WO2014104302A1 - 化学強化用フロートガラス - Google Patents
化学強化用フロートガラス Download PDFInfo
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- WO2014104302A1 WO2014104302A1 PCT/JP2013/085125 JP2013085125W WO2014104302A1 WO 2014104302 A1 WO2014104302 A1 WO 2014104302A1 JP 2013085125 W JP2013085125 W JP 2013085125W WO 2014104302 A1 WO2014104302 A1 WO 2014104302A1
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- concentration
- ion exchange
- chemical strengthening
- top surface
- glass
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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
- 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
- C03C21/005—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 introduce in the glass such metals or metallic ions as Ag, Cu
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B18/00—Shaping glass in contact with the surface of a liquid
- C03B18/02—Forming sheets
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B18/00—Shaping glass in contact with the surface of a liquid
- C03B18/02—Forming sheets
- C03B18/18—Controlling or regulating the temperature of the float bath; Composition or purification of the float bath
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B18/00—Shaping glass in contact with the surface of a liquid
- C03B18/02—Forming sheets
- C03B18/20—Composition of the atmosphere above the float bath; Treating or purifying the atmosphere above the float bath
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B25/00—Annealing glass products
- C03B25/04—Annealing glass products in a continuous way
- C03B25/06—Annealing glass products in a continuous way with horizontal displacement of the glass products
- C03B25/08—Annealing glass products in a continuous way with horizontal displacement of the glass products of glass sheets
-
- 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
- C03C23/00—Other surface treatment of glass not in the form of fibres or filaments
- C03C23/008—Other surface treatment of glass not in the form of fibres or filaments comprising a lixiviation step
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
- C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
- C03C3/087—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal containing calcium oxide, e.g. common sheet or container glass
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
- G01N23/22—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material
- G01N23/223—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material by irradiating the sample with X-rays or gamma-rays and by measuring X-ray fluorescence
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
- G01N23/22—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material
- G01N23/225—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material using electron or ion
- G01N23/2255—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material using electron or ion using incident ion beams, e.g. proton beams
- G01N23/2258—Measuring secondary ion emission, e.g. secondary ion mass spectrometry [SIMS]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/50—Glass production, e.g. reusing waste heat during processing or shaping
- Y02P40/57—Improving the yield, e-g- reduction of reject rates
Definitions
- the present invention relates to a float glass for chemical strengthening.
- a thin plate-like cover glass is formed on the front surface of the display so as to be wider than the image display portion in order to enhance the protection and aesthetics of the display. It has been done to arrange.
- 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 float glass manufactured by the float process is chemically strengthened to form a compressive stress layer on the surface to enhance the scratch resistance of the cover glass.
- Patent Document 1 It has been reported that the float glass is warped after chemical strengthening and the flatness is impaired (Patent Document 1).
- the warpage is caused by chemical strengthening between a glass surface that is not in contact with molten tin (hereinafter also referred to as a top surface) and a glass surface that is in contact with molten tin (hereinafter also referred to as a bottom surface) during float forming. It is supposed to be caused by different ways of entering.
- Patent Document 1 the plate-like body manufactured and processed by the float process is chemically polished after being immersed in or contacted with Li ions, Na ions, or a mixed inorganic salt thereof without polishing the surface. Improvements are disclosed.
- the strengthening stress due to chemical strengthening is reduced, or the top surface and the bottom surface of the float glass are subjected to grinding treatment or polishing treatment, and then chemically strengthened after removing the surface heterogeneous layer.
- Patent Document 1 it is necessary to immerse the float glass in the mixed inorganic salt before chemical strengthening, which is complicated. Moreover, there is a possibility that the strength of the float glass after chemical strengthening becomes insufficient by the method of reducing the strengthening stress.
- the method of grinding or polishing the top and bottom surfaces of the float glass before chemical strengthening has a problem from the viewpoint of improving productivity, and it is preferable to omit these grinding or polishing treatments. .
- an object of the present invention is to provide a float glass for chemical strengthening that can effectively suppress warping after chemical strengthening.
