides of a substantially wedge-shaped cross-section (forming body) downward.
  • the molten glass overflowing from both sides of the molded body flows down along both side surfaces of the molded body and joins below the molded body. Therefore, in the overflow downdraw method, the surface of the glass ribbon does not come into contact with anything other than air and is formed by surface tension. Therefore, even if the surface is not polished after molding, foreign matter does not adhere to the surface and the surface is flat. Glass substrate can be obtained. Further, according to the overflow downdraw method, there is an advantage that a thin glass substrate can be easily formed.
  • examples of the method for melting the non-alkali glass substrate include electric melting described in Patent Document 1.
  • Patent Document 1 has a problem that lumps are easily generated.
  • the present invention has been made in view of such circumstances, and an object of the present invention is to provide a method for manufacturing a non-alkali glass substrate having a small number of lumps.
  • the method for producing non-alkali glass of the present invention is a method for continuously producing a SiO 2 -Al 2O 3 -RO (RO is one or more of MgO, CaO, BaO, SrO and ZnO) -based non-alkali glass substrate. Therefore, the step of preparing a raw material batch so as to contain a tin compound and substantially no arsenic compound and an antimony compound, and the prepared raw material batch are electrically melted in a melting kiln capable of energizing and heating with an electrode.
  • the ⁇ -OH value of the obtained glass is 0.05 / mm or more, and the number of metal lumps is 20 pieces / ton or less. It is characterized by being.
  • the "metal lump” is observed with a stereoscopic microscope, and when a metal lump of 1 ⁇ m or more is observed in the observation field, it is counted as a metal lump, and the metal lump per ton is counted from the size of the glass used for the measurement. The number of is calculated.
  • Equation 1 (x and y are coefficients, M indicates Fe, Cr and / or Ni), in the raw material batch. It was found that SnO 2 in the glass was reduced by Fe, Cr, Ni and the like contained in the glass, and metal lumps containing Sn were deposited in the glass. Further, by increasing the ⁇ -OH value of the glass, Fe, Cr, Ni and the like are contained in the glass as shown in Equation 2 (z is a coefficient and M indicates Fe, Cr and / or Ni). It has also been found that since it binds to an OH group, it becomes difficult to reduce SnO 2 and it becomes difficult for metal lumps to precipitate in the glass.
  • non-alkali glass is a glass to which an alkali metal oxide component is not intentionally added, and specifically, the alkali metal oxides (Li 2 O, Na 2 O, and K 2 O) in the glass composition.
  • ) Means glass having a content of 2000 ppm (mass) or less.
  • Continuous manufacturing means that glass is continuously manufactured for a certain period of time in a continuous melting kiln such as a tank kiln.
  • SiO 2 -Al 2 O 3 -RO system means a glass composition system containing SiO 2 , Al 2 O 3 and RO as essential components.
  • “Substantially free of arsenic and antimony” means that glass raw materials and glass cullet containing these components are not intentionally added to the glass batch. More specifically, it means that arsenic is 50 ppm or less as As 2 O 3 and antimony is 50 ppm or less as Sb 2 O 3 in the obtained glass on a molar basis.
  • the "down draw method” is a general term for a molding method in which molten glass is formed while being continuously stretched downward.
  • the present invention is characterized in that the glass is melted by using energization heating.
  • energization heating is used, the amount of energy per mass for obtaining molten glass is reduced, so that the environmental load can be reduced.
  • the present invention it is preferable to adjust the ⁇ -OH value of the obtained glass and the number of metal particles according to the glass raw material and / or the melting conditions.
  • the effect becomes more remarkable when radiant heating by burner combustion is not used in combination.
  • "Do not use radiant heating by burner combustion together” means that radiant heating by burner combustion is not performed at all during normal production, and does not exclude the use of a burner at the start of production (at the time of temperature rise). In addition, it does not exclude the combined use of radiant heating with a heater at the time of production start-up or normal production.
  • the start-up of production refers to the period until the raw material batch is melted into a glass melt and can be heated by energization.
  • orthoboric acid when producing a non - alkali glass substrate further containing B2O3 as a glass composition, it is preferable to use orthoboric acid as at least a part of a glass raw material as a boron source.
  • the boron component (B 2 O 3 ) is a component that improves the meltability of the glass, if the above configuration is adopted, it becomes easy to obtain a glass having excellent productivity.
