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WO2015046112A1 - Plaque de verre - Google Patents

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Publication number
WO2015046112A1
WO2015046112A1 PCT/JP2014/075012 JP2014075012W WO2015046112A1 WO 2015046112 A1 WO2015046112 A1 WO 2015046112A1 JP 2014075012 W JP2014075012 W JP 2014075012W WO 2015046112 A1 WO2015046112 A1 WO 2015046112A1
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WO
WIPO (PCT)
Prior art keywords
glass
glass plate
fluorine
chemical strengthening
warpage
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/JP2014/075012
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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
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
AGC Inc
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 JP2015539186A priority Critical patent/JPWO2015046112A1/ja
Publication of WO2015046112A1 publication Critical patent/WO2015046112A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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.
  • the present invention is as follows. 1. A glass plate in which the surface F enrichment on one surface is 5 or more larger than the surface F enrichment on the other surface. 2. 2. The glass plate according to item 1, which is a glass plate produced by a float process. 3. A glass plate obtained by chemically strengthening the glass plate according to item 1 or 2. 4). A chemically strengthened glass plate, wherein the surface layer F enrichment on one surface is 5 or more larger than the surface layer F enrichment on the other surface. 5. 5. The glass plate according to any one of items 1 to 4, which has a thickness of 1.5 mm or less. 6). 6. The glass plate according to any one of items 1 to 5, wherein the thickness is 0.8 mm or less. 7). 7. The glass plate according to any one of items 1 to 6, wherein the surface roughness Ra is 2.5 nm or less. 8). 8. A flat panel display device comprising a cover glass, wherein the cover glass is the glass plate according to any one of 3 to 7 above.
  • the glass plate of the present invention suppresses a difference in the way of entering the chemical strengthening between one side and the other side of the glass due to the surface being treated with fluorine, and the stress value by the chemical strengthening is desired.
  • the value can be 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. 4A shows a typical fluorine concentration profile by SIMS of an aluminosilicate glass.
  • FIG. 4B 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.4 (c) shows the figure which expanded the dotted-line part in FIG.4 (b).
  • FIG. 5A is a schematic explanatory diagram of a method for processing the surface of a glass ribbon by supplying a gas containing molecules having fluorine atoms in the structure thereof by a beam in the production of a glass plate by a float process.
  • FIG. 5B is a cross-sectional view taken along the line AA in FIG.
  • FIGS. 6A to 6D 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. 7A to 7C show typical fluorine concentration profiles by SIMS of a fluorine-treated aluminosilicate glass.
  • FIG. 8 is a diagram showing a method for calculating the amount of fluorine contained in the glass from the SIMS profile.
  • FIG. 9 is a diagram showing the relationship between the amount of fluorine contained in the glass of the glass plate (soda lime glass) according to the present invention determined by SIMS and the amount of warp displacement after the glass is chemically strengthened.
  • FIG. 10 is a diagram showing the relationship between the amount of fluorine contained in the glass of the glass plate (aluminosilicate glass) according to the present invention determined by SIMS and the amount of warp displacement after the glass is chemically strengthened.
  • 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.
  • one surface of the glass plate and the other surface are treated by fluorine treatment on the glass plate so that the difference between the fluorine concentration on one surface and the fluorine concentration on the other surface is not less than a specific range.
  • the diffusion rate of ions in can be adjusted to balance the way of chemical strengthening on one 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 surface F enrichment on one side is preferably 5 or more and 7 or more greater than the surface F enrichment on the other side.
  • the absolute value of the difference between the surface F enrichment on one surface and the surface F enrichment on the other surface (hereinafter sometimes referred to as ⁇ surface F enrichment) is usually 300 or less. Is more preferable, 250 or less is more preferable, and 210 or less is further preferable. The same applies to a glass plate after chemical strengthening.
  • surface F enrichment means the ratio of the average fluorine concentration on the surface (0 to 1 ⁇ m depth) to the average fluorine concentration in the bulk, and the average fluorine concentration on the surface is measured by fluorescent X-ray analysis ( XRF).