- the main cause of the warpage occurring when the soda lime glass produced by the float process is chemically strengthened is caused by a difference in the way of entering the chemical strengthening between the bottom surface and the top surface, and is not necessarily in contact with the molten metal during the float forming. It was found that the difference between the top surface and the bottom surface is not the metal that penetrates the glass surface, but the difference between the top surface and the bottom surface, that is, the difference between the hydration and dealkalization.
- the present invention is as follows. 1. A bottom surface in contact with molten metal at the time of molding, a chemically strengthened float glass having a top surface opposed to the bottom surface, the concentration of Na 2 O in said top surface in concentration of Na 2 O the depth 100 ⁇ m position The normalized Na 2 O concentration at the bottom surface, which is the value obtained by dividing the Na 2 O concentration at the bottom surface by the Na 2 O concentration at the depth of 100 ⁇ m from the square of the normalized Na 2 O surface concentration at the top surface, which is the value obtained by dividing the value. A float glass for chemical strengthening, wherein a difference ⁇ (N—Na 2 O 2 ) obtained by subtracting the square of 2 O surface concentration is 0.040 or less.
- each Na 2 O concentration is a value measured by fluorescent X-ray analysis using Na—K ⁇ rays.
- a float glass for chemical strengthening having a bottom surface in contact with a molten metal during molding and a top surface facing the bottom surface, wherein the ion exchange amount 1 on the bottom surface is reduced from the ion exchange amount 1 on the top surface.
- the float glass for chemical strengthening whose ⁇ ion exchange amount 1 which is a value is 0.32 or less.
- the ion exchange amount 1 is a value obtained by the following equation (2-1).
- Ion exchange amount 1 5.51 ⁇ (standardized Na 2 O surface concentration) ⁇ 0.038 ⁇ (Sn concentration) Formula (2-1)
- normalized Na 2 O surface concentration is a value obtained by dividing the concentration of Na 2 O surface concentration of Na 2 O the depth 100 ⁇ m position.
- the Na 2 O concentration is a value measured by fluorescent X-ray analysis using Na—K ⁇ rays.
- the Sn concentration is the Sn adhesion amount per unit area of the top and bottom surfaces (unit: as SnO 2 ⁇ g / cm 2 ).
- the unit of the Sn deposition amount per unit area is “as SnO 2 ⁇ g / cm 2 ” when the Sn deposition amount per unit area is assumed to be Sn in the form of SnO 2. This is to clearly show that the amount of Sn deposited per 1 cm 2 is expressed in terms of SnO 2 equivalent, and in this specification, the amount of deposited Sn per unit area (unit: ⁇ g / cm 2 ) is the amount of deposited Sn per unit area (unit: ⁇ g / cm 2 ). Unit: as SnO 2 ⁇ g / cm 2 ) 3.
- a chemically strengthened float glass having a bottom surface in contact with a molten metal at the time of molding and a top surface facing the bottom surface, wherein W1 obtained by the following formula (3-1) is 56 or less Glass.
- W1 ⁇ 16 ⁇ ( ⁇ H / Si) ⁇ 6.47 ⁇ (Sn concentration difference) ⁇ 43.8 ⁇ ( ⁇ ion exchange amount 1) Equation (3-1)
- ⁇ H / Si is a value obtained by subtracting the normalized hydrogen concentration at the bottom surface from the normalized hydrogen concentration at the top surface.
- the normalized hydrogen concentration is a value obtained by dividing the average hydrogen concentration at a depth of 0 to 10 ⁇ m by the average hydrogen concentration at a depth of 105 to 110 ⁇ m, and an average hydrogen concentration at a depth of 0 to 10 ⁇ m and an average at a depth of 105 to 110 ⁇ m.
- the hydrogen concentration is a value measured under the following analytical conditions.
- Measuring device Secondary ion mass spectrometer having a quadrupole mass analyzer
- 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 200 ⁇ 200 ⁇ m 2
- Detection area 40 ⁇ 40 ⁇ m 2
- Secondary ion polarity Use of electron gun for negative neutralization Formula (3-1)
- the difference in Sn concentration is the amount of Sn adhered per unit area of the bottom surface (unit: as SnO 2 ⁇ g / cm 2 ) This is a difference obtained by subtracting the Sn adhesion amount per unit (unit: ⁇ g / cm 2 ), and is equal to the Sn adhesion amount per unit area of the bottom surface when the glass does not contain SnO 2 .
