WO2015046118A1 - Plaque de verre - Google Patents

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Publication number
WO2015046118A1
WO2015046118A1 PCT/JP2014/075019 JP2014075019W WO2015046118A1 WO 2015046118 A1 WO2015046118 A1 WO 2015046118A1 JP 2014075019 W JP2014075019 W JP 2014075019W WO 2015046118 A1 WO2015046118 A1 WO 2015046118A1
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WIPO (PCT)
Prior art keywords
glass
glass plate
fluorine
fluorine concentration
depth
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PCT/JP2014/075019
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English (en)
Japanese (ja)
Inventor
聡史 宮坂
亮祐 加藤
正信 白井
信彰 井川
丈宜 三浦
山中　一彦
泰夫 林
史朗 谷井
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旭硝子株式会社
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Priority to JP2015539192A priority Critical patent/JPWO2015046118A1/ja
Publication of WO2015046118A1 publication Critical patent/WO2015046118A1/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
    • C03C23/00—Other surface treatment of glass not in the form of fibres or filaments
    • C03C23/0005—Other surface treatment of glass not in the form of fibres or filaments by irradiation
    • C03C23/0055—Other surface treatment of glass not in the form of fibres or filaments by irradiation by ion implantation
    • 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
    • C03C21/001—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions
    • C03C21/002—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions to perform ion-exchange between alkali ions
    • 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

Definitions

  • the present invention relates to a glass plate.
  • a thin plate-like cover glass is disposed on the front surface of the display.
  • Such a flat panel display device is required to be lightweight and thin, and accordingly, a cover glass used for display protection is also required to be thin.
  • the conventional cover glass raises the damage resistance of the cover glass by forming the compressive-stress layer on the surface by chemically strengthening the glass manufactured by the float method (henceforth a float glass). .
  • the warpage includes a glass surface that is not in contact with a molten metal such as molten tin (hereinafter also referred to as a top surface) and a glass surface that is in contact with the molten metal (hereinafter also referred to as a bottom surface). It is said that this is caused by the different ways of entering chemical strengthening on both sides.
  • a molten metal such as molten tin
  • a bottom surface a glass surface that is in contact with the molten metal
  • the warp of the float glass increases as the chemical strengthening becomes stronger. Therefore, when the surface compressive stress is made higher than ever, particularly 600 MPa or higher in order to meet the demand for high scratch resistance, the problem of warp becomes more obvious.
  • Patent Document 1 discloses a glass strengthening method in which the amount of ions entering the glass during chemical strengthening is adjusted by chemically strengthening after forming a SiO 2 film on the glass surface.
  • Patent Documents 2 and 3 disclose a method of reducing warpage after chemical strengthening by setting the surface compressive stress on the top surface side within a specific range.
  • the method of grinding or polishing at least one surface of the glass before chemical strengthening has a problem from the viewpoint of improving productivity, and it is preferable to omit these grinding or polishing treatments.
  • ITO Indium Tin Oxide
  • the gap between the glass and the stage becomes too large when printing the black frame of the cover glass, and the glass may not be adsorbed on the stage.
  • ITO Indium Tin Oxide
  • the cover glass has a certain amount of warpage, uneven brightness or Newton rings may occur.
  • an object of the present invention is to provide a glass plate that can effectively suppress warping after chemical strengthening and can omit or simplify the polishing treatment before chemical strengthening.
  • the present inventors have found that by treating the glass surface with fluorine, it is possible to suppress a difference in the way of entering the chemical strengthening between one side and the other side of the glass and to reduce the warp after the chemical strengthening. Based on this finding, the present invention has been completed.
  • F 0-3 [average fluorine concentration (mol%) by SIMS (Secondary Ion Mass Spectrometry) at a depth of 0 to 3 ⁇ m on a surface with a large fluorine concentration] ⁇ 3 (II)
  • F 0-30 is determined by the following formula (III).
  • F 0-30 [Average fluorine concentration (mol%) by SIMS at a depth of 0 to 30 ⁇ m on a surface with a large fluorine concentration] ⁇ 30 (III) 2.
  • ⁇ F is an average fluorine concentration (mol%) by SIMS at a depth of 1 to 24 ⁇ m on a surface with a low fluorine concentration from an average fluorine concentration (mol%) by SIMS at a depth of 1 to 24 ⁇ m on a surface with a high fluorine concentration. %).
  • ⁇ H 2 O is an average of SIMS having a depth of 1 to 24 ⁇ m on a surface having a high fluorine concentration from an average H 2 O concentration (mol%) of SIMS having a depth of 1 to 24 ⁇ m on a surface having a low fluorine concentration.
  • a flat panel display device comprising a cover glass, wherein the cover glass is the glass plate according to item 8 above.
  • the glass plate of the present invention has a surface treated with fluorine, thereby suppressing a difference in the way of chemical strengthening between one side and the other side of the glass, and a desired stress value due to chemical strengthening. Can be a value. Further, even if the polishing treatment before chemical strengthening is simplified or omitted, the warp of the glass after chemical strengthening can be reduced and excellent flatness can be obtained.
  • FIG. 1 is a diagram schematically showing a double-flow type injector that can be used in the present invention.
  • FIG. 2 is a diagram schematically showing a single-flow injector that can be used in the present invention.
  • FIG. 3 is a cross-sectional view of a flat panel display used as a cover glass for a flat panel display after chemically strengthening the chemically strengthened float glass of the present invention.
