WO2022239741A1 - 無アルカリガラス板 - Google Patents

無アルカリガラス板 Download PDF

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Publication number
WO2022239741A1
WO2022239741A1 PCT/JP2022/019703 JP2022019703W WO2022239741A1 WO 2022239741 A1 WO2022239741 A1 WO 2022239741A1 JP 2022019703 W JP2022019703 W JP 2022019703W WO 2022239741 A1 WO2022239741 A1 WO 2022239741A1
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Prior art keywords
glass plate
alkali
mol
sro
still
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PCT/JP2022/019703
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English (en)
French (fr)
Japanese (ja)
Inventor
未侑 西宮
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Nippon Electric Glass Co Ltd
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Nippon Electric Glass Co Ltd
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Priority to JP2023521015A priority Critical patent/JPWO2022239741A1/ja
Priority to KR1020237038876A priority patent/KR20240006551A/ko
Priority to CN202280034539.1A priority patent/CN117295698A/zh
Priority to US18/290,031 priority patent/US20240262737A1/en
Publication of WO2022239741A1 publication Critical patent/WO2022239741A1/ja
Anticipated expiration legal-status Critical
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    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B5/00—Recording by magnetisation or demagnetisation of a record carrier; Reproducing by magnetic means; Record carriers therefor
    • G11B5/62—Record carriers characterised by the selection of the material
    • G11B5/73—Base layers, i.e. all non-magnetic layers lying under a lowermost magnetic recording layer, e.g. including any non-magnetic layer in between a first magnetic recording layer and either an underlying substrate or a soft magnetic underlayer
    • G11B5/739—Magnetic recording media substrates
    • G11B5/73911—Inorganic substrates
    • G11B5/73921—Glass or ceramic substrates
    • 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
    • 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
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/02—Details
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional [2D] radiating surfaces
    • H05B33/14—Light sources with substantially two-dimensional [2D] radiating surfaces characterised by the chemical or physical composition or the arrangement of the electroluminescent material, or by the simultaneous addition of the electroluminescent material in or onto the light source
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K77/00—Constructional details of devices covered by this subclass and not covered by groups H10K10/80, H10K30/80, H10K50/80 or H10K59/80
    • H10K77/10—Substrates, e.g. flexible substrates
    • 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 an alkali-free glass plate, and more particularly to an alkali-free glass plate suitable for organic EL displays and magnetic recording media.
  • Organic EL displays are thin, excellent in displaying moving images, and have low power consumption, so they are used for applications such as flexible devices and mobile phone displays.
  • Glass plates are widely used as substrates for organic EL displays.
  • the following properties are mainly required for glass sheets for this application.
  • (1) In order to prevent alkali ions from diffusing into the semiconductor material formed as a film in the heat treatment process, it should contain almost no alkali metal oxides. is 0.5 mol% or less),
  • (2) In order to reduce the cost of the glass sheet, it should be formed by an overflow down-draw method that facilitates improvement of surface quality, and should have excellent productivity, especially excellent meltability and devitrification resistance.
  • Glass plates are widely used as substrates for information recording media in place of conventional aluminum alloy substrates.
  • magnetic recording media using an energy-assisted magnetic recording system ie, energy-assisted magnetic recording media
  • a glass plate is also used for the energy-assisted magnetic recording medium, and a magnetic layer or the like is formed on the surface of the glass plate.
  • an ordered alloy having a large magnetic anisotropy coefficient Ku hereinafter referred to as "high Ku" is used as the magnetic material of the magnetic layer.
  • organic EL devices are also widely used in organic EL televisions.
  • glass sheets for these applications are required to have thermal dimensional stability that can withstand the demand for high resolution while being large and thin.
  • low cost is required, and glass plates are similarly required to be low cost.
  • the glass plate tends to bend, and the manufacturing cost rises.
  • a glass sheet formed by a glass manufacturer goes through processes such as cutting, annealing, inspection, and cleaning. During these processes, the glass sheet is put into and taken out of a cassette with multiple shelves formed. . Normally, this cassette can be held horizontally by placing opposite sides of the glass plate on shelves formed on the left and right inner surfaces, but a large and thin glass plate has a large amount of deflection. Therefore, when the glass plate is put into the cassette, part of the glass plate comes into contact with the cassette and is damaged, and when it is carried out, it swings greatly and becomes unstable.
  • Such a form of cassette is also used by electronic device makers, so similar problems occur. In order to solve this problem, it is effective to increase the Young's modulus of the glass plate to reduce the amount of deflection.
  • glass plates for magnetic recording media are required to have high rigidity (Young's modulus) so as not to cause large deformation during high-speed rotation. More specifically, in a disk-shaped magnetic recording medium, information is written and read along the direction of rotation while rotating the medium around its central axis at high speed and moving the magnetic head in the radial direction. In recent years, the number of rotations for increasing the writing speed and reading speed has been increasing from 5400 rpm to 7200 rpm and further to 10000 rpm. A position is assigned to record the information. Therefore, if the glass plate is deformed during rotation, the position of the magnetic head is shifted, making it difficult to read accurately.