  • the hydroxide raw material in the raw material batch.
  • glass cullet when glass cullet is added to a raw material batch to produce a non-alkali glass substrate, at least a part of the glass cullet is provided with a glass cullet made of glass having a ⁇ -OH value of 0.05 / mm or more. It is preferable to use it.
  • glass cullet means defective glass generated during the production of glass, recycled glass recovered from the market, and the like.
  • ⁇ -OH value refers to a value obtained by measuring the transmittance of glass using FT-IR and using the following formula.
  • ⁇ -OH value (1 / X) log (T 1 / T 2 )
  • X Glass wall thickness (mm)
  • T 1 Transmittance (%) at a reference wavelength of 3846 cm -1
  • T 2 Minimum transmittance (%) near hydroxyl group absorption wavelength 3600 cm -1
  • the step of removing the metal twice or more by passing the glass cullet through a magnetic sorter it is preferable to perform the step of removing the metal twice or more by passing the glass cullet through a magnetic sorter.
  • Metals containing Fe, Cr, Ni, etc. used in compounding equipment etc. are mixed in the reused glass cullet.
  • the metal containing Fe, Cr, Ni, etc. can be sufficiently removed, and the metal containing Fe, Cr, Ni, etc. is less likely to be mixed in the raw material batch.
  • metal particles containing Sn are less likely to precipitate in the glass.
  • the strain point of the obtained glass is 690 ° C. or higher.
  • the "distortion point” is a value measured based on the method of ASTM C336-71.
  • the heat shrinkage of the obtained glass is preferably 25 ppm or less.
  • the "heat shrinkage rate” was measured under the condition that the temperature of the glass was raised from room temperature to 500 ° C. at a rate of 5 ° C./min, held at 500 ° C. for 1 hour, and then lowered at a rate of 5 ° C./min. The value of time.
  • the heat shrinkage rate is measured by the following method.
  • a strip-shaped sample G having a size of 160 mm ⁇ 30 mm is prepared as a sample of the glass plate 1. Marking M is formed on each of both ends of the strip-shaped sample G in the long side direction at a position 20 to 40 mm away from the edge using # 1000 water-resistant abrasive paper.
  • the strip-shaped sample G on which the marking M is formed is folded in two along the direction orthogonal to the marking M to prepare sample pieces Ga and Gb.
  • only one sample piece Gb is subjected to a heat treatment in which the temperature is raised from room temperature (25 ° C.) to 500 ° C.
  • the markings M of the two sample pieces Ga and Gb are arranged in parallel with the heat-treated sample piece Ga and the heat-treated sample piece Gb.
  • the amount of misalignment ( ⁇ L 1 , ⁇ L 2 ) is read with a laser microscope, and the heat shrinkage rate is calculated by the following formula. Note that l 0 in the equation is the distance between the initial markings M.
  • Heat shrinkage rate [ ⁇ L 1 ( ⁇ m) + ⁇ L 2 ( ⁇ m) ⁇ ⁇ 10 3 ] / l 0 (mm) (ppm)
  • the present invention is preferably used for manufacturing a glass substrate on which an oxide TFT is formed.
  • the method of the present invention includes a step of preparing a raw material batch, a step of electrically melting the prepared batch, and a step of forming the melted glass into a plate shape.
  • a glass raw material is prepared so as to have a composition of SiO 2 -Al 2O 3 -RO (RO is one or more of MgO, CaO, BaO, SrO and ZnO).
  • RO is one or more of MgO, CaO, BaO, SrO and ZnO.
  • silica sand silica sand, stone powder (SiO 2 ) or the like can be used.
  • alumina Al 2 O 3
  • aluminum hydroxide Al (OH) 3
  • orthoboric acid H 3 BO 3
  • anhydrous boric acid B 2 O 3
  • orthoboric acid contains water of crystallization
  • the water content of the glass can be adjusted to be relatively high when the usage ratio is large. Therefore, it is preferable to use both orthoboric acid and anhydrous boric acid and adjust the usage ratio according to the target ⁇ -OH content.
  • Alkaline earth metal sources include calcium carbonate (CaCO 3 ), magnesium oxide (MgO), magnesium hydroxide (Mg (OH) 2 ), barium carbonate (BaCO 3 ), barium nitrate (Ba (NO 3 ) 2 ), Strontium carbonate (SrCO 3 ), strontium nitrate (Sr (NO 3 ) 2 ) and the like can be used.