  • FIG. 4 (a) shows a schematic explanatory diagram of a method for treating the surface of a glass ribbon by supplying a gas containing a molecule having fluorine atoms in the structure thereof by a beam in the production of a glass plate by a float method.
  • FIG. 4B is a cross-sectional view taken along the line AA in FIG. FIGS.
  • FIGS. 5A to 5D are cross-sectional views of beams that can be adjusted by dividing the amount of gas into three in the width direction of the glass ribbon.
  • FIGS. 6A to 6C show typical fluorine concentration profiles by SIMS of a fluorine-treated aluminosilicate glass.
  • FIGS. 7 (a) to (c) show typical H 2 O concentration profiles by SIMS of aluminosilicate glass.
  • FIG. 8 shows a typical IR spectrum of an aluminosilicate glass.
  • FIG. 9A shows a typical fluorine concentration profile by SIMS of an aluminosilicate glass.
  • FIG. 9B is a diagram in which the horizontal axis represents the depth and the vertical axis represents the slope at an arbitrary point x i represented by the formula (a).
  • FIG. 9C shows an enlarged view of the dotted line portion in FIG.
  • the “glass plate” includes those in which molten glass is formed into a plate shape.
  • a so-called glass ribbon in a float bath is also a glass plate.
  • the warpage after chemical strengthening of the glass plate is caused by the difference in the way of chemical strengthening on one side and the other side of the glass plate.
  • chemical strengthening is performed on the glass surface (top surface) that is not in contact with the molten metal (usually tin) and the glass surface (bottom surface) that is in contact with the molten metal during float forming. Warping after chemical strengthening occurs due to the difference in the way of entering.
  • the glass plate of the present invention typically, one side of the glass plate is treated with fluorine to adjust the diffusion rate of ions on one side and the other side of the glass plate, It is possible to adjust the way of chemical strengthening on the other side and the other side. Therefore, the glass plate of the present invention can reduce the warpage of the glass plate after chemical strengthening without adjusting the strengthening stress or without performing processing such as grinding and polishing before the chemical strengthening treatment.
  • the glass plate of the present invention is a glass plate in which the fluorine concentration on one surface facing in the thickness direction is larger than the fluorine concentration on the other surface, and the surface layer fluorine ratio represented by the following formula (I) is 0.5 or more. It is a glass plate which is 0.95 or less.
  • Surface layer fluorine ratio F 0-3 / F 0-30 (I)
  • F 0-3 is the fluorine amount on the glass surface (depth 0 to 3 ⁇ m from the glass surface), and is determined by the following formula (II).
  • F 0-3 [Average fluorine concentration (mol%) by SIMS at a depth of 0 to 3 ⁇ m on a surface with a large fluorine concentration] ⁇ 3 (II)
  • F 0-30 is the amount of fluorine taken into the glass by the fluorine treatment, and is determined by the following formula (III).
  • F 0-30 [Average fluorine concentration (mol%) by SIMS at a depth of 0 to 30 ⁇ m on a surface with a large fluorine concentration] ⁇ 30 (III)
  • the average fluorine concentration is calculated from the profile according to the following procedures (a1) to (a3) after measuring the fluorine concentration profile in the glass with a SIMS apparatus.
  • 6 (a) to 6 (c) show typical fluorine concentration profiles by SIMS of a fluorine-treated aluminosilicate glass.
  • A1 Measure the fluorine concentration profile by SIMS of a standard sample with a known concentration and a sample to be measured [FIG. 6A].
  • a calibration curve is created from the measurement results of the standard sample, and a coefficient for converting 19 F / 30 Si into a fluorine concentration (mol%) is calculated [FIG. 6 (b)].
  • the fluorine concentration (mol%) of the sample to be measured is obtained from the coefficient calculated in step (a2).
  • the average fluorine concentration (mol%) by SIMS at a depth of 0 to 3 ⁇ m is a value obtained by integrating the fluorine concentrations at a depth of 0 to 3 ⁇ m and dividing by the depth of 3 ⁇ m [FIG. 6 (c)].
  • the average fluorine concentration (mol%) by SIMS at a depth of 0 to 30 ⁇ m can be obtained in the same manner.
  • the curvature of the glass after chemical strengthening can be effectively suppressed by setting the surface layer fluorine ratio to 0.5 or more and 0.95 or less.
  • a gas or liquid containing a molecule having a fluorine atom in its structure (hereinafter also referred to as a fluorine-containing fluid).
  • the glass transition temperature of the glass plate is defined as Tg, preferably (Tg + 100 ° C.) or more, more preferably The method of (Tg + 200 degreeC) or more is mentioned.
  • a method for setting the surface layer fluorine ratio to 0.5 or more and 0.95 or less a method of lengthening the treatment time with fluorine, the surface fluorine is volatilized by performing the heat treatment again after the glass is treated with fluorine. Methods, etc.
  • the secondary ion intensity I M1 of the isotope M 1 of the element M in SIMS is the primary ion intensity I P , the sputtering rate Y of the matrix, the concentration C M of the element M (ratio to the total concentration), and the existence probability of the isotope M 1 It is proportional to ⁇ 1 , the secondary ionization rate ⁇ M of the element M, and the transmission efficiency ⁇ (including the detection efficiency of the detector) of the mass spectrometer.
  • I M1 A ⁇ I P ⁇ Y ⁇ C M ⁇ ⁇ 1 ⁇ ⁇ M ⁇ ⁇ (Formula w)
  • A is the ratio of the secondary ion detection area to the scanning range of the primary ion beam.
