WO2008004480A1 - Procédés destinés à produire un substrat de verre sans alcali - Google Patents

Procédés destinés à produire un substrat de verre sans alcali Download PDF

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Publication number
WO2008004480A1
WO2008004480A1 PCT/JP2007/062913 JP2007062913W WO2008004480A1 WO 2008004480 A1 WO2008004480 A1 WO 2008004480A1 JP 2007062913 W JP2007062913 W JP 2007062913W WO 2008004480 A1 WO2008004480 A1 WO 2008004480A1
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WO
WIPO (PCT)
Prior art keywords
glass substrate
alkali
free glass
producing
supply step
Prior art date
Application number
PCT/JP2007/062913
Other languages
English (en)
Japanese (ja)
Inventor
Satoshi Takeda
Shirou Tanii
Seiji Higashi
Original Assignee
Asahi Glass Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Asahi Glass Co., Ltd. filed Critical Asahi Glass Co., Ltd.
Priority to CN200780025869XA priority Critical patent/CN101489946B/zh
Priority to KR1020097000251A priority patent/KR101107369B1/ko
Priority to JP2008523658A priority patent/JP5239859B2/ja
Publication of WO2008004480A1 publication Critical patent/WO2008004480A1/fr

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Classifications

    • 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
    • C03C21/00—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface
    • C03C21/007—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in gaseous phase
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
    • 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
    • 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
    • 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
    • C03C23/00—Other surface treatment of glass not in the form of fibres or filaments
    • 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
    • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
    • 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
    • C03C2217/00—Coatings on glass
    • C03C2217/20—Materials for coating a single layer on glass
    • C03C2217/28—Other inorganic materials
    • 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
    • C03C2217/00—Coatings on glass
    • C03C2217/20—Materials for coating a single layer on glass
    • C03C2217/28—Other inorganic materials
    • C03C2217/283—Borides, phosphides
    • 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
    • C03C2218/00—Methods for coating glass
    • C03C2218/30—Aspects of methods for coating glass not covered above
    • C03C2218/355—Temporary coating
    • 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
    • G02F1/133302—Rigid substrates, e.g. inorganic 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 a method for producing an alkali-free glass substrate.
  • Many glass substrates including a glass substrate for display are manufactured by a float process or a fusion process. Unlike the fusion method, the float method is superior in that it can efficiently produce large-area glass substrates.
  • This float method generally includes a molding step for forming molten glass on a glass substrate on molten tin in a molten tin bath, and a slow cooling step for gradually cooling the glass substrate formed by the molding step. It is a life.
  • the glass substrate molded by this molding process is transported by the roller after leaving the molten tin bath, so the back surface (the surface that hits the roller) is damaged during transportation! Teshima! There was a problem that the quality of the glass substrate deteriorated.
  • SO gas sulfurous acid gas
  • Patent Document 1 and Non-Patent Document 1 See) o
  • Patent Document 1 International Publication No. 2002Z051767 Pamphlet
  • Non-Patent Document 1 U. Senturk etc, J. Non— Cryst. Solids, No. 222, p. 160 (199 7)
  • non-alkali glass when manufacturing a glass substrate composed of glass that does not substantially contain an alkali metal (hereinafter also referred to as “non-alkali glass”), depending on the method of blowing sulfurous acid gas, sodium sulfate may be used. It is not formed, and salts such as calcium sulfate and strontium sulfate, which are reaction products with alkaline earth metals, are formed on the glass substrate. Although these salts derived from alkaline earth metals act as protective films to prevent scratches on the glass substrate, their production efficiency is significantly lower than that of sodium sulfate, so their effects may not be sufficient. there were. Moreover, since it is a hardly water-soluble salt even if it is produced, there is a problem that it is extremely difficult to remove in a subsequent washing step.
  • non-alkali glass is required to have a high-quality surface such as a flat panel display, and if there is a scratch on the glass substrate, it will cause defects such as poor disconnection, so that scratches smaller than those for window glass and automotive glass are also a problem. .
  • the present invention is a method for producing a glass substrate made of alkali-free glass (hereinafter also referred to as “alkali-free glass substrate”) used in a liquid crystal display, and is easily removed in a cleaning process.
  • An object is to provide an alkali-free glass substrate obtained by the above.
  • an inorganic substance containing an alkali metal is in contact with the molten tin of the glass substrate in the production process by the float process. Blow the surface to supply alkali metal, then blow SO gas to the surface.