  • high rigidity Young's modulus
  • the DFH mechanism is a mechanism in which a heating portion such as a very small heater is provided in the vicinity of the recording/reproducing element portion of the magnetic head, and only the periphery of the element portion is thermally expanded toward the medium surface direction.
  • the gap between the recording/reproducing element portion of the magnetic head and the surface of the magnetic recording medium is extremely small, for example, 2 nm or less, even a slight impact may cause the magnetic head to collide with the surface of the magnetic recording medium. . This tendency becomes more conspicuous as the rotation speed increases. Therefore, during high-speed rotation, it is important to prevent the bending and fluttering of the glass plate, which cause this collision.
  • the base material including the glass plate is heat-treated at a high temperature of about 800° C. during the film formation of the magnetic layer, or before and after the film formation. I have something to do. Since the higher the recording density, the higher the heat treatment temperature, the higher the heat resistance, that is, the higher the strain point, than the conventional glass plates for magnetic recording media.
  • the substrate including the glass plate is irradiated with a laser after the magnetic layer is formed. Such heat treatment and laser irradiation also have the purpose of increasing the annealing temperature and coercive force of the magnetic layer containing the FePt-based alloy or the like.
  • the present invention has been invented in view of the above circumstances, and a technical problem thereof is to provide an alkali-free glass plate which is excellent in productivity and has sufficiently high strain point and Young's modulus.
  • the inventor found that the above technical problems can be solved by strictly controlling the glass composition of the alkali-free glass plate, and proposes it as the present invention. That is, the alkali-free glass plate of the present invention has a glass composition of SiO 2 64 to 72%, Al 2 O 3 12 to 16%, B 2 O 3 0 to 3%, Li 2 O + Na 2 O + K 2 in mol%.
  • Li2O + Na2O + K2O refers to the total amount of Li2O, Na2O and K2O .
  • SrO/SiO 2 is a value obtained by dividing the mol % content of SrO by the mol % content of SiO 2 .
  • the alkali-free glass plate of the present invention has a glass composition of SiO 2 64 to 72%, Al 2 O 3 12 to 16%, B 2 O 3 0 to less than 1%, Li 2 O + Na 2 O + K in mol%. 2 O 0-0.5%, MgO 6-12%, CaO 9-13%, SrO >0-2%, BaO 0-1%, mol% ratio SrO/SiO 2 0-0.008 is preferably
  • the alkali-free glass plate of the present invention does not substantially contain As 2 O 3 and Sb 2 O 3 in the glass composition.
  • substantially free of As 2 O 3 means that the content of As 2 O 3 is 0.05 mol % or less.
  • substantially free of Sb 2 O 3 means that the content of Sb 2 O 3 is 0.05 mol % or less.
  • the alkali-free glass plate of the present invention preferably further contains 0.001 to 1 mol % of SnO 2 .
  • the alkali-free glass plate of the present invention preferably has a Young's modulus of 83 GPa or higher, a strain point of 730° C. or higher, and a liquidus temperature of 1350° C. or lower.
  • Young's modulus refers to a value measured by a bending resonance method. 1 GPa corresponds to approximately 101.9 Kgf/mm 2 .
  • Stress point refers to a value measured according to the method of ASTM C336.
  • “Liquidus temperature” is the temperature at which crystals precipitate after passing through a 30-mesh (500 ⁇ m) standard sieve and remaining on the 50-mesh (300 ⁇ m) glass powder in a platinum boat and holding it in a temperature gradient furnace for 24 hours. point to
  • the alkali-free glass plate of the present invention preferably has a strain point of 735°C or higher.
  • the alkali-free glass plate of the present invention preferably has a Young's modulus higher than 84 GPa.
  • the alkali-free glass plate of the present invention preferably has an average thermal expansion coefficient of 30 ⁇ 10 -7 to 50 ⁇ 10 -7 /°C in the temperature range of 30 to 380°C.
  • the "average coefficient of thermal expansion in the temperature range of 30 to 380° C.” can be measured with a dilatometer.
  • the alkali-free glass plate of the present invention preferably has a liquidus viscosity of 10 4.0 dPa ⁇ s or more.
  • the "liquidus viscosity” refers to the viscosity of the glass at the liquidus temperature, and can be measured by the platinum ball pull-up method.
  • the alkali-free glass plate of the present invention is preferably used for an organic EL device.
  • the alkali-free glass plate of the present invention is preferably used for magnetic recording media.
  • FIG. 3 is a top perspective view for showing the disk shape
  • the alkali-free glass plate of the present invention has a glass composition of SiO 2 64 to 72%, Al 2 O 3 12 to 16%, B 2 O 3 0 to 3%, Li 2 O + Na 2 O + K 2 O 0 in mol%. ⁇ 0.5%, MgO 6-12%, CaO 9-13%, SrO 0-2%, BaO 0-1%, and the mol% ratio SrO/ SiO2 is 0-0.03. Characterized by The reasons for limiting the content of each component as described above are as follows. In addition, in description of content of each component, % display represents mol% unless otherwise specified.