  • ⁇ is eliminated by using a main component element or the like in the same sample as a reference element and taking a ratio with (formula w).
  • F corresponds to M 1 and Si corresponds to R j . Therefore, (Equation x) ratio of the intensities from the (F / Si) is equal to fluorine concentration C M in divided by K. That is, F / Si is a direct indicator of fluorine concentration.
  • SIMS analysis conditions include the following conditions.
  • the analysis conditions shown below are examples, and should be changed as appropriate depending on the measurement device, sample, and the like.
  • the depth of the horizontal axis of the profile in the depth direction obtained by SIMS can be obtained by measuring the depth of the analysis crater with a stylus type film thickness meter (for example, Dektak 150 manufactured by Veeco).
  • More specific analysis conditions include, for example, the following conditions.
  • ADEPT 1010 manufactured by ULVAC-PHI can be mentioned.
  • Parameters for defining an appropriate fluorine addition amount for improving warpage Warpage due to chemical strengthening of glass is caused by a difference in the way of chemical strengthening on the top surface and the bottom surface.
  • the difference in the way of chemical strengthening is largely influenced by the amount of moisture in the glass.
  • Addition of fluorine to the glass surface layer improves the warpage due to chemical strengthening of the glass due to various factors, but considering the difference in moisture content between the top and bottom surfaces, the appropriate amount of fluorine added to the glass is as follows: Set the parameters.
  • the glass plate of the present invention is a glass plate in which the fluorine concentration on one surface facing in the thickness direction is larger than the fluorine concentration on the other surface, and preferably satisfies the following formula (1). 0.1 ⁇ ⁇ F / ⁇ H 2 O (1)
  • ⁇ F is an average fluorine concentration (mol%) by SIMS at a depth of 1 to 24 ⁇ m on a surface with a low fluorine concentration from an average fluorine concentration (mol%) by SIMS at a depth of 1 to 24 ⁇ m on a surface with a high fluorine concentration. %).
  • the average fluorine concentration can be obtained by the above procedure.
  • ⁇ H 2 O is an average of SIMS having a depth of 1 to 24 ⁇ m on a surface having a high fluorine concentration from an average H 2 O concentration (mol%) of SIMS having a depth of 1 to 24 ⁇ m on a surface having a low fluorine concentration.
  • the average H 2 O concentration (mol%) is calculated from the profile according to the following procedures (b1) to (b3) after measuring the fluorine concentration profile in the glass with a SIMS apparatus.
  • FIGS. 7A to 7C show typical H 2 O concentration profiles by SIMS of aluminosilicate glass.
  • B1 concentration is measured of H 2 O concentration profiles by SIMS of the known standard samples and measuring sample [Fig. 7 (a)].
  • B2) A calibration curve is created from the measurement result of the standard sample, and a coefficient for converting 1 H / 30 Si into H 2 O concentration (mol%) is calculated [FIG. 7 (b)].
  • B3) The H 2 O concentration (mol%) of the measurement target sample is obtained from the coefficient calculated in step (b2).
  • the average H 2 O concentration (mol%) by SIMS at a depth of 1 to 24 ⁇ m is a value obtained by integrating the H 2 O concentration at a depth of 1 to 24 ⁇ m and dividing by 23 [FIG. 7 (c)].
  • the absolute value of the difference between the values obtained by calculating the average H 2 O concentration (mol%) by SIMS at a depth of 1 to 24 ⁇ m for both surfaces facing in the thickness direction of the glass by the steps (b1) to (b3) is ⁇ H 2 O It becomes.
  • the H 2 O concentration in the standard sample is obtained by polishing both the top surface and the bottom surface of the sample to be measured so that there is no distribution of the H 2 O concentration in the thickness direction of the glass.
  • An IR spectrum of the glass is obtained using an FT-IR apparatus, and the H 2 O concentration (mol%) is calculated from the intensity of the peak due to water in the glass.
  • a typical IR spectrum of an aluminosilicate glass is shown in FIG.
  • a H2O ⁇ H2O ⁇ C ⁇ l (i) ⁇ H2O : molar extinction coefficient of H 2 O in glass (L mol ⁇ 1 cm ⁇ 1 ) C: H 2 O concentration in glass (mol L ⁇ 1 ) l: Optical path length (cm)
  • ⁇ F / ⁇ H 2 O obtained by the formula (1) By setting ⁇ F / ⁇ H 2 O obtained by the formula (1) to be 0.1 or more, warping after chemical strengthening can be effectively suppressed.
  • ⁇ F / ⁇ H 2 O is preferably 0.1 or more, and more preferably 0.4 or more. If ⁇ F / ⁇ H 2 O is less than 0.1, no significant difference is observed in the warpage displacement, which is inappropriate. Moreover, it is practically preferable that ⁇ F / ⁇ H 2 O is 10 or less.
  • the glass plate of the present invention is a glass plate in which the fluorine concentration on one surface facing in the thickness direction is larger than the fluorine concentration on the other surface, and preferably satisfies the following formula (2). 1 ⁇ x (2)
  • F (x i ) represents the fluorine concentration (mol%) by SIMS at the depth x i ( ⁇ m).
  • FIG. 9 (a) shows a typical fluorine concentration profile by SIMS of a fluorine-treated aluminosilicate glass.
  • FIG. 9B is a graph plotting the depth at the horizontal axis and the slope at an arbitrary point x i represented by the following equation (a) on the vertical axis.