  • the present invention provides the following (1) to (14).
  • a non-alkali glass substrate manufacturing method comprising: a second supplying step.
  • the glass substrate is a mass percentage display based on oxide
  • Alkali metal component 0.5% or less
  • Alkali metal component 0.5% or less
  • a protective coating that can be easily removed in a cleaning process is efficiently generated, and the amount of sulfurous acid gas used is reduced while reducing the amount of sulfur dioxide used.
  • a method for producing an alkali-free glass substrate that suppresses the generation of scratches and an alkali-free glass substrate obtained by the production method can be provided.
  • FIG. 1 is a conceptual diagram showing an example of a glass production line by a float process.
  • FIG. 2 is a cross-sectional view of the large tubular furnace used in the examples.
  • FIG. 3 is an explanatory view showing a portion (wear portion) hit by a wear ring and a site for measuring the number of scratches (measurement portion) of the Taber experimental machine used for evaluation of scratch resistance.
  • the method for producing an alkali-free glass substrate according to the first aspect of the present invention is a method for producing an alkali-free glass substrate for producing an alkali-free glass substrate by a float process.
  • an inorganic substance containing an alkali metal (hereinafter also referred to as “alkali metal-containing inorganic substance”) is sprayed on the surface of the glass substrate that contacts the molten tin (hereinafter also referred to as “bottom surface”).
  • the surface of the glass substrate on the side in contact with the molten tin, that is, the bottom surface on which the inorganic substance is sprayed is SO.
  • a method for producing an alkali-free glass substrate comprising a second supply step of blowing gas.
  • the manufacturing method of the present invention further includes a cleaning step for removing the protective film.
  • the forming step is a step of forming molten glass on a glass substrate on molten tin in a molten tin bath, and is a conventionally known step in a general float method.
  • FIG. 1 is a conceptual diagram showing an example of a glass production line by a float process.
  • molten glass 4 flows continuously from the melting furnace 3 to form a glass ribbon.
  • the glass ribbon is advanced along the bath surface of the molten tin bath 2 while being buoyant, so that the glass ribbon is formed into a plate shape as the temperature decreases.
  • the glass substrate thus produced is drawn out by the drawing roll 5 and is conveyed to the slow cooling furnace 6 in a continuous state in the longitudinal direction.
  • the forming step is a step until the molten glass 4 is formed into a plate shape through a glass ribbon.
  • the molten tin bath 2 is composed of a tin bath furnace and a ceiling wall lined with a special refractory on the inside of a metal case, and tin oxide is used. To prevent this, use a sealed structure.
  • a mixed gas composed of hydrogen and nitrogen hydrogen content: 2 to 10% by volume
  • the temperature condition in the molten tin bath in the molding step is 600 to 1050 ° C., that is, the temperature of the molten glass flowing into the molten tin bath is 900 to 1050 ° C. Therefore, it is possible to achieve a force S of 600-800 ° C on the downstream side. Note that this temperature is normally maintained by the amount of heat of the molten glass. A heater or cooler may be used to adjust the temperature.
  • an alkali-free glass substrate is formed on molten tin by the above-described forming step.
  • the non-crisp glass is glass that does not substantially contain an alkali metal as described above.
  • the alkali-free glass is represented by a mass percentage display based on an oxide,
  • alkali metal component refers to an alkali metal component inevitably contained regardless of the first supply step described later.
  • the slow cooling step is a step of slowly cooling the glass substrate formed by the forming step.
  • the glass substrate that has been made is pulled out by the pulling roll 5 and then transferred to the slow cooling furnace 6 in a continuous state in the longitudinal direction until it is gradually cooled. It is this process.
  • the slow cooling furnace may be the same as that used in a general float method, and a heater or the like may be provided for temperature control.
  • the annealing conditions in the annealing furnace in the annealing process can be set to temperatures of 550 to 750 ° C at the inlet of the annealing furnace and 200 to 300 ° C at the outlet, as in the general float method. Yes, the speed of temperature drop can be 90 ° C ⁇ 10 ° C / m.
  • the first supply step is a step of spraying an alkali metal-containing inorganic substance onto the bottom surface of the glass substrate to supply the alkali metal to the bottom surface.