  • Zinc oxide (ZnO) or the like can be used as the zinc source.
  • Zircon (ZrSiO 4 ) or the like can be used as the zirconia source.
  • a Zr-containing refractory such as zirconia electrocasting refractory or dense zircon
  • the zirconia component is eluted from the refractory.
  • These eluted components may also be used as a zirconia source.
  • Titanium oxide (TiO 2 ) or the like can be used as the titanium source.
  • aluminum metaphosphate (Al (PO 3 ) 3 ), magnesium pyrophosphate (Mg 2 P 2 O 7 ) and the like can be used as the phosphorus source.
  • Tin oxide (SnO 2 ) or the like can be used as the tin compound.
  • tin oxide it is preferable to use tin oxide having an average particle size D 50 in the range of 0.3 to 50 ⁇ m, 2 to 50 ⁇ m, and particularly 5 to 50 ⁇ m. If the average particle size D 50 of the tin oxide powder is small, agglomeration between the particles occurs, and clogging in the compounding plant is likely to occur. On the other hand, if the average particle size D50 of the tin oxide powder is large, the dissolution reaction of the tin oxide powder in the glass melt is delayed, and the clarification of the melt does not proceed.
  • the carbonate raw material may be contained in the raw material batch.
  • the carbonate raw material can efficiently function SnO 2 , which is a clarifying agent.
  • As the carbonate raw material for example, calcium carbonate (CaCO 3 ), barium carbonate (BaCO 3 ), strontium carbonate (SrCO 3 ) and the like can be used.
  • the nitrate raw material may be contained in the raw material batch.
  • the nitrate raw material can efficiently function SnO 2 , which is a clarifying agent.
  • SnO 2 which is a clarifying agent.
  • the nitrate raw material for example, barium nitrate (Ba (NO 3 ) 2 ), strontium nitrate (Sr (NO 3 ) 2 ) and the like can be used.
  • the hydroxide raw material may be contained in the raw material batch.
  • the hydroxide raw material can increase the water content in the glass.
  • aluminum hydroxide (Al (OH) 3 ), magnesium hydroxide (Mg (OH) 2 ), calcium hydroxide (Ca (OH) 2 ) and the like can be used as the hydroxide raw material.
  • the batch contains substantially no arsenic compound and antimony compound. If these components are contained, the electrodes are eroded, which makes it difficult to stably electromelt for a long period of time. Moreover, these components are environmentally unfavorable.
  • the ratio of the glass cullet to the total amount of the raw material batch is preferably 1% by mass or more, 5% by mass or more, and particularly preferably 10% by mass or more.
  • the upper limit of the usage ratio of the glass cullet is preferably 50% by mass or less, 40% by mass or less, and particularly preferably 30% by mass or less.
  • the glass cullet used is a glass cullet made of glass having a ⁇ -OH value of 0.05 / mm or more, 0.07 / mm or more, particularly 0.1 / mm or more. If the ⁇ -OH value of the glass cullet is too high, the strain point of the glass may be lowered too much. Therefore, the upper limit of the ⁇ -OH value of the glass cullet is preferably 0.4 / mm or less.
  • the step of removing the metal by passing the glass cullet through a magnetic sorter is performed twice or more, preferably three times or more, and particularly preferably five times or more.
  • the metal containing Fe, Cr, Ni, etc. that reduces SnO 2 in the glass is less likely to be mixed in the raw material batch.
  • metal particles containing Sn are less likely to precipitate. If the number of the steps is increased, the amount of the metal containing Fe, Cr, Ni and the like mixed is reduced, but from the viewpoint of cost, the number of the steps is preferably 10 or less.
  • Step of electrically melting the prepared raw material batch Next, the prepared raw material batch is put into a melting kiln and electrically melted.
  • the melting kiln has a plurality of electrodes, and by applying electricity between the electrodes, electricity is energized in the glass melt, and the glass is continuously melted by the Joule heat.
  • radiant heating by a heater or a burner may be used in combination as an auxiliary.
  • Molybdenum electrodes are used as electrodes because the optimum electrode placement and electrode shape can be adopted even for non-alkali glass, which has a high degree of freedom in placement location and electrode shape and is difficult to conduct electricity, and energization heating is easy. It is preferable to adopt it.