  • F (x) represents the fluorine concentration (mol%) at the point x. [F (x i + ⁇ x) ⁇ F (x i )] / ⁇ x (a)
  • the maximum depth x ( ⁇ m) at which the slope represented by the formula (a) is ⁇ 0.015 is preferably 1 or more, more preferably 2 or more. Preferably, it is 2.8 or more, more preferably 3 or more.
  • x is less than 1, there is no significant difference in warpage displacement.
  • FIG. 9 (c) is an enlarged view of the dotted line portion of the graph of FIG. 9 (b).
  • ⁇ x is 0.1
  • the maximum depth x ( ⁇ m) at which the slope represented by the formula (a) is ⁇ 0.015 is 6.5.
  • the manufacturing method of a glass plate is not specifically limited, As long as it has a composition which can be strengthened by a chemical strengthening process, the thing of various compositions can be used. For example, appropriate amounts of various raw materials are prepared, heated and melted, then homogenized by defoaming or stirring, and formed into a plate shape by a well-known float method, downdraw method (for example, fusion method) or press method, After slow cooling, it is cut into a desired size and polished to produce.
  • a well-known float method, downdraw method (for example, fusion method) or press method After slow cooling, it is cut into a desired size and polished to produce.
  • glass produced by the float process is preferable because the improvement of warpage after chemical strengthening, which is the effect of the present invention, is particularly easily exhibited.
  • the glass plate used in the present invention include a glass plate typically made of soda lime silicate glass, aluminosilicate glass, borate glass, lithium aluminosilicate glass, or borosilicate glass.
  • glass having a composition containing Al is preferable.
  • Al coexists with Al, it takes 4-coordination and participates in the formation of a network that becomes a glass skeleton like Si.
  • tetracoordinate Al increases, movement of alkali ions becomes easy, and ion exchange easily proceeds during chemical strengthening treatment.
  • the thickness of the glass plate is not particularly limited, and examples thereof include 2 mm, 0.8 mm, 0.73 mm, 0.7 mm, 0.56 mm, and 0.4 mm. In order to carry out, it is usually preferably 5 mm or less, more preferably 3 mm or less, further preferably 1.5 mm or less, and particularly preferably 0.8 mm or less.
  • the warp amount after chemical strengthening of a 0.7 mm thick glass plate is required to be 40 ⁇ m or less.
  • the amount of warpage after chemical strengthening is about 130 ⁇ m.
  • the amount of warpage of the glass plate after chemical strengthening is inversely proportional to the square of the plate thickness, so the amount of warpage when the thickness of the glass plate is 2.0 mm is about 16 ⁇ m, and the warpage is substantially a problem.
  • the problem of warpage after chemical strengthening may occur when the thickness of the glass plate is less than 2 mm, typically 1.5 mm or less.
  • the composition of the glass plate of the present invention is a composition expressed in mol%, SiO 2 is 50 to 80%, Al 2 O 3 is 0.1 to 25%, Li 2 O + Na 2 O + K 2 O is 3 to 30%.
  • a glass containing 0 to 25% MgO, 0 to 25% CaO and 0 to 5% ZrO 2 but is not particularly limited. More specifically, the following glass compositions may be mentioned. For example, “containing 0 to 25% of MgO” means that MgO is not essential but may contain up to 25%.
  • the glass of (i) is contained in soda lime silicate glass, and the glass of (ii) and (iii) is contained in aluminosilicate glass.
  • the composition expressed as mol% is SiO 2 50 to 74%, Al 2 O 3 1 to 10%, Na 2 Contains 6-14% O, 3-11% K 2 O, 2-15% MgO, 0-6% CaO and 0-5% ZrO 2 , and contains SiO 2 and Al 2 O 3 composition total 75% or less, and displayed in the total content of Na 2 O content and K 2 O 12 to 25% glass (iii) mol percent total of 7 to 15% of the content of MgO and CaO 0 but the SiO 2 68 ⁇ 80%, the Al 2 O 3 4 ⁇ 10% , a Na 2 O 5 ⁇ 15%, the K 2 O 1%, the MgO 4 ⁇ 15% and ZrO 2 are compositions displaying 0-1% glass containing (iv) mol%, a SiO 2 67 ⁇ 75%, the Al 2 O 3 0 ⁇ 4% , Na 2 O the 7 ⁇ 15% K 2 O 1-9% of MgO 6 ⁇ 14% and the ZrO 2 and contains 0 to 1.
  • surface treatment is performed by bringing a fluorine-containing fluid into contact with at least one surface of the glass plate or the glass ribbon.
  • the temperature of the glass ribbon is preferably 640 ° C. or higher. By setting it as 640 degreeC or more, the curvature amount of the glass after chemical strengthening can be reduced.
  • fluorine-containing fluid examples include hydrogen fluoride (HF), flon (for example, chlorofluorocarbon, fluorocarbon, hydrochlorofluorocarbon, hydrofluorocarbon, and halon), hydrofluoric acid, fluorine alone, trifluoroacetic acid, and carbon tetrafluoride.
  • HF hydrogen fluoride
  • flon for example, chlorofluorocarbon, fluorocarbon, hydrochlorofluorocarbon, hydrofluorocarbon, and halon
  • hydrofluoric acid fluorine alone, trifluoroacetic acid
  • carbon tetrafluoride examples include silicon tetrafluoride, phosphorus pentafluoride, phosphorus trifluoride, boron trifluoride, nitrogen trifluoride, chlorine trifluoride and the like, but are not limited to these gases or liquids.