  • the alkali metal-containing inorganic substance means an inorganic substance containing an alkali metal as described above, and includes, for example, lithium (Li), sodium (Na), potassium (K), cesium (Cs) and the like. This applies to inorganic substances.
  • an alkali metal is supplied to the bottom surface of the glass substrate, and then SO gas is blown to form an alkali sulfate salt.
  • a protective coating can be produced efficiently.
  • this protective film can be easily removed by a cleaning process. Furthermore, the same protective effect can be obtained even if the amount of SO gas is reduced.
  • alkali metal-containing inorganic substance It reacts preferentially with the alkali metal generated, and it is a water-insoluble solution that exists even in alkali-free glass. This is thought to be because the reaction with alkaline earth metals (Ca, Sr, etc.) is suppressed.
  • alkali metal source called an alkali metal-containing inorganic substance
  • the same protective effect can be achieved with a small amount of SO gas compared to the amount of SO gas used to obtain reactive organisms (calcium sulfate, strontium sulfate, etc.) as a protective coating.
  • inorganic substance containing Na include, for example, NaOH, Na S, NaCl, N
  • Na and the like can be mentioned, and these may be used alone or in combination of two or more.
  • inorganic substances containing K include, for example, KOH, KC1, KF, KBr, KI, KCN, KCO, potassium gnoleconate, KHF, KNO, KBO-4H O (tetraboric acid Cali
  • the inorganic substance containing Cs include CsOH, CsCl, CsF, CsBr, Csl, cesium acetylethylacetonate, HCO Cs, and CsNO.
  • Species may be used alone or in combination of two or more.
  • the alkali metal-containing inorganic substance is an inorganic substance containing Na
  • the production efficiency of the protective film (sodium sulfate) formed in the second supply step, which will be described later, is further improved and easy to remove with water. Preferred because it becomes.
  • the alkali metal-containing inorganic material strength Na and boron-containing inorganic material are alkali-free glass substrate strength obtained by the production method of the present invention, and further have wear resistance even after the cleaning step described later. Therefore, it is more preferable.
  • Na B sodium B
  • Na B O is preferred Na B O—10H O is more preferred
  • a high level of scratch resistance can be satisfied by utilizing this diffusion of boron to a glass substrate for a black chip / biochip.
  • the first supply step is a force for supplying alkali metal to the bottom surface by spraying such an alkali metal-containing inorganic substance onto the bottom surface of the glass substrate.
  • the spraying method the following modes are suitably exemplified.
  • the timing of spraying the alkali metal-containing inorganic substance is not particularly limited as long as it is before the second supply step described later. Specifically, even at the same time as the molding step described above, the timing is gradually decreased. Although it may be simultaneous with the cooling step, it is preferable that it is between the molding step and the slow cooling step because the occurrence of scratches on the back surface of the glass substrate can be further suppressed.
  • “simultaneously with the molding process” means a stage immediately after forming the glass substrate in the molding process and included in the molding process, for example, a forming furnace, a molten tin bath (float bath), and the entire furnace.
  • an exit portion shield rare
  • “simultaneously with the slow cooling step” means that the spraying may be performed near the inlet of the slow cooling furnace or upstream of the slow cooling furnace.
  • between the forming step and the slow cooling step means that the glass substrate may be sprayed between the forming furnace and the slow cooling furnace.
  • the method of spraying the alkali metal-containing inorganic substance is, for example, a method of heating and vaporizing the alkali metal-containing inorganic substance and spraying the vaporized substance onto the bottom surface of the glass substrate using a nozzle;
  • a method of heating and vaporizing an alkali metal-containing inorganic substance by heating, infrared lamp heating, laser heating, etc. is preferred.
  • the vaporizing substance is sprayed at a temperature in the range of the glass transition temperature of the glass substrate ⁇ 100 ° C.
  • the glass transition point of the glass substrate is preferably in the range of 30 ° C to glass transition point + 100 ° C. This is because if the spraying is performed within this temperature range, the glass becomes soft at the glass transition point, so that a film can be formed in that region, thereby preventing damage more effectively.
  • the force applied at 600-800 ° C vaporizes the substance efficiently, and the glass This is preferable in that the substrate temperature does not drop abruptly when sprayed onto the substrate surface.
  • spraying of the vaporized material 0. 2:
  • the LOLZm that is 2 to is preferred instrument 0. 2 ⁇ 3L / m 2 is more preferred instrument 0. 2 ⁇ lL / m 2 Is particularly preferred.