  • the average fluorine concentration in the bulk is a value obtained by analyzing the fluorine content on the surface of a glass plate polished by 50 ⁇ m by XRF.
  • the fluorine concentration in the bulk is the fluorine content in the average composition of the entire glass plate. Amount.
  • the horizontal axis is the depth when the glass surface is zero, and the depth profile by secondary ion mass spectrometry (SIMS) in which the vertical axis is the fluorine concentration (mol%),
  • SIMS secondary ion mass spectrometry
  • the vertical axis is the fluorine concentration (mol%)
  • a glass plate in which the amount of fluorine contained in the glass is more than 0.23 mol% ⁇ ⁇ m and not more than 21 mol% ⁇ ⁇ m is preferable.
  • the amount of fluorine contained in the glass is the depth ( ⁇ m) when the horizontal axis on the depth profile in SIMS is zero on the glass surface, and the fluorine concentration (mol) in the vertical axis. %) Can be obtained by integration (mol% ⁇ ⁇ m). The calculation method of the fluorine concentration in SIMS will be described later.
  • the amount of fluorine contained in the glass is precisely the amount of fluorine atoms contained in the entire glass plate, but it is considered that there is a limit to the depth at which fluorine can penetrate into the glass by the fluorine treatment. Therefore, in practice, it can be regarded as the same value as the integrated value when the depth profile from the glass surface to the depth of 0 to 30 ⁇ m is measured.
  • the fluorine content (mol% ⁇ ⁇ m) contained in the glass and the warpage displacement ( ⁇ m) after the glass is chemically strengthened are in a first-order proportional relationship (FIGS. 9 and 10).
  • the warpage displacement amount is obtained by the following equation.
  • 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 This is a value obtained by reducing 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 fluorine contained in the glass is within the above range, the warp when chemically strengthened can be improved regardless of the type of the glass.
  • glass produced by the float process is preferable because more warping improvement effects can be seen.
  • the amount of fluorine contained in the glass is preferably more than 0.23 mol% ⁇ ⁇ m, and more preferably 0.7 mol% ⁇ ⁇ m or more. By setting the amount of fluorine contained in the glass to more than 0.23 mol% ⁇ ⁇ m, a significant difference in warpage displacement is observed. Further, the amount of fluorine contained in the glass is preferably 21 mol% ⁇ ⁇ m or less, and more preferably 9 mol% ⁇ ⁇ m or less from a practical standpoint.
  • the glass plate of the present invention is a glass plate after chemical strengthening, it is determined by secondary ion mass spectrometry (SIMS) in which the horizontal axis represents depth ( ⁇ m) and the vertical axis represents fluorine concentration (mol%).
  • SIMS secondary ion mass spectrometry
  • the horizontal axis represents depth ( ⁇ m) and the vertical axis represents fluorine concentration (mol%).
  • the amount of fluorine contained in the glass is preferably more than 0.23 mol% ⁇ ⁇ m and not more than 21 mol% ⁇ ⁇ m.
  • the glass plate of the present invention may contain fluorine on both sides or may contain fluorine only on one side. Among these, the latter is preferable from the viewpoint of improving warpage.
  • the one surface and the other surface of the glass plate refer to the one surface and the other surface facing each other in the thickness direction.
  • the both surfaces of a glass plate mean the both surfaces which oppose a plate
  • the secondary ion intensity I M1 of the isotope M 1 of the element M in secondary ion mass spectrometry is the primary ion intensity I P , the sputtering rate Y of the matrix, the concentration M M of the element M (ratio to the total concentration), and the isotope M. It is proportional to the existence probability ⁇ 1 of 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 (Equation w).
  • 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.
  • FIGS. 7A to 7C 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. 7 (a)].
  • 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. 7 (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. 7 (c)].
  • the average fluorine concentration (mol%) by SIMS at a depth of 0 to 30 ⁇ m can be obtained in the same manner.
  • the integrated value when the fluorine concentration (mol%) is on the vertical axis and the depth ( ⁇ m) is on the horizontal axis is defined as the amount of fluorine (mol% ⁇ ⁇ m) contained in the glass.