  • hydrogen fluoride, chlorofluorocarbon or hydrofluoric acid is preferable because of its high reactivity with the glass plate surface. Moreover, you may mix and use 2 or more types among these gases. Further, since the oxidizing power is too strong in the float bath, it is preferable not to use fluorine alone.
  • the liquid When a liquid is used, the liquid may be supplied to the glass plate surface by spray coating, for example, or may be supplied to the glass plate surface after vaporizing the liquid. Moreover, you may dilute with another liquid or gas as needed.
  • the fluorine-containing fluid may contain a liquid or a gas other than those liquids or gases, and is preferably a liquid or a gas that does not react with molecules having fluorine atoms at room temperature.
  • liquid or gas examples include, but are not limited to, N 2 , air, H 2 , O 2 , Ne, Xe, CO 2 , Ar, He, and Kr. Moreover, 2 or more types of these gases can also be mixed and used.
  • gas carrier gas containing molecules having fluorine atoms in its structure it is preferable to use an inert gas such as N 2 or argon. Further, the gas containing a molecule having a fluorine atom in its structure may further contain SO 2 . SO 2 is used when a glass plate is continuously produced by a float process or the like, and has a function of preventing wrinkles from being generated on the glass due to the conveyance roller coming into contact with the glass plate in the slow cooling region. Moreover, the gas decomposed
  • the fluorine-containing fluid may contain water vapor or water.
  • Water vapor can be extracted by bubbling an inert gas such as nitrogen, helium, argon, carbon dioxide in heated water.
  • an inert gas such as nitrogen, helium, argon, carbon dioxide in heated water.
  • Specific examples of the method for producing a glass plate of the present invention include a method for producing a glass plate represented by the float process.
  • a glass manufacturing apparatus having a melting furnace for melting glass raw materials, a float bath for floating glass on a molten metal (such as tin) to form a glass ribbon, and a slow cooling furnace for gradually cooling the glass ribbon Is used to produce a glass plate.
  • HF gas is supplied from the side not touching the metal surface to the glass plate conveyed on the molten metal bath to treat the surface of the glass plate. May be.
  • the glass plate is conveyed by a roller.
  • FIG. 4 (a) shows a schematic explanatory diagram of a method for processing a glass surface by supplying HF gas in the production of a glass plate by a float method.
  • HF gas is blown onto the glass ribbon 101 by a beam 102 inserted into the float bath.
  • the HF gas is preferably blown onto the glass ribbon 101 from the side where the glass ribbon 101 does not touch the molten metal surface.
  • An arrow Ya indicates a direction in which the glass ribbon 101 flows in the float bath.
  • the glass ribbon 101 is preferably 600 to 900 ° C. or 650 to 900 ° C., more preferably 700 ° C. to 900 ° C. More preferably, it is at a position of 750 to 850 ° C., typically 800 ° C. Further, the position of the beam 102 may be upstream or downstream of the radiation gate 103.
  • the amount of HF gas blown onto the glass ribbon 101 is preferably 1 ⁇ 10 ⁇ 6 to 5 ⁇ 10 ⁇ 3 mol / cm 2 of the glass ribbon.
  • Fig. 4 (b) shows a cross-sectional view along the line AA in Fig. 4 (a).
  • the HF gas blown to the glass ribbon 101 by the beam 102 from the Y1 direction flows in from “IN” and flows out from the “OUT” direction. That is, it moves in the directions of arrows Y4 and Y5 and is exposed to the glass ribbon 101.
  • the HF gas that has moved in the direction of arrow Y4 flows out from the direction of arrow Y2, and the HF gas that has moved in the direction of arrow Y5 flows out from the direction of arrow Y3.
  • the amount of warpage of the glass plate after chemical strengthening may change depending on the position of the glass ribbon 101 in the width direction. In such a case, it is preferable to adjust the amount of HF gas. That is, it is preferable to increase the amount of blowing HF gas at a position where the amount of warping is large, and to reduce the amount of blowing HF gas at a position where the amount of warping is small.
  • the structure of the beam 102 is made so that the HF gas can be adjusted in the width direction of the glass ribbon 101.
  • the amount of warpage may be adjusted in the width direction.
  • FIG. 5A shows a cross-sectional view of a beam 102 that adjusts the amount of HF gas by dividing it into I to III in the width direction 110 of the glass ribbon 101.
  • the gas systems 111 to 113 are divided by partition walls 114 and 115, and HF gas is caused to flow out from the gas blowing holes 116 and sprayed onto the glass.
  • the arrow in Fig.5 (a) shows the flow of HF gas.
  • the arrows in FIG. 5B indicate the flow of HF gas in the gas system 111.
  • the arrows in FIG. 5C indicate the flow of HF gas in the gas system 112.
  • An arrow in FIG. 5D indicates the flow of HF gas in the gas system 113.
  • Examples of a method for supplying a fluorine-containing fluid such as HF gas to the glass surface include a method using an injector and a method using an introduction tube.
  • FIG. 1 and 2 are schematic views of an injector used for the surface treatment of a glass plate that can be used in the present invention.
  • FIG. 1 is a diagram schematically showing a double-flow type injector that can be used in the present invention.
  • FIG. 2 is a diagram schematically showing a single-flow injector that can be used in the present invention.
  • HF gas is discharged from the central slit 1 and the outer slit 2 toward the glass plate 20, flows on the glass plate 20 through the flow path 4, and is exhausted from the exhaust slit 5.