  • SiO2 is a component that forms the skeleton of glass. If the content of SiO2 is too low, the coefficient of thermal expansion will be high and the density will increase. Therefore, the lower limit of SiO2 is preferably 64%, more preferably 64.2%, more preferably 64.5%, more preferably 64.8%, more preferably 65%, more preferably 65.5%. %, more preferably 65.8%, more preferably 66%, more preferably 66.3%, still more preferably 66.5%, most preferably 66.7%.
  • the upper limit of SiO2 is preferably 72%, more preferably 71.8%, more preferably 71.6%, more preferably 71.4%, more preferably 71.2%, more preferably 71% %, more preferably 70.8%, more preferably 70.6%, most preferably 70.4%.
  • Al 2 O 3 is a component that forms the skeleton of the glass, a component that increases the Young's modulus, and a component that increases the strain point. If the content of Al 2 O 3 is too small, the Young's modulus tends to decrease, and the strain point tends to decrease. Therefore, the lower limit of Al 2 O 3 is preferably 12%, more preferably 12.2%, more preferably 12.4%, even more preferably more than 12.4%, even more preferably 12.5%, most preferably Preferably it is more than 12.5%. On the other hand, if the content of Al 2 O 3 is too high, devitrified crystals such as mullite are likely to precipitate and the liquidus viscosity tends to decrease.
  • the upper limit of Al 2 O 3 is preferably 16%, more preferably 15.8%, even more preferably 15.5%, even more preferably 15.3%, even more preferably 15%, even more preferably 14%. .8%, more preferably 14.6%, more preferably 14.4%, more preferably 14.2%, more preferably 14%, more preferably 13.9%, more preferably 13.8%, More preferably 13.7%, most preferably 13.6%
  • B 2 O 3 is not an essential component, but if it is included, it can have the effect of improving meltability and devitrification resistance. Therefore, the lower limit amount of B 2 O 3 is preferably 0%, more preferably over 0%, more preferably 0.1%, still more preferably 0.2%, still more preferably 0.3%, still more preferably 0.4%, most preferably 0.5%. On the other hand, if the B 2 O 3 content is too high, the Young's modulus and strain point tend to decrease.
  • the upper limit of B 2 O 3 is preferably 3%, more preferably 2.9%, more preferably 2.8%, still more preferably 2.7%, still more preferably 2.6%, even more preferably is 2.5%, more preferably 2%, more preferably 2.8%, more preferably 2.6%, more preferably 2.4%, more preferably 2.2%, more preferably 2%, More preferably 1.8%, more preferably 1.6%, more preferably 1.4%, more preferably 1.2%, more preferably 1%, most preferably less than 1%.
  • Li 2 O, Na 2 O and K 2 O are components that are unavoidably mixed from the glass raw material, and the total amount thereof is 0 to 0.5%, preferably 0 to 0.4%, more preferably 0-0.3%, more preferably 0.005-0.2%, most preferably 0.01-0.1%. If the total amount of Li 2 O, Na 2 O and K 2 O is too large, there is a risk that alkali ions will diffuse into the semiconductor material deposited in the heat treatment process.
  • the individual contents of Li 2 O, Na 2 O and K 2 O are each preferably 0 to 0.5%, more preferably 0 to 0.4%, still more preferably 0 to 0.3%, and further preferably Preferably 0.005-0.2%, most preferably 0.01-0.1%.
  • MgO is a component that significantly increases Young's modulus among alkaline earth metal oxides. If the content of MgO is too small, the meltability and Young's modulus tend to decrease. Therefore, the lower limit of MgO is preferably 6%, more preferably 6.1%, more preferably 6.3%, still more preferably 6.5%, still more preferably 6.6%, still more preferably 6.5%. 7%, more preferably 6.8%, most preferably 7%. On the other hand, if the MgO content is too high, devitrified crystals such as mullite are likely to precipitate, and the liquidus viscosity tends to decrease.
  • the upper limit of MgO is preferably 12%, more preferably 11.8%, more preferably 11.5%, more preferably 11.3%, more preferably 11%, more preferably less than 11%, More preferably 10.8%, more preferably 10.6%, still more preferably 10.4%, still more preferably 10.2%, still more preferably 10%, most preferably 9.8%.
  • the mol % ratio B 2 O 3 /MgO is an important component ratio for increasing Young's modulus and increasing devitrification resistance. If the mol % ratio B 2 O 3 /MgO is too small, the resistance to devitrification is lowered, and the manufacturing cost of the glass plate tends to rise. Therefore, the lower limit of the mol % ratio B 2 O 3 /MgO is preferably 0, more preferably 0.0001, even more preferably 0.001, most preferably 0.005. On the other hand, if the mol % ratio B 2 O 3 /MgO is too large, the Young's modulus tends to decrease.
  • the upper limit of the mol% ratio B 2 O 3 /MgO is preferably 0.2, more preferably 0.1, still more preferably 0.08, more preferably 0.05, still more preferably 0.03, and further preferably Preferably 0.02, most preferably 0.01.