  • SIMS analysis conditions include the following conditions.
  • the analysis conditions shown below are illustrations 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.
  • Examples of the secondary ion mass spectrometer having a quadrupole mass spectrometer include ADEPT 1010 manufactured by ULVAC-PHI.
  • 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. Therefore, 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 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).
  • F (x i ) represents the fluorine concentration (mol%) by SIMS at the depth x i ( ⁇ m).
  • FIG. 4A shows a fluorine concentration profile by SIMS of a typical soda lime glass.
  • FIG. 4B 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 1 or more, a significant difference is observed in the warpage displacement.
  • FIG. 4 (c) is an enlarged view of the dotted line portion of the graph of FIG. 4 (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 method for forming molten glass into a plate-like glass plate is not particularly limited, and as long as the glass has a composition that can be strengthened by a chemical strengthening treatment, it has various compositions. Things can be used. For example, appropriate amounts of various raw materials are prepared, heated and melted, then homogenized by defoaming or stirring, etc., and formed into a plate shape by a well-known float method, down draw 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, down draw 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, borosilicate glass, and the like.
  • 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 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.
  • composition expressed in mol% with SiO 2 being 63 to 73%, Al 2 O 3 being 0.1 to 5.2%, Na 2 O being 10 to 16%, and K 2 O being 0 to 1. Glass containing 5%, MgO 5 to 13% and CaO 4 to 10%
  • the composition expressed in 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 Glass with a total of 75% or less, a total content of Na 2 O and K 2 O of 12 to 25%, and a total content of MgO and CaO of 7 to 15%.
  • 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% , 7 to 15% of Na 2 O, 1 to 9% of K 2 O, 6 to 14% of MgO and 0 to 1.5% of ZrO 2 , and the total content of SiO 2 and Al 2 O 3 is A glass having a total content of 71 to 75%, Na 2 O and K 2 O of 12 to 20%, and when CaO is contained, the content is less than 1%
  • a gas or liquid containing a molecule having a fluorine atom in its structure (hereinafter referred to as a fluorine-containing fluid) is brought into contact with at least one surface of the glass plate or the glass ribbon.
  • a fluorine-containing fluid a gas or liquid containing a molecule having a fluorine atom in its structure
  • the surface temperature of the glass ribbon is preferably 600 ° C. or higher, and more preferably over 650 ° C.
  • the fluorine-containing fluid can be easily sprayed with a total fluorine contact amount sufficient to reduce the amount of warpage of the glass after chemical strengthening with respect to the obtained glass.
  • glass plate may be used as a generic term for a glass plate and a glass ribbon.
  • fluorine-containing fluid examples include hydrogen fluoride (HF), chlorofluorocarbon (for example, chlorofluorocarbon, fluorocarbon, hydrochlorofluorocarbon, hydrofluorocarbon, and halon), hydrofluoric acid, fluorine alone, trifluoroacetic acid, and tetrafluoride.
  • HF hydrogen fluoride
  • chlorofluorocarbon for example, chlorofluorocarbon, fluorocarbon, hydrochlorofluorocarbon, hydrofluorocarbon, and halon
  • hydrofluoric acid fluorine alone, trifluoroacetic acid
  • fluorine alone trifluoroacetic acid
  • tetrafluoride examples include carbon, silicon tetrafluoride, phosphorus pentafluoride, phosphorus trifluoride, boron trifluoride, nitrogen trifluoride, and chlorine trifluoride, 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, when the glass is produced by the float process, when the fluorine-containing fluid is sprayed on the glass ribbon, it is preferable not to use a single fluorine because the oxidizing power is too strong in the float bath.
  • 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.
  • the carrier gas for the fluorine-containing fluid it is preferable to use an inert gas such as N 2 or argon.
  • the fluorine-containing fluid may further contain SO 2 .
  • SO 2 is used when continuously producing a glass plate 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.
  • disassembled at high temperature may be included.
  • the fluorine-containing fluid may contain water vapor or water.
  • Water vapor can be taken out by bubbling an inert gas such as nitrogen, helium, argon, carbon dioxide in the heated water.