  • symbol 21 in FIG.1 and FIG.2 is a direction through which the glass plate 20 flows, and is parallel to the flow path 4.
  • the distance between the gas discharge port of the injector and the glass plate is preferably 50 mm or less.
  • the gas By setting the distance to 50 mm or less, the gas can be prevented from diffusing into the atmosphere, and a sufficient amount of gas can reach the glass plate with respect to the desired gas amount.
  • the distance from the glass plate is too short, for example, when the glass plate produced by the float process is processed online, the glass plate and the injector may come into contact with each other due to the fluctuation of the glass ribbon.
  • the fluorine-containing fluid supplied from the injector is a liquid
  • the distance between the liquid discharge port of the injector and the glass plate there is no particular limitation on the distance between the liquid discharge port of the injector and the glass plate, and it may be arranged so that the glass plate can be processed uniformly.
  • the injector may be used in any manner such as double flow or single flow, and two or more injectors may be arranged in series in the flow direction of the glass plate to treat the glass plate surface.
  • the double-flow injector is an injector in which the gas flow from discharge to exhaust is equally divided in the forward direction and the reverse direction with respect to the moving direction of the glass plate.
  • This double-flow injector is common and is also known for use in producing low reflection glass.
  • asahi glass soda lime silicate glass glass transition point 560 ° C.
  • HF gas from the central slit 1 is 1.12 SLM (liters per minute as standard gas) and a nitrogen (N 2) gas was mixed gas 9SLM heated to 0.99 ° C. flow rate 64cm / s, to blow 45.5SLM the N 2 gas from the outer slit 2, which may be used.
  • the surface roughness (arithmetic mean roughness) Ra of the glass surface sprayed with HF gas in this manner is 30.6 nm, and the value of x described above is 2.5 ⁇ m.
  • the single-flow injector is an injector in which the gas flow from discharge to exhaust is fixed in either the forward direction or the reverse direction with respect to the moving direction of the glass plate.
  • the gas flow on the glass plate and the moving direction of the glass plate are the same in terms of airflow stability.
  • a fluorine-containing fluid supply port a gas generated by reacting with an unreacted fluorine-containing fluid and a glass plate, or a gas exhaust port generated by reacting two or more kinds of gases among fluorine-containing fluids It is preferable that it exists in the surface of the same side of a glass plate.
  • two or more conveyors may be arranged in series, and an injector may be installed between adjacent conveyors to supply the gas from the side touching the conveyor to treat the glass plate surface.
  • an injector may be installed between adjacent conveyors to supply the gas from the side touching the conveyor to treat the glass plate surface.
  • the glass plate when flowing on the roller, it may be supplied from the side not touching the roller, or may be supplied from between adjacent rollers on the side touching the roller.
  • the same or different gas may be supplied from both sides of the glass plate.
  • the glass plate may be surface-treated by supplying gas from both the side not touching the roller and the side touching the roller.
  • the side that is not touching the roller Gas may be supplied from both sides of the side touching the roller.
  • the injector arranged on the side touching the roller and the injector arranged on the side not touching the roller may be arranged at different positions in the flow direction of the glass plate. In arranging at different positions, any of them may be arranged upstream or downstream with respect to the flow direction of the glass plate.
  • a glass plate with a functional film is manufactured online by combining glass manufacturing technology using a float process and CVD technology.
  • the transparent conductive film and the underlying film are formed on the glass plate by supplying gas from the surface not touching the tin or the surface not touching the roller. Yes.
  • an injector may be disposed on the surface in contact with the roller, and a fluorine-containing fluid may be supplied from the injector to the glass plate to treat the glass plate surface.
  • the surface temperature of the glass plate when the fluorine-containing fluid is supplied to the surface of the glass plate being conveyed to treat the surface is (Tg + 50) when the glass transition temperature of the glass plate is Tg. ° C) to (Tg + 460 ° C), more preferably (Tg + 90 ° C) to (Tg + 460 ° C).
  • the temperature is usually higher on the upstream side in the direction in which the glass ribbon flows.
  • the diffusion of fluorine in the glass is more active as the temperature is higher, that is, as the viscosity is lower. Therefore, the fluorine treatment in the float bath is effective when performed upstream in order to increase the penetration depth of fluorine. Or the same effect can be acquired also by raising the temperature of the glass ribbon of a process position.
  • the glass ribbon may go through a process of thinning in the float bath after processing.
  • the penetration depth of fluorine becomes shallower with the glass ribbon, the penetration depth of fluorine in the finally obtained glass plate is shallower than the penetration depth of fluorine in the glass plate that has been processed the same downstream. There is. Therefore, when the fluorine treatment is performed in the float bath, it is not always effective to provide the treatment position significantly upstream in order to increase the fluorine penetration depth.
  • the case where HF is used as the fluorine-containing fluid will be described as an example.
  • the higher the HF flow rate the greater the warp improvement effect during the chemical strengthening treatment, which is preferable.
  • the higher the HF concentration the better the warp improvement effect during the chemical strengthening treatment. Becomes larger.
  • the warpage after chemical strengthening is improved as the conveyance speed of the glass plate is lower. Even in facilities where the total gas flow rate and HF flow rate cannot be controlled well, the warpage after chemical strengthening can be improved by appropriately controlling the conveying speed of the glass plate.
  • Chemical strengthening is performed by ion exchange at a temperature below the glass transition point to convert an alkali metal ion (typically Li ion or Na ion) having a small ion radius on the glass surface to an alkali metal ion having a larger ion radius. This is a process of forming a compressive stress layer on the glass surface by exchanging with (typically K ions).