  • “B 2 O 3 /MgO” is a value obtained by dividing the mol % content of B 2 O 3 by the mol % content of MgO.
  • CaO is a component that lowers the high-temperature viscosity and significantly increases the meltability without lowering the strain point. It is also a component that increases Young's modulus. If the content of CaO is too small, the meltability tends to deteriorate. Therefore, the lower limit of CaO is preferably 9%, more preferably more than 9%, more preferably 9.1%, still more preferably 9.2%, still more preferably 9.3%, still more preferably 9.4 %, more preferably 9.5%, more preferably 9.6%, most preferably 10%. On the other hand, when the content of CaO is too high, the liquidus temperature increases. Therefore, the upper limit of CaO is preferably 13%, more preferably 12.9%, more preferably 12.8%, more preferably 12.6%, more preferably 12.5%, still more preferably 12.5%. 4%, more preferably 12.2%, most preferably 12%.
  • the mol% ratio MgO/CaO is an important component ratio in order to increase devitrification resistance. If the mol% ratio MgO/CaO is too small, the devitrification resistance tends to be low. Therefore, the lower limit of the mol% ratio MgO/CaO is preferably 0.6, more preferably 0.7, even more preferably 0.8, and most preferably 0.9. On the other hand, if the mol % ratio of MgO/CaO is too large, the liquidus viscosity will decrease and the manufacturing cost of the glass plate will tend to rise.
  • the upper limit of the mol% ratio MgO/CaO is preferably 2.0, more preferably 1.8, even more preferably 1.6, even more preferably 1.4, most preferably 1.2.
  • the "mol% ratio MgO/CaO" is a value obtained by dividing the mol% content of MgO by the mol% content of CaO.
  • the lower limit of SrO is preferably 0%, more preferably over 0%, more preferably 0.1%, still more preferably over 0.1%, still more preferably 0.2%, still more preferably 0.2%. 3%, more preferably greater than 0.3%, more preferably 0.4%, more preferably greater than 0.4%, most preferably 0.5%.
  • the upper limit of SrO is preferably 2%, more preferably less than 2%, still more preferably 1.8%, still more preferably 1.6%, still more preferably 1.5%, still more preferably 1.4% %, more preferably 1.2%, more preferably 1%, more preferably less than 1%, more preferably 0.9%, more preferably less than 0.9%, more preferably 0.8%, more preferably is less than 0.8%, more preferably less than 0.7%, more preferably less than 0.7%, more preferably less than 0.6%, most preferably less than 0.6%.
  • the lower limit of BaO is preferably 0%, more preferably over 0%, more preferably 0.1%, still more preferably over 0.1%, still more preferably 0.2%, still more preferably 0.2%. 3%, more preferably 0.4%, more preferably greater than 0.4%, most preferably 0.5%.
  • the upper limit of BaO is preferably 1%, more preferably less than 1%, more preferably 0.9%, still more preferably less than 0.9%, still more preferably 0.8%, still more preferably 0.9%. Less than 8%, most preferably 0.7%.
  • SrO and BaO are components that increase devitrification resistance.
  • the lower limit of SrO+BaO is preferably 0%, more preferably over 0%, more preferably 0.1%, still more preferably over 0.1%, still more preferably 0.2%, still more preferably 0.3% , more preferably 0.4%, more preferably greater than 0.4%, and most preferably 0.5%.
  • the content of SrO+BaO is too high, the Young's modulus tends to decrease and the density tends to increase. As a result, the specific Young's modulus increases, and the glass sheet becomes more flexible.
  • the upper limit of SrO+BaO is preferably 2%, more preferably less than 1%, more preferably 0.9%, still more preferably less than 0.9%, still more preferably 0.8%, still more preferably 0.9%. Less than 8%, most preferably 0.7%.
  • SrO+BaO refers to the total amount of SrO and BaO.
  • B 2 O 3 , SrO and BaO are components that improve devitrification resistance.
  • the lower limit amount of B 2 O 3 +SrO+BaO is preferably 0%, more preferably over 0%, more preferably 0.1%, even more preferably over 0.1%, still more preferably 0.2%, still more preferably 0.3%, more preferably 0.4%, more preferably greater than 0.4%, most preferably 0.5%.
  • the content of B 2 O 3 +SrO+BaO is too high, the Young's modulus tends to decrease.
  • the upper limit of B 2 O 3 +SrO+BaO is preferably 2%, more preferably less than 1%, more preferably 0.9%, even more preferably less than 0.9%, still more preferably 0.8%, and further preferably Preferably less than 0.8%, most preferably 0.7%.
  • B2O3 + SrO+BaO refers to the total amount of B2O3 , SrO and BaO.
  • the mol % ratio SrO/SiO 2 is an important component ratio in order to achieve both Young's modulus and liquidus viscosity. If the mol % ratio SrO/SiO 2 is too small, the Young's modulus tends to be low. Therefore, the lower limit of the mol % ratio SrO/SiO 2 is preferably 0, more preferably above 0, still more preferably 0.001, most preferably above 0.001. On the other hand, if the mol % ratio SrO/SiO 2 is too large, the liquidus viscosity will decrease and the manufacturing cost of the glass plate will tend to increase.