  • the electrode shape is preferably rod-shaped. If it is rod-shaped, it is possible to arrange a desired number of electrodes at arbitrary positions on the side wall surface and the bottom wall surface of the melting kiln while maintaining a desired distance between the electrodes.
  • the arrangement of the electrodes it is preferable to arrange a plurality of pairs on the wall surface of the melting kiln (side wall surface, bottom wall surface, etc.), particularly on the bottom wall surface with a short distance between the electrodes. If the glass contains an arsenic component or an antimony component, it cannot be used because it erodes the molybdenum electrode. Instead, it is necessary to use a tin electrode that is not eroded by these components. However, since the tin electrode has a very low degree of freedom in the arrangement location and the electrode shape, it is difficult to electrically melt the non-alkali glass.
  • the raw material batch put into the melting kiln is melted by energizing and heating to become a glass melt (molten glass).
  • the tin compound contained in the raw material batch dissolves in the glass melt and acts as a clarifying agent. More specifically, the tin component releases oxygen bubbles during the heating process. The released oxygen bubbles expand and float the bubbles contained in the glass melt and remove them from the glass. In addition, the tin component absorbs oxygen bubbles in the temperature lowering process to eliminate the bubbles remaining in the glass.
  • the glass melted in the melting kiln is supplied to the molding apparatus.
  • a clarification tank, a stirring tank, a state control tank, etc. are arranged between the melting kiln and the molding apparatus, and after passing through these, the forming apparatus is used. It may be supplied. Further, in order to prevent the glass from being contaminated, it is preferable that at least the contact surface with the glass is made of platinum or a platinum alloy in the connecting flow path connecting the melting kiln and the molding apparatus (or each tank provided between them).
  • Step of forming molten glass into a plate shape the molten glass in a melting kiln is supplied to a molding apparatus and formed into a plate shape by a downdraw method.
  • the overflow down draw method is a method in which molten glass overflows from both sides of a gutter-shaped refractory with a wedge-shaped cross section, and the overflowed molten glass is merged at the lower end of the gutter-shaped refractory while being stretched downward to form a plate. It is a method of molding into a shape.
  • the surface of the glass substrate which should be the surface, does not come into contact with the gutter-shaped refractory and is formed in a free surface state. Therefore, it is possible to inexpensively manufacture a glass substrate that is unpolished and has good surface quality, and it is easy to increase the size and thickness of the glass.
  • the structure and material of the gutter-shaped refractory used in the overflow downdraw method are not particularly limited as long as they can achieve desired dimensions and surface accuracy.
  • the method of applying a force when performing downward stretching molding is not particularly limited.
  • a method of rotating and stretching a heat-resistant roll having a sufficiently large width in contact with the glass may be adopted, or a plurality of pairs of heat-resistant rolls may be brought into contact with only the vicinity of the end face of the glass. You may adopt the method of letting and stretching.
  • a slot down method or the like can be adopted.
  • the glass formed into a plate shape in this way is cut into a predetermined size and subjected to various chemical or mechanical processing as necessary to form a glass substrate.
  • composition of non-alkali glass in terms of mass%, SiO 2 50 to 70%, Al 2 O 3 15 to 25%, B 2 O 3 2 ⁇ 7.5%, MgO 0 ⁇ 10%, CaO 0 ⁇ 10%, SrO 0 ⁇ 10%, BaO 0 ⁇ 15%, ZnO 0 ⁇ 5%, ZrO 20 ⁇ 1%, TiO 20 ⁇ 5%,
  • An example is a glass containing P 2 O 50 to 10% and SnO 2 0.1 to 0.5%, and substantially free of As 2 O 3 and Sb 2 O 3 .
  • the reasons for limiting the content of each component as described above are shown below.
  • the% display represents mass% unless otherwise specified.
  • SiO 2 is a component that forms the skeleton of glass.
  • the lower limit of the content of SiO 2 is preferably 50%, 51%, 51.5%, 52%, 55%, 56%, 57%, particularly 58%.
  • the upper limit of the content of SiO 2 is preferably 70%, 69%, 68%, 67%, 66%, 65%, 64%, 63%, particularly 62%. If the content of SiO 2 is too small, the density becomes too high and the acid resistance tends to decrease. On the other hand, if the content of SiO 2 is too large, the high-temperature viscosity becomes high and the meltability tends to decrease. In addition, devitrified crystals such as cristobalite are likely to precipitate, and the liquidus temperature is likely to rise.