  • the spraying amount is within this range, the bottom surface of the glass substrate is suppressed while suppressing the amount of SO gas spraying.
  • the supply amount of the alkali metal to be supplied becomes sufficient, and the production efficiency of the protective film formed by reacting with the SO gas sprayed in the second supply step described later is further improved.
  • sodium tetraborate decahydrate When sodium tetraborate decahydrate is used as the alkali metal-containing inorganic substance, it is 850 ° in a furnace other than a glass substrate forming furnace and a slow cooling furnace (for example, a large tube furnace used in the examples). After vaporizing sodium tetraborate at a temperature of about C, the vaporized material is about 700 ° C. using a nozzle, and the glass substrate transported between these forming furnaces or slow cooling furnaces or between these furnaces is used. A method of spraying on the bottom surface is a preferred embodiment.
  • the alkali metal is supplied to the bottom surface of the glass substrate.
  • the presence of alkali metal on the bottom surface of the glass substrate can be confirmed by X-ray photoelectron spectroscopy (XPS) or fluorescent X-ray analysis of the bottom surface of the glass substrate.
  • XPS X-ray photoelectron spectroscopy
  • This second supply step is different from a conventionally known step in a general float method in that a protective film is formed on the bottom surface of the glass substrate supplied with the alkali metal.
  • the alkali metal and the SO gas are sprayed by blowing SO gas onto the bottom surface of the glass substrate to which the alkali metal has been supplied in the first supply step.
  • alkali sulfate eg, sodium sulfate
  • Timing (timing) and spraying of SO gas in the second supply step About the method, the aspect shown below is illustrated suitably.
  • the timing of blowing the SO gas is not particularly limited as long as it is after the first supply step.
  • a method of blowing SO gas is a conventionally known method in a general float method.
  • the same protective effect is ensured as compared with the conventional example using a sulfate (eg, calcium sulfate) derived from an alkaline earth metal as a protective coating on the alkali-free glass substrate.
  • a sulfate eg, calcium sulfate
  • SO gas SO gas
  • the amount of spray can be reduced. As described above, this is because the SO gas sprayed in the second supply process was supplied to the bottom surface.
  • alkali metals (Ca, Sr, etc.), which reacts preferentially with alkali metals and is less reactive than alkali-free glasses, is suppressed.
  • SO particularly 0.05 to 0.3.
  • LZm 2 can be reduced.
  • the SO gas is sprayed at a temperature in the range of ⁇ 100 ° C of the glass transition point of the glass substrate.
  • the so 2 gas spraying is more preferably performed at 600 to 800 ° C.
  • a protective coating made of sulfate that can be easily removed in the cleaning process is generated more efficiently, and the occurrence of scratches on the back surface of the glass substrate is further suppressed. It is the power that can be.
  • the cleaning step performed as desired is a step of cleaning and removing the protective film formed in the second supply step, and is a conventionally known step in a general float method.
  • the timing (timing) of the cleaning step and the cleaning method the following modes are preferably exemplified.
  • the timing of the cleaning step is not particularly limited as long as it is after the second supply step, but the protective coating is made against a scratch on the surface (bottom surface) of the glass substrate that occurs during roller conveyance. Therefore, the final stage of the slow cooling step or immediately after the slow cooling step is preferable.
  • the cleaning method in the above-described cleaning step is an easy method because a protective film made of a sulfate derived from alkali metal (for example, a water-soluble salt such as sodium sulfate) is formed in the present invention. For example, it can be removed by washing with water. If the first supply process is not performed and SO gas is sprayed, the glass substrate
  • the protective coating formed on the tom surface becomes a sulfate derived from an alkaline earth metal (for example, a poorly water-soluble salt such as calcium sulfate), which makes it difficult to clean easily.
  • an alkaline earth metal for example, a poorly water-soluble salt such as calcium sulfate
  • the smoothness of the obtained alkali-free glass substrate is improved, and the distortion, undulation, microcorrugation, scratches and foreign matter defects of the glass substrate are reduced, and the uniformity is high.
  • a polishing step may be provided as necessary after the cleaning step.
  • This polishing process is a conventionally known process in a general float process. Specifically, the polishing process is a glass substrate placed on urethane foam using an acid-cerium-based abrasive. The method of polishing is mentioned.