  • the upper limit of the mol% ratio SrO/ SiO2 is preferably 0.03, more preferably 0.02, more preferably 0.015, more preferably 0.01, more preferably less than 0.01, and more preferably is less than 0.009, more preferably less than 0.009, more preferably less than 0.008, most preferably less than 0.008.
  • the mol% ratio (MgO+CaO)/(MgO+CaO+SrO+BaO) is an important component ratio in order to achieve both Young's modulus and meltability. If the mol % ratio (MgO+CaO)/(MgO+CaO+SrO+BaO) is too small, Young's modulus and meltability tend to be low. Therefore, the lower limit of the mol% ratio (MgO + CaO) / (MgO + CaO + SrO + BaO) is preferably 0.6, more preferably 0.7, still more preferably 0.8, still more preferably 0.9, most preferably 0.95. be.
  • the upper limit of the mol % ratio (MgO+CaO)/(MgO+CaO+SrO+BaO) is preferably 1, more preferably 0.99, still more preferably 0.98, and most preferably 0.97.
  • the "mol% ratio (MgO + CaO) / (MgO + CaO + SrO + BaO)" is a value obtained by dividing the total mol% content of MgO and CaO by the total mol% content of MgO, CaO, SrO and BaO.
  • the mol % ratio (B 2 O 3 +SrO+BaO)/Al 2 O 3 is an important component ratio for increasing Young's modulus and devitrification resistance. If the mol % ratio (B 2 O 3 +SrO+BaO)/Al 2 O 3 is too small, the devitrification resistance is lowered, and the manufacturing cost of the glass sheet tends to rise. Therefore, the lower limit of the mol% ratio (B 2 O 3 +SrO + BaO)/Al 2 O 3 is preferably 0.001, more preferably 0.005, still more preferably 0.008, still more preferably 0.01, still more preferably is 0.02, more preferably 0.03, more preferably 0.04, most preferably 0.05.
  • the upper limit of the mol% ratio (B 2 O 3 +SrO + BaO)/Al 2 O 3 is preferably 0.3, more preferably 0.25, still more preferably 0.2, still more preferably 0.15, still more preferably is 0.12, more preferably 0.1 and most preferably 0.09.
  • the mol % ratio (B 2 O 3 +SrO+BaO)/MgO is an important component ratio for increasing Young's modulus and devitrification resistance. If the mol % ratio (B 2 O 3 +SrO+BaO)/MgO is too small, the resistance to devitrification is lowered, and the manufacturing cost of the glass plate tends to rise. Therefore, the lower limit of the mol% ratio (B 2 O 3 +SrO+BaO)/MgO is preferably 0.001, more preferably 0.005, still more preferably 0.008, still more preferably 0.01, still more preferably 0.01. 02, more preferably 0.03, more preferably 0.04, most preferably 0.05.
  • the upper limit of the mol % ratio (B 2 O 3 +SrO+BaO)/MgO is preferably 0.5, more preferably 0.4, still more preferably 0.3, still more preferably 0.27, still more preferably 0.27. 24, more preferably 0.22, most preferably 0.2.
  • " ( B2O3 + SrO+BaO)/MgO” is a value obtained by dividing the total mol% content of B2O3 , SrO and BaO by the mol% content of MgO.
  • a suitable glass composition range can be obtained by appropriately combining the suitable content ranges of each component. 72%, Al 2 O 3 12-16%, B 2 O 3 0-1%, Li 2 O + Na 2 O + K 2 O 0-0.5%, MgO 6-12%, CaO 9-13%, SrO 0 It is particularly preferred to contain more than ⁇ 2%, BaO 0-1% and a mol% ratio SrO/SiO 2 of 0-0.008.
  • the following ingredients may be added as optional ingredients.
  • the total content of other components other than the above components is preferably 10% or less, particularly 5% or less.
  • P 2 O 5 is a component that raises the strain point and is a component that can remarkably suppress the precipitation of alkaline earth aluminosilicate-based devitrified crystals such as anorthite.
  • the content of P 2 O 5 is preferably 0 to 2.5%, more preferably 0 to 1.5%, still more preferably 0 to 0.5%, still more preferably 0 to 0.3%, particularly preferably is 0 to less than 0.1%.
  • TiO 2 is a component that lowers high-temperature viscosity and enhances meltability, as well as a component that suppresses solarization. However, if a large amount of TiO 2 is contained, the glass is colored and the transmittance tends to decrease. .
  • the content of TiO 2 is preferably 0-2.5%, more preferably 0.0005-1%, still more preferably 0.001-0.5%, particularly preferably 0.005-0.1%. be.
  • ZnO is a component that increases Young's modulus. However, if a large amount of ZnO is contained, the glass tends to devitrify and the strain point tends to decrease.
  • the content of ZnO is preferably 0-6%, more preferably 0-5%, even more preferably 0-4%, and particularly preferably 0.001-3%.
  • ZrO2 is a component that increases Young's modulus. However, if ZrO 2 is contained in a large amount, the glass tends to devitrify.