  • the chemical strengthening treatment can be performed by a conventionally known method.
  • a glass plate with improved warpage after chemical strengthening can be obtained by chemically strengthening the glass plate into which fluorine has been introduced.
  • the amount of warpage (warpage variation) of the glass plate after chemical strengthening relative to the glass plate before chemical strengthening is measured by a three-dimensional shape measuring machine (for example, manufactured by Mitaka Kogyo Co., Ltd.), or surface roughness and contour shape measurement It can be measured with a machine (for example, manufactured by Tokyo Seimitsu Co., Ltd.).
  • the improvement of warpage after chemical strengthening is evaluated by the amount of warpage displacement obtained by the following formula in the experiment under the same conditions except that the surface treatment is performed with a fluorine-containing fluid.
  • Warpage displacement ⁇ X ⁇ Y ⁇ X: amount of warpage change due to chemical strengthening of untreated glass plate
  • ⁇ Y amount of warpage change due to chemical strengthening of treated glass plate
  • the amount of warpage change is the amount of warpage of the glass plate after chemical strengthening, and the glass plate before chemical strengthening The value obtained by subtracting the amount of warpage.
  • the amount of change in warping is ⁇ X> 0. If ⁇ Y warps in the same direction as ⁇ X, ⁇ Y> 0, and if it warps in the opposite direction to ⁇ X, ⁇ Y ⁇ 0.
  • the amount of warpage change due to chemical strengthening of untreated glass sheets varies greatly depending on various conditions. That the amount of warp displacement is larger than a predetermined value means that the warp can be controlled regardless of the above-mentioned variation. Therefore, a glass plate having a warp displacement amount of a predetermined value, specifically, 10 ⁇ m or more can reduce the warp problem.
  • the CS (surface compressive stress) and DOL (compressive stress layer depth) of the glass plate can be measured with a surface stress meter.
  • the surface compressive stress of the chemically strengthened glass is preferably 600 MPa or more, and the depth of the compressive stress layer is preferably 15 ⁇ m or more.
  • FIG. 3 is a cross-sectional view of a display device in which a cover glass is disposed.
  • front, rear, left and right are based on the direction of the arrow in the figure.
  • the display device 40 includes a display panel 45 provided in the housing 15 and a cover glass 30 that covers the entire surface of the display panel 45 and surrounds the front of the housing 15.
  • the cover glass 30 is installed mainly for the purpose of improving the aesthetics and strength of the display device 40, preventing impact damage, and the like, and the overall shape is formed from a single plate-like glass having a substantially planar shape. As shown in FIG. 3, the cover glass 30 may be installed so as to be separated from the display side (front side) of the display panel 45 (having an air layer), and has a translucent adhesive film (FIG. (Not shown) may be attached to the display side of the display panel 45.
  • a translucent adhesive film FOG. (Not shown) may be attached to the display side of the display panel 45.
  • a functional film 41 is provided on the front surface of the cover glass 30 that emits light from the display panel 45, and a functional film 42 is provided on the rear surface on which the light from the display panel 45 is incident at a position corresponding to the display panel 45.
  • the functional films 41 and 42 are provided on both surfaces in FIG. 3, the functional films 41 and 42 are not limited to this and may be provided on the front surface or the back surface, or may be omitted.
  • the functional films 41 and 42 have functions such as anti-reflection of ambient light, prevention of impact breakage, electromagnetic wave shielding, near-infrared shielding, color tone correction, and / or scratch resistance improvement, and thickness and shape are used for applications. It is selected as appropriate.
  • the functional films 41 and 42 are formed, for example, by attaching a resin film to the cover glass 30. Or you may form by thin film formation methods, such as a vapor deposition method, a sputtering method, or CVD method.
  • Reference numeral 44 denotes a black layer, which is, for example, a coating formed by applying ink containing pigment particles to the cover glass 30, irradiating it with ultraviolet rays, or heating and baking it, and then cooling it.
  • a black layer which is, for example, a coating formed by applying ink containing pigment particles to the cover glass 30, irradiating it with ultraviolet rays, or heating and baking it, and then cooling it.
  • the display panel and the like cannot be seen from the outside, and the appearance is improved.
  • the surface roughness (arithmetic average roughness) Ra is preferably 2.5 nm or less, and more preferably 1.5 nm or less. . Thereby, it can prevent impairing the clearness of the display image of a display apparatus with a cover glass.
  • the surface roughness Ra of the glass plate can be measured as follows based on JIS B0601 (2001). Using an AFM (Atomic Force Microscope), for example, Park Systems, XE-HDM as a measuring device, measure 3 locations at a scan size of 1 ⁇ m ⁇ 1 ⁇ m, and average the 3 locations. Ra value.
  • Glass plates of glass materials A and B having the following composition were used.
  • Glass A In terms of mol%, SiO 2 is 72.0%, Al 2 O 3 is 1.1%, Na 2 O is 12.6%, K 2 O is 0.2%, and MgO is 5.5. %, Glass containing 8.6% CaO (glass transition temperature 566 ° C.)
  • Glass B In terms of mol%, SiO 2 is 64.3%, Al 2 O 3 is 8.0%, Na 2 O is 12.5%, K 2 O is 4.0%, and MgO is 10.5. %, CaO 0.1%, SrO 0.1%, BaO 0.1% and ZrO 2 0.5% (glass transition temperature 604 ° C.)