  • Al 2 O 3 is a component that forms the skeleton of glass, is a component that increases the strain point and Young's modulus, and is a component that further suppresses phase separation.
  • the lower limit of the content of Al 2 O 3 is preferably 15%, 15.5%, 16%, 16.5%, 17%, 17.5%, particularly 18%.
  • the upper limit of the content of Al 2 O 3 is preferably 25%, 24%, 23%, 22%, 21.5%, and particularly preferably 21%. If the content of Al 2 O 3 is too small, the strain point and Young's modulus tend to decrease, and the glass tends to be phase-separated. On the other hand, if the content of Al 2 O 3 is too large, devitrified crystals such as mullite and anorthite are likely to precipitate, and the liquidus temperature is likely to rise.
  • B 2 O 3 is a component that enhances meltability and devitrification resistance.
  • the lower limit of the content of B 2 O 3 is preferably 2%, 2.2%, and particularly preferably 2.5%.
  • the upper limit of the content of B 2 O 3 is preferably 7.5%, particularly preferably 7%. If the content of B 2 O 3 is too small, the meltability and devitrification resistance tend to decrease, and the resistance to hydrofluoric acid-based chemicals such as buffered hydrofluoric acid tends to decrease. In addition, the amount of water brought in from the batch may be too small. On the other hand, if the content of B 2 O 3 is too large, the strain point and Young's modulus tend to decrease.
  • MgO is a component that lowers high-temperature viscosity and enhances meltability, and is a component that significantly increases Young's modulus among alkaline earth metal oxides.
  • the lower limit of the MgO content is preferably 0%, 0.1%, 0.5%, 1%, 1.5%, particularly 2%.
  • the upper limit of the MgO content is preferably 10%, 9%, 8%, 7.5%, 7%, 6%, and particularly preferably 5%. If the content of MgO is too small, the meltability and Young's modulus tend to decrease. On the other hand, if the content of MgO is too large, the devitrification resistance tends to decrease and the strain point tends to decrease.
  • CaO is a component that lowers the high-temperature viscosity and remarkably enhances the meltability without lowering the strain point. Further, among the alkaline earth metal oxides, since the introduced raw material is relatively inexpensive, it is a component that reduces the raw material cost.
  • the lower limit of the CaO content is preferably 0%, 0.1%, 1%, 2%, 3%, particularly 3.5%.
  • the upper limit of the CaO content is preferably 10%, 9%, 8%, and particularly preferably 7%. If the CaO content is too low, it becomes difficult to enjoy the above effects. On the other hand, if the CaO content is too high, the glass tends to be devitrified and the coefficient of thermal expansion tends to be high.
  • SrO is a component that suppresses phase separation and enhances devitrification resistance. Further, it is a component that lowers the high-temperature viscosity and enhances the meltability without lowering the strain point. It is also a component that suppresses the rise in liquid phase temperature.
  • the lower limit of the SrO content is preferably 0%, 0.1%, and particularly preferably 0.3%.
  • the upper limit of the SrO content is preferably 10%, 9%, 8%, 7%, 6%, particularly 5%. If the content of SrO is too small, it becomes difficult to enjoy the above effect. On the other hand, if the content of SrO is too large, the density becomes too high, and devitrification crystals containing SrO tend to precipitate, so that the devitrification resistance tends to decrease.
  • BaO is a component that significantly enhances devitrification resistance.
  • the lower limit of the BaO content is preferably 0%, 0.1%, 0.5%, particularly 1%.
  • the upper limit of the BaO content is preferably 15%, 14%, 13%, 12%, 11%, particularly 10.5%. If the BaO content is too low, it becomes difficult to enjoy the above effects. On the other hand, if the BaO content is too high, the density becomes too high and the meltability tends to decrease. In addition, devitrified crystals containing BaO are likely to precipitate, and the liquidus temperature is likely to rise.
  • ZnO is a component that enhances meltability.
  • the ZnO content is preferably 0 to 5%, 0 to 4%, 0 to 3%, and particularly preferably 0 to 2%. If the ZnO content is too high, the glass tends to be devitrified and the strain point tends to decrease.
  • ZrO 2 is a component that enhances chemical durability.