  • the content of ZrO 2 is preferably 0-2.5%, more preferably 0.0005-1%, still more preferably 0.001-0.5%, particularly preferably 0.005-0.1% .
  • Y 2 O 3 , Nb 2 O 5 and La 2 O 3 have the function of increasing the strain point and Young's modulus.
  • the total amount and individual content of these components are preferably 0 to 5%, more preferably 0 to 1%, even more preferably 0 to 0.5%, and particularly preferably 0 to less than 0.5%. If the total amount of Y 2 O 3 , Nb 2 O 5 and La 2 O 3 and the individual content are too large, the density and raw material costs tend to increase.
  • SnO 2 is a component that has a good refining action in a high temperature range, a component that raises the strain point, and a component that lowers the high-temperature viscosity.
  • the SnO 2 content is preferably 0-1%, 0.001-1%, 0.01-0.5%, especially 0.05-0.3%. When the SnO 2 content is too high, devitrified crystals of SnO 2 tend to precipitate. If the SnO 2 content is less than 0.001%, it becomes difficult to obtain the above effects.
  • SnO 2 is suitable as a refining agent, but as a refining agent instead of SnO 2 or together with SnO 2 , F, SO 3 , C, or Al, Si up to 5% (preferably up to 1%, especially up to 0.5%) of metal powders such as CeO 2 , F and the like can also be added up to 5% each (preferably up to 1%, especially up to 0.5%) as clarifiers.
  • As 2 O 3 and Sb 2 O 3 are also effective as clarifiers. However, As 2 O 3 and Sb 2 O 3 are components that increase environmental loads. As 2 O 3 is a component that lowers solarization resistance. Therefore, the alkali-free glass plate of the present invention preferably does not substantially contain these components.
  • Cl is a component that promotes the initial melting of the glass batch. Also, the addition of Cl can promote the action of the clarifier. As a result, it is possible to extend the life of the glass manufacturing kiln while reducing the melting cost. However, if the Cl content is too high, the strain point tends to decrease. Therefore, the Cl content is preferably 0 to 3%, more preferably 0.0005 to 1%, and particularly preferably 0.001 to 0.5%.
  • a raw material for introducing Cl a raw material such as a chloride of an alkaline earth metal oxide such as strontium chloride or aluminum chloride can be used.
  • Fe 2 O 3 is a component that is unavoidably mixed in from the glass raw material, and is a component that lowers the electric resistivity.
  • the content of Fe 2 O 3 is preferably 0-300 ppm by weight, 80-250 ppm by weight, especially 100-200 ppm by weight. If the content of Fe 2 O 3 is too small, raw material costs tend to rise. On the other hand, if the Fe 2 O 3 content is too high, the electric resistivity of the molten glass increases, making it difficult to perform electric melting.
  • the alkali-free glass plate of the present invention preferably has the following properties.
  • the average coefficient of thermal expansion in the temperature range of 30 to 380° C. is preferably 30 ⁇ 10 ⁇ 7 to 50 ⁇ 10 ⁇ 7 /° C., 32 ⁇ 10 ⁇ 7 to 48 ⁇ 10 ⁇ 7 /° C., 33 ⁇ 10 ⁇ 7 to 45 ⁇ 10 -7 /°C, 34 ⁇ 10 -7 to 44 ⁇ 10 -7 /°C, especially 35 ⁇ 10 -7 to 43 ⁇ 10 -7 /°C. In this way, it becomes easier to match the thermal expansion coefficient of Si used for TFTs.
  • Young's modulus is preferably 83 GPa or more, 83 GPa or more, 83.3 GPa or more, 83.5 GPa or more, 83.8 GPa or more, 84 GPa or more, 84.3 GPa or more, 84.5 GPa or more, 84.8 GPa or more, 85 GPa or more, 85. 3 GPa or more, 85.5 GPa or more, 85.8 GPa or more, 86 GPa or more, especially more than 86 to 120 GPa. If the Young's modulus is too low, defects due to bending of the glass plate are likely to occur.
  • Specific Young's modulus is preferably 32 GPa/g ⁇ cm ⁇ 3 or more, 32.5 GPa/g ⁇ cm ⁇ 3 or more, 33 GPa/g ⁇ cm ⁇ 3 or more, 33.3 GPa/g ⁇ cm ⁇ 3 or more, 33.5 GPa /g ⁇ cm ⁇ 3 or more, 33.8 GPa/g ⁇ cm ⁇ 3 or more, 34 GPa/g ⁇ cm ⁇ 3 or more, 34 GPa/g ⁇ cm ⁇ 3 or more, 34.2 GPa/g ⁇ cm ⁇ 3 or more, 34. 4 GPa/g ⁇ cm ⁇ 3 or more, particularly 34.5 to 37 GPa/g ⁇ cm ⁇ 3 . If the specific Young's modulus is too low, defects due to bending of the glass plate are likely to occur.
  • the strain point is preferably 730°C or higher, 732°C or higher, 734°C or higher, 735°C or higher, 736°C or higher, 738°C or higher, particularly 740 to 800°C. In this way, thermal shrinkage of the glass plate can be suppressed in the LTPS process.