- the ⁇ ion exchange amount 1 is a value obtained by subtracting the ion exchange amount 1 on the bottom surface from the ion exchange amount 1 on the top surface.
- the ion exchange amount 1 is obtained by the following equation.
- Ion exchange amount 1 5.51 ⁇ (standardized Na 2 O surface concentration) ⁇ 0.038 ⁇ (Sn concentration)
- normalized Na 2 O surface concentration is a value obtained by dividing the concentration of Na 2 O surface concentration of Na 2 O the depth 100 ⁇ m position.
- the Na 2 O concentration is a value measured by fluorescent X-ray analysis using Na—K ⁇ rays. 4).
- a chemically strengthened float glass having a bottom surface in contact with a molten metal at the time of molding and a top surface facing the bottom surface, wherein the absolute value of W2 obtained by the following formula (4-1) is 56 or less Tempered float glass.
- W2 9.18 ⁇ ⁇ [(ion exchange amount) / (H / Si)] + 49 (Equation (4-1))
- ⁇ [(ion exchange amount) / (H / Si)] is obtained by dividing the ion exchange amount 1 on the top surface by the normalized hydrogen concentration H / Si on the same surface, on the bottom surface.
- ion exchange amount 1 5.51 ⁇ (standardized Na 2 O surface concentration) ⁇ 0.038 ⁇ (Sn concentration)
- normalized Na 2 O surface concentration is a value obtained by dividing the concentration of Na 2 O surface concentration of Na 2 O the depth 100 ⁇ m position.
- the Na 2 O concentration is a value measured by fluorescent X-ray analysis using Na—K ⁇ rays.
- Sn concentration is the Sn adhesion amount per unit area of the top and bottom surfaces (unit: as SnO 2 ⁇ g / cm 2 ).
- the normalized hydrogen concentration is a value obtained by dividing an average hydrogen concentration at a depth of 1 to 10 ⁇ m by an average hydrogen concentration at a depth of 105 to 110 ⁇ m, and an average hydrogen concentration at a depth of 1 to 10 ⁇ m and an average at a depth of 105 to 110 ⁇ m.
- the hydrogen concentration is a value measured under the following analytical conditions.
- Measuring device Secondary ion mass spectrometer having a quadrupole mass analyzer
- 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 200 ⁇ 200 ⁇ m 2
- Detection area 40 ⁇ 40 ⁇ m 2
- Secondary ion polarity Use of electron gun for negative neutralization 5.
- a chemically strengthened float glass having a bottom surface in contact with a molten metal at the time of molding and a top surface facing the bottom surface, wherein W3 obtained by the following formula (5-1) is 58 or less Glass.
- ⁇ N-Na 2 O normalized Na 2 O surface of the top surface is a value obtained by dividing the concentration of Na 2 O the depth 100 ⁇ m positions concentration of Na 2 O of the surface at the top surface is a value obtained by subtracting the normalized Na 2 O surface concentration of the bottom surface of the concentration of Na 2 O is a value obtained by dividing the concentration of Na 2 O the depth 100 ⁇ m position of the surface at the bottom surface from the concentration.
- each Na 2 O concentration is a value measured by fluorescent X-ray analysis using Na—K ⁇ rays.
- the Sn concentration difference is defined as Sn adhesion amount per unit area of bottom surface (unit: as SnO 2 ⁇ g / cm 2 ) to Sn adhesion amount per unit area of top surface (unit: as SnO 2 ⁇ g). / Cm 2 ), and when the glass does not contain SnO 2 , it is equal to the Sn adhesion amount per unit area of the bottom surface.
- a float glass for chemical strengthening having a bottom surface in contact with a molten metal at the time of molding and a top surface opposite to the bottom surface, wherein the ion exchange amount 2 on the bottom surface is reduced from the ion exchange amount 2 on the top surface.
- the float glass for chemical strengthening whose ⁇ ion exchange amount 2 as a value is 0.33 or less.