  • a method for producing an alkali-free glass substrate according to the second aspect of the present invention is a method for producing an alkali-free glass substrate by a float method, wherein the molten glass is glass on molten tin.
  • a molding process for molding on a substrate is a method for producing an alkali-free glass substrate by a float method, wherein the molten glass is glass on molten tin.
  • 2 is a method for producing an alkali-free glass substrate, comprising a second supplying step.
  • the forming step in the second aspect of the present invention is the same as that described in the first aspect of the present invention, and the temperature is set to 600 for the first supply step and the second supply step. Except for the range of ⁇ 800 ° C., the same as described in the first embodiment of the present invention. Also in the second aspect of the present invention, it is preferable to include the above-described cleaning step, and it is possible to further include the above-described polishing step.
  • the present invention can be obtained by the production method of the present invention when an inorganic substance containing Na and boron is used in the production method of the present invention (including the second aspect, the same shall apply hereinafter).
  • the present invention also provides a non-alkali glass substrate.
  • an alkali-free glass substrate is provided by spraying an inorganic substance containing Na and boron onto the bottom surface of the glass substrate in the first supply step, and then performing the cleaning step as necessary. be able to.
  • the alkali-free glass substrate of the present invention preferably has the following composition.
  • the glass substrate is expressed in terms of mass percentage based on oxide
  • Alkali metal component 0.5% or less
  • the average boron concentration of the bottom surface of the glass substrate is 4 to: L0 atomic%, and the diffusion depth of boron into the glass substrate is 5 nm or more.
  • the SiO content (expressed in terms of mass percentage based on oxide) is 50 to 80%.
  • the content of Al 2 O (expressed in terms of mass percentage based on oxide) is preferably 0 to 30%.
  • 3-22% is more preferred 3-20% is more preferred 15-20 % Is particularly preferred, with 15-19% being most preferred.
  • the content of B 2 O (expressed in terms of mass percentage based on oxide) is preferably 0 to 30%.
  • the content of MgO (expressed in terms of mass percentage based on oxide) is preferably 0 to 20%, more preferably 0 to 8%, and even more preferably 0 to 6%. .
  • the content of CaO (expressed in terms of mass percentage based on oxide) is preferably 0 to 20%, more preferably 0 to 9%, and even more preferably 0 to 8%. .
  • the SrO content (expressed as a percentage by mass on the oxide basis) is preferably 0 to 20%, more preferably 0 to 12.5%, and 3 to 12.5%. Is more preferable. Further, the BaO content (expressed in terms of mass percentage based on oxide) is preferably 0 to 20%, more preferably 0% or more and less than 2%.
  • the content of alkali metal component (expressed in terms of mass percentage based on oxide) is preferably 0.5% or less, more preferably 0.2% or less, and more preferably 0.1% or less. More preferably.
  • the content of the alkali metal component is in the range of the composition of the alkali-free glass used for the alkali-free glass substrate.
  • the average boron concentration on the bottom surface of the glass substrate can be obtained as an average value when arbitrarily measured at five points by X-ray photoelectron spectroscopy.
  • X-ray photoelectron spectroscopy an XPS spectrometer (5500 type, manufactured by PHI) was used, and X-rays ⁇ rays monochromatized with a monochromator were used as the X-ray source.
  • the X-ray photoelectron detection angle was 75 °, and measurement was performed by irradiating an electron shower to correct charging.
  • the diffusion depth of boron into the glass substrate is estimated from the depth at which the secondary ion intensity reaches the same level as the background by secondary ion mass spectrometry (SIMS). Is pretty.
  • the diffusion depth was measured at five points on each of the five points on the glass substrate using a secondary ion mass spectrometer (ADEPT1010, ULVAC “Phine”), and the average value was obtained.
  • the primary ion is an oxygen ion beam
  • the acceleration voltage is 5 keV
  • the beam current is 400 ⁇
  • the incident angle of the primary ion is 45 degrees with respect to the normal of the sample surface
  • the beam scanning range is 400 X 400 ⁇ m 2 Measured with
  • the average boron concentration of the bottom surface of the glass substrate is 4 to: L0 atomic%, and the diffusion depth of boron into the glass substrate is 5 nm or more and 80 nm.
  • the thickness is preferably 50 nm or less, the strength of the glass substrate itself is improved, the wear resistance is excellent, and the transportation and processing steps after the protective coating is removed! Even if it is, it will be excellent in scratch resistance.