  • the liquidus temperature is preferably 1350°C or less, less than 1350°C, 1300°C or less, 1290°C or less, 1285°C or less, 1280°C or less, 1275°C or less, 1270°C or less, particularly 1260 to 1200°C. By doing so, it becomes easy to prevent a situation in which devitrification crystals are generated during glass production and the productivity is lowered. Furthermore, since it becomes easy to shape
  • the liquidus temperature is an index of devitrification resistance, and the lower the liquidus temperature, the better the devitrification resistance.
  • the liquidus viscosity is preferably 10 4.0 dPa ⁇ s or more, 10 4.1 dPa ⁇ s or more, or 10 4.2 dPa ⁇ s or more, particularly 10 4.3 to 10 7.0 dPa ⁇ s.
  • devitrification is less likely to occur during molding, making it easier to mold by the overflow down-draw method.
  • the liquidus viscosity is an index of devitrification resistance and moldability, and the higher the liquidus viscosity, the better the devitrification resistance and moldability.
  • the temperature at a high temperature viscosity of 10 2.5 dPa ⁇ s is preferably 1650°C or less, 1630°C or less, 1610°C or less, especially 1400 to 1600°C. If the temperature at the high-temperature viscosity of 10 2.5 dPa ⁇ s is too high, it becomes difficult to melt the glass batch, and the manufacturing cost of the glass plate rises.
  • the temperature at a high-temperature viscosity of 10 2.5 dPa ⁇ s corresponds to the melting temperature, and the lower the temperature, the better the meltability.
  • the ⁇ -OH value is an index that indicates the amount of water in the glass, and lowering the ⁇ -OH value can raise the strain point. Further, even when the glass composition is the same, the smaller the ⁇ -OH value, the smaller the thermal shrinkage at a temperature below the strain point.
  • the ⁇ -OH value is preferably 0.35/mm or less, 0.30/mm or less, 0.28/mm or less, 0.25/mm or less, in particular 0.20/mm or less. In addition, if the ⁇ -OH value is too small, the meltability tends to decrease.
  • the ⁇ -OH value is therefore preferably greater than or equal to 0.01/mm, in particular greater than or equal to 0.03/mm.
  • Methods for lowering the ⁇ -OH value include the following methods. (1) Select raw materials with low water content. (2) adding components (Cl, SO3 , etc.) that lower the ⁇ -OH value into the glass; (3) Reduce the moisture content in the furnace atmosphere. (4) N2 bubbling in the molten glass; (5) Use a small melting furnace. (6) Increase the flow rate of molten glass. (7) Adopt an electric melting method.
  • ⁇ -OH value refers to the value obtained by measuring the transmittance of the glass using FT-IR and using Equation 1 below.
  • the alkali-free glass plate of the present invention is preferably formed by an overflow down-draw method.
  • the overflow down-draw method molten glass is overflowed from both sides of a heat-resistant gutter-shaped structure, and the overflowed molten glass is drawn downward while joining at the lower end of the gutter-shaped structure to produce a glass sheet.
  • the method In the overflow down-draw method, the surface to be the surface of the glass plate does not come into contact with the gutter-shaped refractory and is molded in the state of a free surface. Therefore, an unpolished glass plate having a good surface quality can be manufactured at low cost, and thinning is easy.
  • the alkali-free glass plate of the present invention is also preferably formed by the float method.
  • a large glass plate can be manufactured at low cost.
  • the alkali-free glass plate of the present invention preferably has a polished surface. Polishing the glass surface can reduce the total plate thickness deviation TTV. As a result, the magnetic film can be properly formed, making it suitable for substrates of magnetic recording media.
  • the plate thickness of the alkali-free glass plate of the present invention is not particularly limited. 05 to 0.5 mm is preferred. As the plate thickness becomes thinner, the weight of the organic EL device can be reduced. The plate thickness can be adjusted by adjusting the flow rate, drawing speed, etc. during glass production. On the other hand, when used for a magnetic recording medium, the plate thickness is preferably 1.5 mm or less, 1.2 mm or less, 0.2 to 1.0 mm, particularly 0.3 to 0.9 mm. If the plate thickness is too thick, etching must be performed to the desired plate thickness, which may increase the processing cost.
  • the alkali-free glass plate of the present invention is preferably used for organic EL devices, particularly substrates for organic EL television display panels and carriers for manufacturing organic EL display panels.
  • organic EL devices particularly substrates for organic EL television display panels and carriers for manufacturing organic EL display panels.
  • each device is divided and cut to reduce costs (so-called multi-panel production). Since the alkali-free glass plate of the present invention can be easily formed into a large glass plate, it can meet such requirements precisely.
  • the alkali-free glass plate of the present invention is excellent in productivity and sufficiently high in strain point and Young's modulus, it is preferably used as a substrate for magnetic recording media, particularly energy-assisted magnetic recording media.
  • the substrate including the glass plate is heat-treated at a high temperature of about 800° C. during or before or after forming the magnetic layer.