- the ion exchange amount 2 is a value obtained by the following formula (6-1).
- Ion exchange amount 2 ⁇ 0.02 ⁇ (H / Si) + 5.54 ⁇ (N—Na 2 O concentration) ⁇ 0.037 ⁇ (Sn concentration)
- Formula (6-1) In Formula (6-1), H / Si is the normalized hydrogen concentration, and the normalized hydrogen concentration is a value obtained by dividing the average hydrogen concentration at a depth of 0 to 10 ⁇ m by the average hydrogen concentration at a depth of 105 to 110 ⁇ m.
- the average hydrogen concentration at a depth of 0 to 10 ⁇ m and the average hydrogen concentration at a depth of 105 to 110 ⁇ m are values measured under the following analytical conditions.
- Measuring device Secondary ion mass spectrometer having a quadrupole mass analyzer
- 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 200 ⁇ 200 ⁇ m 2
- Negative neutralizing N-concentration of Na 2 O electron gun used chromatic formula (6-1) for is a value obtained by dividing the concentration of Na 2 O depth 100 ⁇ m position of the surface concentration of Na 2 O Standards Na 2 O surface concentration.
- the Na 2 O concentration is a value measured by fluorescent X-ray analysis using Na—K ⁇ rays.
- the Sn concentration is the Sn adhesion amount per unit area (unit: as SnO 2 ⁇ g / cm 2 ). 7).
- a bottom surface in contact with molten metal at the time of molding, a chemically strengthened float glass having a top surface opposed to the bottom surface, the concentration of Na 2 O in said top surface in concentration of Na 2 O the depth 100 ⁇ m position normalized Na 2 O surface of the bottom surface is a value obtained by dividing the concentration of Na 2 O the depth 100 ⁇ m positions concentration of Na 2 O from normalized Na 2 O surface concentration at the bottom surface of the top surface is divided by the A float glass for chemical strengthening in which the difference ⁇ N ⁇ Na 2 O squared ( ⁇ N ⁇ Na 2 O) 2 with reduced concentration is 5.0 ⁇ 10 ⁇ 4 or less.
- Each Na 2 O concentration is a value measured by fluorescent X-ray analysis using Na—K ⁇ rays. 8).
- Chemical strengthening temperature T unit: K
- chemical tempering time t used in the chemical strengthening (unit time)
- dol ⁇ 0.13 ⁇ Al 2 O 3 ⁇ 1.88 ⁇ MgO ⁇ 2.41 ⁇ CaO ⁇ 1.85 ⁇ SrO ⁇ 1.35 ⁇ BaO ⁇ 1.59 ⁇ ZrO 2 + 1.50 ⁇ Na 2 O + 2. 42 ⁇ K 2 O-129359 / T + 9.28 ⁇ t 0.5 +182.88 Al 2 O 3 , MgO, CaO, SrO, BaO, ZrO 2 , Na 2 O and K 2 O are not essential components.
- the salt used for chemical strengthening typically has a KNO 3 concentration of 95 to 100% by mass. 9.
- K 2 O is contained in 0 to 7% means that K 2 O is not essential but may be contained up to 7%.
- Preferred composition ranges are SiO 2 64 to 77%, Al 2 O 3 0.01 to 7%, Na 2 O 10 to 18%, K 2 O 0 to 5%, MgO 1 to 10%.
- CaO is 1 to 12%, SrO is 0 to 5%, BaO is 0 to 5%, and ZrO 2 is 0 to 3%. 10. 10. The float glass for chemical strengthening according to any one of 1 to 9 above, wherein in terms of mass percentage, SiO 2 is 60 to 80%, Al 2 O 3 is 0.01 to 8%, and Na 2 O is 8 -22%, K 2 O 0-7%, ZrO 2 0-5%, and MgO, CaO, SrO or BaO is contained. The total content of MgO, CaO, SrO and BaO is 5-25. %, And the ratio of Na 2 O and Al 2 O 3 content ratio Na 2 O / Al 2 O 3 float glass for chemical strengthening is 1.5 or more. 11.