  • the reason why boron has a bottom surface force also diffuses into the glass substrate and remains on the surface of the glass substrate, so that the wear resistance and the scratch resistance are improved is because the glass network structure is strengthened. Conceivable.
  • the alkali-free glass substrate of the present invention is not limited to the glass substrate because boron remains on the surface layer of the glass substrate not only before the cleaning step but also after the cleaning step if necessary. Since it is possible to continue to suppress the occurrence of scratches on the back surface, it is preferable.
  • the present invention represents the oxide-based mass percentage
  • Alkali metal component 0.5% or less
  • an alkali-free glass substrate having an average boron concentration of at least one surface of 4 to 10 atomic% and a surface force of boron diffusion depth of 5 nm or more inside. Togashi.
  • FIG. 2 is a cross-sectional view of the large tubular furnace used in the examples.
  • a quartz tube 12 is installed in a large-sized tubular furnace 11 whose temperature can be adjusted, and a non-alkali glass substrate 13 (10 cm square) having a thickness of 0.7 mm is placed in the quartz tube 12, and the large tubular furnace 11 is placed.
  • ⁇ Non-alkali glass substrate '' is expressed in terms of mass percentage based on oxide, 68% ⁇ SiO ⁇ 80%, 0% ⁇ A1 O ⁇ 12%, 0% ⁇ B O ⁇ 7
  • the sodium tetraborate decahydrate reagent 15 placed in the alumina boat 14 is locally heated to about 850 ° C to vaporize the vaporized material, and the end force of the quartz tube also moves in the direction indicated by the arrow 16.
  • sodium which is an alkali metal
  • the spray amount of sodium tetraborate decahydrate at this time was 0.4 L / m 2 , and the temperature of the alkali-free glass substrate 13 was 700 ° C.
  • SO gas was sprayed from the direction indicated by the arrow 17 to form a protective coating so that the amount of spraying on the surface of the alkali-free glass substrate 13 was 0.1 lZm 2 .
  • An alkali-free glass substrate was produced.
  • the temperature of the alkali-free glass substrate 13 at this time was 700 ° C.
  • the conditions are the same as those in which an alkali metal-containing inorganic substance was sprayed between the molding step and the slow cooling step and so gas was sprayed immediately thereafter.
  • the protective coating was applied in the same manner as in Example 1 except that the amount of SO gas sprayed was 0.4 LZm 2.
  • the protective coating was applied in the same manner as in Example 1 except that the amount of SO gas sprayed was 1. OLZm 2.
  • a non-alkali glass substrate with a film was produced.
  • Example 2 The same as Example 1 except that sodium tetraborate was not used and only SO gas was sprayed.
  • the alkali-free glass substrate with a protective film was manufactured by the method.
  • Example 2 Same as Example 2 except that sodium tetraborate was not used and only SO gas was sprayed.
  • the alkali-free glass substrate with a protective film was manufactured by the method.
  • Example 3 Same as Example 3 except that sodium tetraborate was not used and only SO gas was sprayed.
  • the alkali-free glass substrate with a protective film was manufactured by the method.
  • a non-alkali glass substrate was produced in the same manner as in Example 1 except that.
  • Example 2 Same as Example 1 except that sodium tetraborate was not used and SO gas was also applied.
  • An alkali-free glass substrate was produced by the method described above.
  • the obtained protective coating of each alkali-free glass substrate with protective coating was dissolved in pure water, sulfur was quantified using ICP emission analysis, and sodium was quantified using atomic absorption spectrometry.
  • the amount of sodium sulfate adhering was calculated as the amount of protective coating adhered. I put it out.
  • the adhesion amount was determined as an average value calculated from 10 sheets of the obtained alkali-free glass substrate.
  • the scratch resistance was evaluated by a Taber test according to JIS R3221 (1990).
  • the Taber test was conducted using a Taber tester (Tdedyne Taber Model 503), with the wear wheel fixed to CS-10F, the load fixed to 250 g, and the wear frequency fixed to 3 times. Thereafter, in order to remove the protective coating of each alkali-free glass substrate with a protective coating used as a test specimen, the substrate was washed with a shower for 30 seconds under flowing pure water (3 liters Z) at 20 ° C.
  • the surface of the glass substrate obtained by removing the protective film was observed with a microscope, and the number of scratches (number of scratches) with a length of 0.2 mm or more in the long axis direction existing within 1 cm ⁇ 1 cm square was measured. .