  • CS and DOL were measured using a surface stress meter (FSM-6000LE) manufactured by Orihara Seisakusho.
  • Example 1 HF treatment is performed in the float bath in which the glass ribbon of glass material B (Examples 1-1 to 1-9, Comparative Example 1-1) or glass material A (Examples 1-10 to 1-21, Comparative Example 1-2) flows. Carried out. The obtained glass was measured by the above-described procedure, and the surface layer fluorine ratio, ⁇ F / ⁇ H 2 O, x was calculated.
  • the obtained glass with a thickness of 0.7 mm was cut into three pieces of 100 mm square, the warpage of two diagonal lines corresponding to the 90 mm square portion of the substrate was measured, and the average value was taken as the amount of warpage before strengthening. . Thereafter, the glass plate of glass material B is immersed in KNO 3 molten salt heated to 450 ° C. for 2 hours, and the glass plate of glass material A is immersed in KNO 3 molten salt heated to 420 ° C. for 2.5 hours. Reinforced. Next, the warpage of two diagonal lines corresponding to the 90 mm square portion of the substrate was measured, and the warpage displacement was calculated by taking the average value as the warpage amount after strengthening.
  • Comparative Example 1-1 and Comparative Example 1-2 are references not subjected to HF treatment.
  • the results are shown in Tables 1 to 3.
  • the total contact amount (mol / cm 2 ) of HF in Table 1 is determined by the following equation.
  • the processing time in the formula is the time during which the HF gas is in contact with the surface of the glass ribbon.
  • [HF total contact amount (mol / cm 2 )] [HF gas concentration (volume%)] / 100 ⁇ [gas flow rate (mol / s / cm 2 )] ⁇ [treatment time (s)] (b)

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Surface Treatment Of Glass (AREA)

Abstract

　La présente invention concerne une plaque de verre dans laquelle la concentration du fluor sur l'une des surfaces en regard dans la direction de l'épaisseur est supérieure à la concentration du fluor sur l'autre surface, la plaque de verre ayant une proportion de fluor, dans la couche superficielle représentée par la formule (I) ci-après, de 0,5 à 0,95 inclus. Proportion de fluor dans la couche superficielle = F0-3/F0-30 … (I). Dans la formule (I), F0-3 est calculé à partir de la formule (II) ci-après. F0-3=[concentration moyenne du fluor (% en moles) à une profondeur de 0 à 3 µm sur la surface dans laquelle la concentration du fluor est élevée, déterminée par une spectrométrie de masse à ions secondaires (SIMS)] × 3 … (II). Dans la formule (I), F0-30 est calculé à partir de la formule (III) ci-après. F0-3=[concentration moyenne du fluor (% en moles) à une profondeur de 0 à 30 µm sur la surface ayant une concentration élevée de fluor, déterminée par SIMS] × 30… (III).
PCT/JP2014/075019 2013-09-25 2014-09-22 Plaque de verre WO2015046118A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016152848A1 (fr) * 2015-03-25 2016-09-29 旭硝子株式会社 Plaque de verre
JP2019034878A (ja) * 2017-08-10 2019-03-07 Ａｇｃ株式会社 Ｔｆｔ用ガラス基板
CN112745017A (zh) * 2019-10-29 2021-05-04 Ａｇｃ株式会社 保护玻璃的制造方法和保护玻璃

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110395903A (zh) * 2018-04-25 2019-11-01 Ａｇｃ株式会社 玻璃基板

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61205641A (ja) * 1985-03-09 1986-09-11 Central Glass Co Ltd フロ−トガラスの化学強化方法
EP2371779A1 (fr) * 2010-03-30 2011-10-05 Linde Aktiengesellschaft Procédé de production de verre plat et panneau de verre produit en fonction de ce procédé
WO2012141310A1 (fr) * 2011-04-15 2012-10-18 旭硝子株式会社 Procédé de fabrication d'un substrat de verre traité en surface
WO2014167842A1 (fr) * 2013-04-08 2014-10-16 日本板硝子株式会社 Plaque de verre et son procédé de fabrication

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61205641A (ja) * 1985-03-09 1986-09-11 Central Glass Co Ltd フロ−トガラスの化学強化方法
EP2371779A1 (fr) * 2010-03-30 2011-10-05 Linde Aktiengesellschaft Procédé de production de verre plat et panneau de verre produit en fonction de ce procédé
WO2012141310A1 (fr) * 2011-04-15 2012-10-18 旭硝子株式会社 Procédé de fabrication d'un substrat de verre traité en surface
WO2014167842A1 (fr) * 2013-04-08 2014-10-16 日本板硝子株式会社 Plaque de verre et son procédé de fabrication

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016152848A1 (fr) * 2015-03-25 2016-09-29 旭硝子株式会社 Plaque de verre
JPWO2016152848A1 (ja) * 2015-03-25 2018-01-18 旭硝子株式会社 ガラス板
JP2019034878A (ja) * 2017-08-10 2019-03-07 Ａｇｃ株式会社 Ｔｆｔ用ガラス基板
JP7070197B2 (ja) 2017-08-10 2022-05-18 Ａｇｃ株式会社 Ｔｆｔ用ガラス基板
CN112745017A (zh) * 2019-10-29 2021-05-04 Ａｇｃ株式会社 保护玻璃的制造方法和保护玻璃
CN112745017B (zh) * 2019-10-29 2023-08-15 Ａｇｃ株式会社 保护玻璃的制造方法和保护玻璃

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