- the float glass for chemical strengthening of the present invention has a small difference between the top surface and the bottom surface, so that the stress due to chemical strengthening is not reduced and the polishing treatment before chemical strengthening is simplified or omitted. Moreover, the curvature of the float glass after chemical strengthening can be reduced, and excellent flatness can be obtained.
- FIG. 1 shows the normalized hydrogen concentration of the surface layer of a soda lime glass plate (base plate) before chemical strengthening [(H / Si) (average H / Si of 0 to 10 ⁇ m, average H / Si of 105 to 110 ⁇ m by SIMS analysis) in a diagram showing the correlation between the divided ones] and the normalized Na 2 O surface concentration (that surface concentration of Na 2 O by X-ray fluorescence analysis divided by concentration of Na 2 O 100 ⁇ m depth position).
- FIG. 2 shows the mechanism of ion exchange between Na + in the glass and H + in the atmosphere in the glass before chemical strengthening.
- FIG. 3 shows the ion exchange amount (K 2 O, wt%) of the soda-lime glass plate after chemical strengthening (fluorescence X-ray analysis) and the normalized Na 2 O surface concentration (fluorescence X) before chemical strengthening (base plate).
- the surface concentration of Na 2 O by line analysis is a graph showing the correlation between the divided by concentration of Na 2 O 100 ⁇ m depth position).
- wt% is mass%.
- FIG. 4 is a schematic diagram showing a method for calculating the ion exchange amount by fluorescent X-ray analysis.
- FIG. 5 (a) to (d) show the mechanism by which the amount of ion exchange decreases when a soda lime glass plate in which Na + and H + are ion-exchanged is immersed in a mixed molten salt of KNO 3 and chemically strengthened. It is a schematic diagram shown.
- FIG. 6 shows ⁇ (N—Na 2 O 2 ) (Top-Bottom), which is the difference between the squares of the normalized Na 2 O surface concentration on the top surface and the bottom surface of the glass subjected to chemical strengthening, with ⁇ warpage. It is the graph which plotted quantity on the vertical axis.
- FIG. 7 is a graph in which the horizontal axis represents the difference in ion exchange amount between the top surface and the bottom surface, and the vertical axis represents the ⁇ warpage amount.
- FIG. 8 shows a graph in which the difference between the values obtained by dividing the ion exchange amount between the top surface and the bottom surface by the hydrogen concentration is plotted on the horizontal axis and the ⁇ warpage amount is plotted on the vertical axis.
- FIG. 9 is a graph in which multiple regression analysis is performed using the normalized Na 2 O surface concentration difference ( ⁇ Na 2 O) and Sn concentration difference (adhesion amount per unit area) and ⁇ warpage amount as factors as the top surface and the bottom surface before chemical strengthening. Indicates.
- FIG. 1 normalized Na 2 O surface concentration difference
- Sn concentration difference asdhesion amount per unit area
- FIG. 10 is a longitudinal sectional view of the chemical strengthening float glass manufacturing apparatus of the present invention.
- FIG. 11 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. 12 shows a graph in which W 1 is plotted on the horizontal axis and ⁇ warpage is plotted on the vertical axis.
- FIG. 13 shows a graph in which W2 is plotted on the horizontal axis and ⁇ warpage is plotted on the vertical axis.
- FIG. 14 shows a graph in which W 3 is plotted on the horizontal axis and ⁇ warpage is plotted on the vertical axis.
- FIG. 15 shows a graph in which the horizontal axis plots the difference between the ion exchange amounts 2 on the top surface and the bottom surface ( ⁇ ion exchange amount 2), and the vertical axis plots the ⁇ warpage amount.
- Figure 16 is the square of the difference obtained by subtracting the normalized Na 2 O surface concentration of the bottom surface from the normalized Na 2 O surface concentration of the top surface to the horizontal axis [ ⁇ N-Na 2 O (Top -Bottom)] 2, vertical The graph which plotted (DELTA) curvature amount on the axis
- FIG. 17 shows a graph in which [( ⁇ N ⁇ Na 2 O) + 0.01 ⁇ (Sn concentration difference)] is plotted on the horizontal axis and W3 is plotted on the vertical axis.
- burn refers to a phenomenon in which the glass surface is eroded by the atmosphere, usually deteriorated by the influence of humidity.