  • the lower limit of the content of ZrO 2 is preferably 0%, particularly preferably 0.01%.
  • the upper limit of the content of ZrO 2 is preferably 1%, 0.5%, 0.2%, 0.1%, and particularly preferably 0.05%. If the content of ZrO 2 is too large, devitrification of ZrSiO 4 is likely to occur.
  • TiO 2 is a component that lowers high-temperature viscosity and enhances meltability. It is also a component that suppresses solarization.
  • the content of TiO 2 is preferably 0 to 5%, 0 to 4%, 0 to 3%, 0 to 2%, 0-1%, and particularly preferably 0 to 0.1%. If the content of TiO 2 is too high, the glass is colored and the transmittance tends to decrease.
  • P 2 O 5 is a component that enhances the strain point and is a component that can suppress the precipitation of devitrified crystals of alkaline earth aluminosilicate type such as anorthite.
  • the content of P 2 O 5 is 0 to 10%, 0 to 9%, 0 to 8%, 0 to 7%, 0 to 6%, 0 to 5%, 0 to 4%, and particularly 0 to 3%. Is preferable. If the content of P 2 O 5 is too large, the glass tends to be phase-separated.
  • SnO 2 is a component having a good clarifying action in a high temperature range, a component that increases a strain point, and a component that lowers a high temperature viscosity. It also has the advantage of not eroding the molybdenum electrode.
  • the lower limit of the SnO 2 content is preferably 0.1%, particularly preferably 0.15%.
  • the upper limit of the SnO 2 content is preferably 0.5%, 0.45%, 0.4%, 0.35%, and particularly preferably 0.3%. If the content of SnO 2 is too small, it becomes difficult to enjoy the above effects. On the other hand, if the content of SnO 2 is too large, the devitrified crystals of SnO 2 are likely to precipitate, and the precipitation of the devitrified crystals of ZrO 2 is likely to be promoted.
  • the glass raw material or glass cullet containing these components is not intentionally added to the glass batch. More specifically, it means that arsenic is 50 ppm or less as As 2 O 3 and antimony is 50 ppm or less as Sb 2 O 3 in the obtained glass. Although these components are useful as clarifying agents, they should not be used as they erode molybdenum electrodes and make electromelting on an industrial scale difficult. It is also preferable not to use it from an environmental point of view.
  • other components can be contained in a total amount of 5% or less.
  • Cl and F may be contained in the glass, but the Cl content is preferably less than 0.1%, particularly preferably less than 0.05%, and the F content is 0.1%. Less than, especially less than 0.05%. Further, Cl + F (total amount of Cl and F) is preferably less than 0.1%.
  • the non-alkali glass substrate obtained by the method of the present invention has a ⁇ -OH value of 0.05 / mm or more, 0.07 / mm or more, 0.1 / mm or more, 0.12 / mm or more, 0.15 /. It is made of glass having a thickness of mm or more, 0.18 / mm or more, and particularly 0.2 / mm or more. By doing so, it is possible to sufficiently reduce the number of metal lumps. If the ⁇ -OH value is too large, the strain point of the glass will not be sufficiently high and it will be difficult to reduce the heat shrinkage rate. Therefore, the upper limit of the ⁇ -OH value is 0.4 / mm or less, especially. It is preferably 0.35 / mm or less.
  • the non-alkali glass substrate obtained by the method of the present invention is made of glass having 20 or less metal pieces / ton, 10 pieces / ton or less, 5 pieces / ton or less, and particularly 3 pieces / ton or less.
  • the lower limit of the metal lumps is not particularly limited, but in reality, it is 0.1 pieces / ton or more.
  • the temperature of the glass was raised from room temperature to 500 ° C. at a rate of 5 ° C./min, held at 500 ° C. for 1 hour, and then lowered at a rate of 5 ° C./min.
  • the heat shrinkage rate is preferably 25 ppm or less, 20 ppm or less, 19 ppm or less, 18 ppm or less, 17 ppm or less, 16 ppm or less, 15 ppm or less, 14 ppm or less, and particularly preferably 13 ppm or less. If the heat shrinkage rate is large, it becomes difficult to use it as a substrate for forming an oxide TFT.
  • the lower limit of the heat shrinkage rate is not limited, but is preferably 2 ppm or more, particularly preferably 3 ppm or more.