  • the measurement part was the central part of the part subjected to the Taber test (see Fig. 3). In FIG. 3, a wear part 19 due to a wear ring is formed on a specimen (non-alkali glass substrate) 18, but the measurement part 20 is the central part of the wear part 19.
  • the number of scratches was measured for 10 arbitrary points on each glass substrate, and the average value was obtained. Furthermore, the number of scratches was determined as an average value obtained by calculating the 10-sheet force of the obtained glass substrate.
  • the primary ions are measured under the conditions of an oxygen ion beam, acceleration voltage is 5 keV, beam current is 400 nA, the incident angle of primary ions is 45 degrees with respect to the normal of the sample surface, and the beam scanning range is 400 X 400 IX m 2. did.
  • Abrasion resistance was determined by examining the rate of change in the haze rate before and after the Taber test (rate of change in haze).
  • the haze ratio of each obtained alkali-free glass substrate was measured with a haze meter.
  • the obtained alkali-free glass substrate was subjected to a Taber test according to JIS R3221 (1990). The Taber test was conducted using a Taber tester (Tdedyne Taber Model 503), with the wear wheel fixed to CS-10F and the load fixed to 500 g.
  • the haze value is defined by the scattered light (Td) and the transmitted light (Tt) as follows.
  • the non-alkali glass substrates of Examples 1 to 3 had a clean surface after the protective coating formed on the surface of the glass substrate was removed after normal water washing.
  • the protective coating formed on the surface of the glass substrate could not be removed even after ordinary water washing, and remained. Further, when the components of the remaining film were measured, they were calcium sulfate and strontium sulfate.
  • the alkali-free glass substrates of Examples 1 to 3 have a reduced haze change rate and improved wear resistance compared to the alkali-free glass substrates of Comparative Examples 1 to 5 due to diffusion of boron. It was a component.
  • a non-alkali which efficiently generates a protective film that can be easily removed in a cleaning process, and suppresses the occurrence of scratches on the back surface of the glass substrate while reducing the amount of sulfurous acid gas used.
  • a method for producing a glass substrate and an alkali-free glass substrate obtained by the production method can be provided.
  • the alkali-free glass substrate of the present invention can be suitably used for high-quality displays.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Glass Compositions (AREA)

Abstract

L'invention concerne un procédé de production d'un substrat de verre sans alcali dans lequel un film de revêtement protecteur pouvant être facilement éliminé au cours d'une étape de nettoyage est fabriqué efficacement et le côté arrière du substrat de verre étant protégé contre les dommages lors de la réduction de la quantité de dioxyde de soufre à utiliser; et un substrat de verre sans alcali obtenu au moyen de ce procédé. Ce procédé destiné à produire un substrat de verre sans alcali produit un substrat de verre sans alcali au moyen d'un procédé de flottage. Il comprend une étape de formation au cours de laquelle un verre fondu est recuit. Le procédé comprend, en outre, une première étape d'alimentation au cours de laquelle une substance minérale contenant un métal alcalin est soufflé contre cette surface de substrat de verre qui était en contact avec l'étain fondu et une seconde étape d'alimentation au cours de laquelle après la première étape d'alimentation, un gaz de SO2 est soufflé contre cette surface de substrat de verre qui était en contact avec l'étain fondu.