- an alkali metal component on the surface layer of the glass typically Na 2 O, is present.
- the degree of glass burn can be analyzed by measuring the Na 2 O concentration by fluorescent X-ray analysis.
- Fig. 1 shows normalized hydrogen concentration (SIMS analysis) and normalized Na 2 O surface concentration (surface Na 2 O concentration by fluorescent X-ray analysis at a depth of 100 ⁇ m) in the surface layer of a soda-lime glass plate (base plate) before chemical strengthening. And the one obtained by dividing by the Na 2 O concentration).
- the normalized hydrogen concentration of the surface layer of the soda lime glass plate before chemical strengthening and the normalized Na 2 O surface concentration are in an inversely proportional relationship.
- FIG. 3 shows the correlation between the ion exchange amount (wt%) (fluorescence X-ray analysis) of the soda-lime glass plate after chemical strengthening and the normalized Na 2 O surface concentration of the base plate.
- the ion exchange amount is defined as a value obtained by subtracting the K 2 O analysis value before chemical strengthening (base plate) from the K 2 O analysis value after chemical strengthening.
- the degree of burn before soda lime glass is chemically strengthened affects the ion exchange amount, and it is considered that the warpage after chemical strengthening occurs when the ion exchange amount differs between the top surface and the bottom surface. From this, in order to control the warpage of the soda lime glass after chemical strengthening, the difference in the degree of burnt of the glass surface layer on the top surface and bottom surface of the glass before chemical strengthening (Na in the top surface and bottom surface). control 2 O concentration difference) is considered to be important.
- Sn concentration The Sn (tin) profile ( 120 Sn ⁇ / 30 Si ⁇ ) on the bottom surface of soda lime glass produced by the float method was analyzed by a secondary ion mass spectrometer (SIMS). The depth and the depth at which Sn penetrated were about 7 ⁇ m. Therefore, when performing chemical strengthening of low DOL such that the ion exchange depth and therefore DOL is typically 20 ⁇ m or less, there is a difference in the way of entering the chemical strengthening between the bottom surface and the top surface. Therefore, it may be necessary to consider the Sn concentration.
- ⁇ (N—Na 2 O 2 ) and ( ⁇ N—Na 2 O) 2 both depend on the degree of burn, but do not depend directly on the Sn concentration.
- Sn intrusion into the bottom surface in the float bath is due to ion exchange with Na on the glass surface layer. Therefore, it is considered that the glass with a large amount of Sn adhesion has a low Na concentration in the surface layer. Therefore, the normalized Na 2 O surface concentration is related to the Sn concentration. That is, it can be said that ⁇ (N—Na 2 O 2 ) and ( ⁇ N—Na 2 O) 2 are not explicit, but depend on the Sn concentration.
- the Sn concentration of the glass is determined by measuring the Sn adhesion amount per unit area. Specifically, for example, the Sn concentration in the solution can be quantified and determined by ICP emission spectroscopic analysis after etching with a hydrofluoric acid solution.
- the float glass for chemical strengthening of the present invention is formed by the float process, and has a bottom surface that contacts the molten metal at the time of forming and a top surface that faces the bottom surface. As described below, it is considered that the difference in hydrogen concentration between the top surface and the bottom surface may be one of the causes of warpage caused by chemically strengthening the float glass.
- molten glass is continuously supplied from the upstream side to the surface of the molten metal stored in the float bath, and a glass ribbon is formed while forming the glass ribbon from the downstream end of the float bath.
- a glass ribbon is drawn out and slowly cooled with a layer to produce a plate glass.
- the glass surface with a high hydrogen concentration is less stressed during chemical strengthening, and the glass surface with a lower hydrogen concentration is susceptible to stress during chemical strengthening. It will be.
- the glass when a float glass with a lower hydrogen concentration on the top surface than the bottom surface is chemically strengthened, the glass has a strong stress on the top surface with a lower hydrogen concentration than the bottom surface with a higher hydrogen concentration, and is convex toward the top surface. It is thought that warping occurs and warping occurs.
- the stress approaches to a state where the stresses are balanced, and the warpage is reduced.