  • the non-alkali glass plate obtained by the method of the present invention is preferably made of glass having a strain point of 690 ° C. or higher, 700 ° C. or higher, 705 ° C. or higher, and particularly 710 ° C. or higher. By doing so, it becomes easy to suppress the heat shrinkage of the glass plate in the manufacturing process of the oxide TFT. If the strain point is too high, the temperature at the time of molding or melting becomes too high, and the manufacturing cost of the glass plate tends to be high. Therefore, the upper limit of the strain point is 750 ° C. or lower, 740 ° C. or lower, particularly 730 ° C. or lower. Is preferable.
  • the non-alkali glass plate obtained by the method of the present invention is a glass having a temperature of 1630 ° C. or lower, 1620 ° C. or lower, 1610 ° C. or lower, 1600 ° C. or lower, 1590 ° C. or lower, particularly 1580 ° C. or lower at 10 2.5 dPa ⁇ s. It is preferably composed of. If the temperature at 10 2.5 dPa ⁇ s is too high, the glass becomes difficult to melt, the manufacturing cost of the glass plate rises, and defects such as bubbles are likely to occur. If the temperature at 10 2.5 dPa ⁇ s is too low, the viscosity at the liquidus temperature will be high and it will be difficult to design.
  • the lower limit of the temperature at 10 2.5 dPa ⁇ s is 1500 ° C. or higher, 1510 ° C. or higher, especially 1520 ° C. The above is preferable.
  • the "temperature corresponding to 10 2.5 dPa ⁇ s" is a value measured by the platinum ball pulling method.
  • the non-alkali glass plate obtained by the method of the present invention is preferably made of glass having a liquid phase temperature of less than 1250 ° C., less than 1240 ° C., less than 1230 ° C., less than 1220 ° C., less than 1210 ° C., and particularly less than 1200 ° C.
  • a liquid phase temperature of less than 1250 ° C., less than 1240 ° C., less than 1230 ° C., less than 1220 ° C., less than 1210 ° C., and particularly less than 1200 ° C.
  • the liquidus temperature is an index of devitrification resistance, and the lower the liquidus temperature, the better the devitrification resistance.
  • the "liquid phase temperature” is set in a temperature gradient furnace set at 1100 ° C. to 1350 ° C. for 24 hours by placing the glass powder that has passed through a standard sieve of 30 mesh (500 ⁇ m) and remains in 50 mesh (300 ⁇ m) in a platinum boat. After holding, the platinum boat is taken out, and it refers to the temperature at which devitrification (crystal foreign matter) is observed in the glass.
  • the non-alkali glass plate obtained by the method of the present invention has a liquid phase viscosity of 10 4.0 dPa ⁇ s or more, 10 4.2 dPa ⁇ s or more, 10 4.4 dPa ⁇ s or more, and 10 4.5 dPa ⁇ . s or more, 10 4.6 dPa ⁇ s or more, 10 4.7 dPa ⁇ s or more, 10 4.8 dPa ⁇ s or more, 10 4.9 dPa ⁇ s or more, especially 10 5.0 dPa ⁇ s or more. It is preferably made of glass.
  • the liquidus viscosity is an index of moldability, and the higher the liquidus viscosity, the better the moldability.
  • the "liquid phase viscosity” refers to the viscosity of the glass at the liquid phase temperature, and can be measured by, for example, a platinum ball pulling method.
  • the non-alkali glass plate obtained by the method of the present invention preferably has a substrate area of 4 m 2 or more. If the substrate area is too small, it becomes difficult to efficiently manufacture a large LCD or OLED display provided with a TFT having an oxide film such as IGZO.
  • Table 1 shows examples (No. 1 to 6) of the present invention.
  • silica sand, aluminum oxide, orthoboric acid, anhydrous boric acid, calcium carbonate, strontium carbonate, strontium nitrate, barium carbonate, and ferric oxide were mixed and prepared so as to have the composition shown in Table 1.
  • a glass cullet having the same composition as the target composition ( ⁇ -OH value 0.2 / mm, 35% by mass based on the total amount of the raw material batch) was used in combination.
  • the step of removing the metal by passing it through a magnetic sorter was performed twice.
  • the glass raw material was supplied to an electric melting kiln that did not use burner combustion to melt it, and then the molten glass was clarified and homogenized in the clarification tank and the adjustment tank, and the viscosity was adjusted to be suitable for molding.