  • an inert gas such as nitrogen, helium, argon, carbon dioxide
  • fluorine By spraying a fluorine-containing fluid onto glass or a glass ribbon, fluorine can enter from the glass surface, and glass containing fluorine can be obtained.
  • the conditions for spraying the fluorine-containing fluid are preferably adjusted so that the fluorine contained in the obtained glass is more than 0.23 mol% ⁇ ⁇ m and less than 21 mol% ⁇ ⁇ m.
  • the fluorine atom concentration in the fluorine-containing fluid is 0.1% to 15% by volume in order to reduce the load on the equipment. And preferably from 0.1% by volume to 10% by volume.
  • the surface temperature of the glass ribbon is preferably 600 ° C. or higher from the viewpoint of allowing fluorine to penetrate deeper into the glass.
  • the surface temperature of the glass ribbon is preferably (Tg + 50 ° C.) to (Tg + 460 ° C.), more preferably (Tg + 150 ° C.) to (Tg + 460 ° C.), where Tg is the glass transition temperature of the glass plate. Preferably, it is (Tg + 230 ° C.) to (Tg + 460 ° C.).
  • the float method will be described in detail as a specific example of a method for forming molten glass into a plate-like glass plate.
  • 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.
  • a fluorine-containing fluid is supplied to the glass plate conveyed on the molten metal bath from the side not touching the metal surface (top surface). You may process the glass plate surface.
  • the glass plate is conveyed by a roller.
  • the slow cooling region includes not only the inside of the slow cooling furnace but also the portion from the time when the molten metal (tin) bath is carried out in the float bath to the time when it is carried into the slow cooling furnace.
  • the gas may be supplied from the side not touching the molten metal (tin).
  • FIG. 5 (a) shows a schematic explanatory diagram of a method for treating a glass surface by supplying a fluorine-containing fluid in the production of a glass plate by a float process.
  • a fluorine-containing fluid is sprayed onto the glass ribbon 101 by a beam 102 inserted into the float bath.
  • the fluorine-containing fluid is preferably sprayed 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 temperature of the glass ribbon 101 is preferably (Tg + 50) ° C. to (Tg + 460) ° C., and (Tg + 150) ° C. (Tg + 460) ° C. is more preferable, and (Tg + 230) ° C. to (Tg + 460) ° C. is more preferable.
  • the preferred glass ribbon temperature depends on the type of fluid to be sprayed, the principle is to increase the amount of fluorine in the resulting glass by spraying a higher concentration and / or more fluid at higher temperatures. Can do.
  • the position of the beam 102 may be upstream or downstream of the radiation gate 103.
  • the amount of the fluorine-containing fluid sprayed onto the glass ribbon 101 is preferably 1 ⁇ 10 ⁇ 6 to 5 ⁇ 10 ⁇ 3 mol / cm 2 of the glass ribbon.
  • FIG. 5 (b) shows a cross-sectional view taken along the line AA in FIG.
  • the fluorine-containing fluid blown to the glass ribbon 101 from the Y1 direction by the beam 102 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 fluorine-containing fluid that has moved in the direction of arrow Y4 flows out from the direction of arrow Y2, and the fluorine-containing fluid 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 the fluorine-containing fluid. That is, it is preferable to increase the amount of the fluorine-containing fluid sprayed at a position where the warpage amount is large, and to decrease the amount of the fluorine-containing fluid sprayed at a position where the warpage amount is small.
  • the structure of the beam 102 is made to be a structure in which the amount of fluorine-containing fluid can be adjusted in the width direction of the glass ribbon 101.
  • the amount of warpage may be adjusted in the width direction of the ribbon 101.
  • FIG. 6A shows a cross-sectional view of a beam 102 that adjusts the amount of a fluorine-containing fluid 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 a fluorine-containing fluid is caused to flow out from the gas blowing holes 116 and sprayed onto the glass.
  • the arrow in Fig. 6 (a) indicates the flow of the fluorine-containing fluid.
  • the arrows in FIG. 6B indicate the flow of the fluorine-containing fluid in the gas system 111.