  • the alkali-free glass plate of the present invention is processed into a disk substrate 1 as shown in FIG. 1 by processing such as cutting.
  • the disk substrate 1 preferably has a disk shape, and more preferably has a circular opening C in the center.
  • Tables 1 to 3 represent examples of the present invention (Sample Nos. 1 to 30).
  • a glass batch prepared by mixing glass raw materials so as to have the glass composition shown in the table was placed in a platinum crucible and melted at 1600 to 1650° C. for 24 hours.
  • the glass batch was melted, it was homogenized by stirring using a platinum stirrer.
  • the molten glass was poured onto a carbon plate, shaped into a plate, and then slowly cooled at a temperature near the annealing point for 30 minutes.
  • average thermal expansion coefficient CTE, density ⁇ , Young's modulus E, specific Young's modulus E / ⁇ , strain point Ps, annealing point Ta, softening point Ts high temperature viscosity in the temperature range of 30 to 380 ° C.
  • the average coefficient of thermal expansion CTE in the temperature range of 30 to 380°C is the value measured with a dilatometer.
  • the density ⁇ is a value measured by the well-known Archimedes method.
  • Young's modulus E is a value measured by a well-known resonance method.
  • the specific Young's modulus E/ ⁇ is the value obtained by dividing the Young's modulus by the density.
  • strain point Ps, annealing point Ta, and softening point Ts are values measured based on the methods of ASTM C336 and C338.
  • the temperatures at high-temperature viscosities of 10 4 dPa ⁇ s, 10 3 dPa ⁇ s, and 10 2.5 dPa ⁇ s are values measured by the platinum ball pull-up method.
  • the liquidus temperature TL is the temperature at which crystals precipitate after passing through a 30-mesh (500 ⁇ m) standard sieve and remaining on the 50-mesh (300 ⁇ m) glass powder in a platinum boat and holding it in a temperature gradient furnace for 24 hours. be.
  • the liquidus viscosity log 10 ⁇ TL is a value obtained by measuring the viscosity of the glass at the liquidus temperature TL by the platinum ball pull-up method.
  • sample no. 1 to 30 have a Young's modulus of 88 GPa or more, a strain point of 738° C. or more, a liquidus temperature of 1300° C. or less, and a liquidus viscosity of 10 4.0 dPa s because the glass composition is regulated within a predetermined range. That's it. Therefore, sample no. 1 to 30 are suitable for substrates of organic EL devices and magnetic recording media because they are excellent in productivity and sufficiently high in strain point and Young's modulus.
  • the alkali-free glass plate of the present invention is suitable as a substrate for an organic EL device, particularly a substrate for an organic EL television display panel, and as a carrier for manufacturing an organic EL display panel. It is also suitable for cover glasses for image sensors such as charge-coupled devices (CCD) and 1:1 proximity solid-state imaging devices (CIS), substrates and cover glasses for solar cells, substrates for organic EL lighting, and the like.
  • CCD charge-coupled devices
  • CIS 1:1 proximity solid-state imaging devices
  • the alkali-free glass plate of the present invention has a sufficiently high strain point and Young's modulus, it is also suitable as a substrate for magnetic recording media.
  • the strain point is high, even if heat treatment at high temperature such as heat assist or laser irradiation is performed, deformation of the glass sheet is difficult to occur.
  • a higher heat treatment temperature can be employed when increasing Ku, making it easier to fabricate a magnetic recording device with a high recording density.
  • the Young's modulus is high, the glass plate is less likely to bend or flutter during high-speed rotation, so collision between the information recording medium and the magnetic head can be prevented.

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JP2000302475A (ja) * 1999-04-12 2000-10-31 Carl Zeiss:Fa アルカリ非含有アルミノ硼珪酸ガラスとその用途
WO2013161902A1 (ja) * 2012-04-27 2013-10-31 旭硝子株式会社 無アルカリガラスおよびその製造方法
WO2014175215A1 (ja) * 2013-04-23 2014-10-30 旭硝子株式会社 無アルカリガラス基板およびその製造方法
JP2015028827A (ja) * 2013-06-27 2015-02-12 旭硝子株式会社 磁気記録媒体用無アルカリガラス、および、これを用いた磁気記録媒体用ガラス基板

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KR102680019B1 (ko) * 2018-03-14 2024-07-02 에이지씨 가부시키가이샤 무알칼리 유리
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Publication number Priority date Publication date Assignee Title
JP2000302475A (ja) * 1999-04-12 2000-10-31 Carl Zeiss:Fa アルカリ非含有アルミノ硼珪酸ガラスとその用途
WO2013161902A1 (ja) * 2012-04-27 2013-10-31 旭硝子株式会社 無アルカリガラスおよびその製造方法
WO2014175215A1 (ja) * 2013-04-23 2014-10-30 旭硝子株式会社 無アルカリガラス基板およびその製造方法
JP2015028827A (ja) * 2013-06-27 2015-02-12 旭硝子株式会社 磁気記録媒体用無アルカリガラス、および、これを用いた磁気記録媒体用ガラス基板

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