  • the molten glass was supplied to an overflow down draw molding apparatus, molded into a plate shape, and then cut to obtain a glass sample having a thickness of 0.5 mm.
  • the molten glass that came out of the molten kiln was supplied to the molding apparatus while in contact with only platinum or a platinum alloy.
  • the obtained glass sample is observed with a 50x stereomicroscope, and if metal lumps of 1 ⁇ m or more are observed in the observation field, they are counted as metal lumps, and the metal per ton is counted from the size of the glass used for measurement. The number of stuff was calculated. The results are shown in Table 1.
  • FIG. 2 shows a plot of the ⁇ -OH value on the horizontal axis and the metal lumps on the vertical axis. As is clear from FIG. 2, the larger the ⁇ -OH value, the smaller the number of metal lumps.
  • the ⁇ -OH value of the glass was determined by measuring the transmittance of the glass using FT-IR and using the following formula.
  • ⁇ -OH value (1 / X) log10 (T 1 / T 2 )
  • X Glass wall thickness (mm)
  • T 1 Transmittance (%) at a reference wavelength of 3846 cm -1
  • T 2 Minimum transmittance (%) near hydroxyl group absorption wavelength 3600 cm -1

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  • Life Sciences & Earth Sciences (AREA)
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  • Geochemistry & Mineralogy (AREA)
  • Electrochemistry (AREA)
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Abstract

La présente invention concerne un procédé de production d'un substrat de verre exempt d'alcali, ledit procédé permettant de produire un substrat de verre exempt d'alcali ayant un petit nombre de bosses. L'invention concerne un procédé de production en continu d'un substrat de verre exempt d'alcali à base de SiO2-Al2O3-RO (dans laquelle RO représente un ou plusieurs oxydes choisis parmi MgO, CaO, BaO, SrO et ZnO), ledit procédé étant caractérisé en ce qu'il comprend : une étape permettant de préparer un lot de matière première qui contient un composé d'étain mais qui ne contient pratiquement pas de composé d'arsenic ni de composé d'antimoine; une étape permettant de faire fondre électriquement le lot de matière première ainsi préparé dans un four de fusion qui peut être chauffé par conduction électrique au moyen d'électrodes; et une étape permettant de façonner le verre fondu en une forme de plaque par un procédé d'étirage vers le bas. Ce procédé est également caractérisé en ce que la valeur de β-OH du verre ainsi obtenu est supérieure ou égale à 0,05/mm, tandis que le nombre de bosses métalliques en son sein est inférieur ou égal à 20/tonne.
PCT/JP2021/041181 2020-12-17 2021-11-09 Procédé servant à produire un substrat de verre exempt d'alcali WO2022130831A1 (fr)

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CN202180084882.2A CN116648438A (zh) 2020-12-17 2021-11-09 无碱玻璃基板的制造方法

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018123505A1 (fr) * 2016-12-26 2018-07-05 日本電気硝子株式会社 Procédé de production de substrat en verre exempt d'alcali
WO2019049768A1 (fr) * 2017-09-05 2019-03-14 日本電気硝子株式会社 Procédé de production d'un substrat en verre sans alcali et substrat en verre sans alcali
JP2020132444A (ja) * 2019-02-14 2020-08-31 ＡｖａｎＳｔｒａｔｅ株式会社 ガラス基板の製造方法
WO2020209271A1 (fr) * 2019-04-12 2020-10-15 Ａｇｃ株式会社 Verre sans alcali et plaque de verre

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KR101449491B1 (ko) 2013-01-02 2014-10-08 경창산업주식회사 치형 부품의 성형 방법

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018123505A1 (fr) * 2016-12-26 2018-07-05 日本電気硝子株式会社 Procédé de production de substrat en verre exempt d'alcali
WO2019049768A1 (fr) * 2017-09-05 2019-03-14 日本電気硝子株式会社 Procédé de production d'un substrat en verre sans alcali et substrat en verre sans alcali
JP2020132444A (ja) * 2019-02-14 2020-08-31 ＡｖａｎＳｔｒａｔｅ株式会社 ガラス基板の製造方法
WO2020209271A1 (fr) * 2019-04-12 2020-10-15 Ａｇｃ株式会社 Verre sans alcali et plaque de verre

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