  • the arrows in FIG. 6C indicate the flow of the fluorine-containing fluid in the gas system 112.
  • the arrows in FIG. 6D indicate the flow of the fluorine-containing fluid in the gas system 113.
  • Examples of a method for supplying a fluorine-containing fluid to a glass surface on a glass plate 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.
  • the fluorine-containing fluid 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 preferably 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 pressure on the glass plate surface when supplying the fluorine-containing fluid to the glass plate surface is preferably an atmosphere in the pressure range of atmospheric pressure ⁇ 100 Pa to atmospheric pressure + 100 Pa, and the pressure of atmospheric pressure ⁇ 50 Pa to atmospheric pressure + 50 Pa. A range of atmospheres is more preferred.
  • the case of using HF as the fluorine-containing fluid will be described as a representative.
  • 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 is formed of a single plate-like glass having an overall 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 damage, electromagnetic wave shielding, near-infrared shielding, color tone correction, and / or scratch resistance improvement, and the thickness and shape of the functional film are used for the purpose. 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 material B mol%, SiO 2 64.3%, Al 2 O 3 8.0%, Na 2 O 12 0.5%, K 2 O 4.0%, MgO 10.5%, CaO 0.1%, SrO 0.1%, BaO 0.1% and ZrO 2 0.5% Glass (glass transition temperature 604 ° C)
  • XRF method Fluorescence X-ray analysis
  • the analysis conditions of the XRF (fluorescence X-ray analysis) method were as follows. Quantification was performed by a calibration curve method using a Na 2 O standard sample. Measuring apparatus: ZSX100 manufactured by Rigaku Corporation Output: Rh 50 kV-72 mA Filter: OUT attenuator: 1/1 slit: Std. Spectroscopic crystal: RX25 detector: PC peak angle (2 ⁇ / deg.): 47.05 Peak measurement time (seconds): 40B. G. 1 (2 ⁇ / deg.): 43.00B. G. 1 measurement time (seconds): 20B. G. 2 (2 ⁇ / deg.): 50.00B. G. 2 measurement time (seconds): 20 PHA: 110-450
  • ADEPT1010 manufactured by ULVAC-PHI Primary ion species: Cs + Primary acceleration voltage: 5.0 kV Primary ion current: 1 ⁇ A Primary ion incident angle (angle from the direction perpendicular to the sample surface): 60 ° Raster size: 200x200 ⁇ m 2 Detection area: 40 ⁇ 40 ⁇ m 2 Secondary ion polarity: Electron gun for negative neutralization Use: Yes
  • the intensity ratio (F / Si) was obtained from the above-mentioned formulas 1 to 4, and further converted into a fluorine concentration (mol%).
  • a depth profile was created with the horizontal axis representing depth and the vertical axis representing fluorine concentration (mol%), and the integrated value was defined as the amount of fluorine (mol% ⁇ ⁇ m) contained in the glass.
  • the depth of the horizontal axis of the depth direction profile obtained by SIMS analysis was determined by measuring the depth of the analysis crater with a stylus type film thickness meter (Dektak 150 manufactured by Veeco).
  • CS and DOL were measured using a surface stress meter (FSM-6000LE) manufactured by Orihara Seisakusho.
  • Total contact amount of HF The total contact amount of HF (mol / cm 2 ) was determined by the following formula.
  • 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)
  • HF treatment Fluorine treatment
  • 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.

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Abstract

La présente invention a pour objet une plaque de verre avec laquelle un gauchissement après trempe chimique peut être efficacement supprimé et un traitement de polissage ou similaire avant trempe chimique peut être omis ou simplifié. À cet effet, l'invention porte sur une plaque de verre dans laquelle le degré d'enrichissement en F de couche de surface dans une surface associée est supérieur, d'une valeur d'au moins 5, à celui dans une autre surface associée.
PCT/JP2014/075012 2013-09-25 2014-09-22 Plaque de verre Ceased WO2015046112A1 (fr)

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Citations (3)

* 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
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 (3)

* 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
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

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