PCT/JP2007/062913 2006-07-07 2007-06-27 Procédés destinés à produire un substrat de verre sans alcali WO2008004480A1 (fr)

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CN200780025869XA CN101489946B (zh) 2006-07-07 2007-06-27 无碱玻璃基板的制造方法
KR1020097000251A KR101107369B1 (ko) 2006-07-07 2007-06-27 무알칼리 유리 기판의 제조 방법
JP2008523658A JP5239859B2 (ja) 2006-07-07 2007-06-27 無アルカリガラス基板の製造方法

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WO2008120535A1 (fr) * 2007-04-03 2008-10-09 Asahi Glass Company, Limited Procédé de production de verre plat, appareil servant à former une couche tampon de verre plat et équipement de production de verre plat
WO2009148141A1 (fr) * 2008-06-06 2009-12-10 旭硝子株式会社 Appareil et procédé de fabrication de glace
WO2014148046A1 (fr) * 2013-03-19 2014-09-25 日本板硝子株式会社 Plaque de verre et procédé pour la fabrication de plaque de verre
JP2014525388A (ja) * 2011-09-02 2014-09-29 エルジー・ケム・リミテッド 無アルカリガラス及びその製造方法
US8895462B2 (en) 2011-09-02 2014-11-25 Lg Chem, Ltd. Alkali-free glass and preparation thereof
KR20200130266A (ko) 2018-03-09 2020-11-18 에이지씨 가부시키가이샤 무알칼리 유리 기판

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EP2641881A4 (fr) * 2010-11-18 2015-01-21 Asahi Glass Co Ltd Appareil pour fabriquer une feuille de verre et procédé de fabrication de ladite feuille de verre
CN103384648A (zh) 2011-02-21 2013-11-06 Lg化学株式会社 用于在玻璃表面上形成润滑剂层的方法以及使用该方法来制造玻璃的方法
WO2013032292A2 (fr) * 2011-09-02 2013-03-07 주식회사 엘지화학 Verre sans alcali et procédé de fabrication de ce verre
WO2013032289A2 (fr) * 2011-09-02 2013-03-07 주식회사 엘지화학 Verre sans alcali et procédé de fabrication de ce verre
CN107759055B (zh) * 2012-03-14 2020-12-04 Ａｇｃ株式会社 浮法玻璃板及其制造方法
JP2014240346A (ja) * 2013-05-15 2014-12-25 日本電気硝子株式会社 強化用ガラス板及び強化ガラス板
CN103936301A (zh) * 2014-04-30 2014-07-23 成都光明光电股份有限公司 浮法玻璃的制造方法、浮法玻璃及制造设备
CN106573830A (zh) * 2014-06-20 2017-04-19 旭硝子株式会社 玻璃板及其制造方法

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JP5223861B2 (ja) * 2007-04-03 2013-06-26 旭硝子株式会社 板ガラスの製造方法、板ガラスの緩衝層形成装置及び板ガラスの製造設備
WO2008120535A1 (fr) * 2007-04-03 2008-10-09 Asahi Glass Company, Limited Procédé de production de verre plat, appareil servant à former une couche tampon de verre plat et équipement de production de verre plat
KR101503964B1 (ko) 2008-06-06 2015-03-18 아사히 가라스 가부시키가이샤 판유리의 제조 장치 및 판유리의 제조 방법
CN102046542A (zh) * 2008-06-06 2011-05-04 旭硝子株式会社 平板玻璃的制造装置及平板玻璃的制造方法
CN102046542B (zh) * 2008-06-06 2013-07-24 旭硝子株式会社 平板玻璃的制造装置及平板玻璃的制造方法
JP5387920B2 (ja) * 2008-06-06 2014-01-15 旭硝子株式会社 板ガラスの製造装置及び板ガラスの製造方法
WO2009148141A1 (fr) * 2008-06-06 2009-12-10 旭硝子株式会社 Appareil et procédé de fabrication de glace
JP2014525388A (ja) * 2011-09-02 2014-09-29 エルジー・ケム・リミテッド 無アルカリガラス及びその製造方法
US8895462B2 (en) 2011-09-02 2014-11-25 Lg Chem, Ltd. Alkali-free glass and preparation thereof
WO2014148046A1 (fr) * 2013-03-19 2014-09-25 日本板硝子株式会社 Plaque de verre et procédé pour la fabrication de plaque de verre
US20160023946A1 (en) * 2013-03-19 2016-01-28 Nippon Sheet Glass Company, Limited Glass sheet and method for producing glass sheet
JPWO2014148046A1 (ja) * 2013-03-19 2017-02-16 日本板硝子株式会社 ガラス板及びガラス板の製造方法
US10399894B2 (en) 2013-03-19 2019-09-03 Nippon Sheet Glass Company, Limited Glass sheet and method for producing glass sheet
KR20200130266A (ko) 2018-03-09 2020-11-18 에이지씨 가부시키가이샤 무알칼리 유리 기판

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CN101489946A (zh) 2009-07-22
KR20090029785A (ko) 2009-03-23
JP5239859B2 (ja) 2013-07-17
TW200811068A (en) 2008-03-01
KR101107369B1 (ko) 2012-01-19
TWI379815B (fr) 2012-12-21
CN101489946B (zh) 2011-12-07
TW201300334A (zh) 2013-01-01

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