- [ 1 H ⁇ / 30 Si ⁇ ] is a value measured under the following analytical conditions.
- Measuring device Secondary ion mass spectrometer having a quadrupole mass analyzer
- Primary ion species Cs +
- Primary acceleration voltage 5.0 kV
- Primary ion current 1 ⁇ A
- Primary ion incident angle 60 °
- Raster size 200 ⁇ 200 ⁇ m 2
- Detection area 40 ⁇ 40 ⁇ m 2
- Secondary ion polarity minus Use of electron gun for neutralization
- 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 1)
- 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 1).
- 1 H ⁇ corresponds to M 1 and 30 Si ⁇ corresponds to R j . Therefore, from (Equation 2), the intensity ratio [ 1 H ⁇ / 30 Si ⁇ ] is equal to the average hydrogen concentration C H divided by K. That is, [ 1 H ⁇ / 30 Si ⁇ ] is a direct indicator of the average hydrogen concentration.
- the normalized strength is a value obtained by dividing [ 1 H ⁇ / 30 Si ⁇ ] at a certain depth x by [ 1 H ⁇ / 30 Si ⁇ ] at a depth of 105 to 110 ⁇ m, that is, C H / K at a certain depth x. It is a value divided by C H / K at a depth of 105 to 110 ⁇ m. K is the same as that obtained by dividing the C H at depth 105 ⁇ 110 [mu] m a C H in the end normalized intensity because they are erased depth x, i.e., a normalized hydrogen concentration at the depth x.
- the reason why the average hydrogen concentration at the depth of 105 to 110 ⁇ m was used as a reference when calculating the normalized hydrogen concentration is that the region of the depth 105 to 110 ⁇ m is considered as an internal region where the average hydrogen concentration does not vary.
- the absolute value of the difference in normalized strength between the top surface and the bottom surface in the float glass is determined by, for example, the following (i) to (iii) by secondary ion mass spectrometry (Secondary Ion Mass Spectrometry, SIMS analysis). The procedure is required.
- the analysis conditions shown below are examples, and should be changed as appropriate depending on the measurement device, sample, and the like.
- More specific analysis conditions are, for example, as follows.
- ADEPT 1010 manufactured by ULVAC-PHI can be mentioned.
- the ion exchange amount is a stress generation factor and is proportional to the K 2 O concentration in the glass after chemical strengthening. Therefore, the difference in ion exchange amount between the top surface and the bottom surface can be analyzed by the difference in K 2 O concentration.
- the K 2 O concentration can be analyzed by fluorescent X-ray analysis.
- the float glass for chemical strengthening of the present invention is a float glass with a small amount of warpage after chemical strengthening.
- the amount of warpage of the float glass can be measured with a contact-type surface shape measuring instrument [for example, Surfcom (trade name) manufactured by Tokyo Seimitsu Co., Ltd.].
- the amount of warpage is measured as the difference between the highest point and the lowest point after performing baseline correction so that the measurement start point and measurement end point are at the same level when measured with a contact-type surface shape measuring instrument.
- it warps in the convex direction of the top surface it is expressed as plus, and when it warps in the convex direction of the bottom surface, it is expressed as minus.
- Warp amount (War amount after chemical strengthening)-(War amount before chemical strengthening)
- the absolute value of the ⁇ warpage when measured on the central 9 cm square portion of the 10 cm square float glass and converted to a sheet thickness of 0.7 mm is 58 ⁇ m or less, 56 ⁇ m or less, 54 ⁇ m or less, or 52 ⁇ m or less. It is preferable.
- the absolute value of the ⁇ warp amount is equal to or less than the upper limit, the warp after chemical strengthening can be reduced.
- the float glass for chemical strengthening of the present invention preferably has a surface compressive stress of chemically strengthened glass of 650 MPa or more, and is particularly suitable for use where the depth of the compressive stress layer is 20 ⁇ m or less.
- the depth of the compressive stress layer is more preferably 15 ⁇ m or less.
- the normalized hydrogen concentration of the surface layer in the glass before chemical strengthening and the normalized Na 2 O surface concentration are in an inversely proportional relationship.
- the normalized Na 2 O surface concentration in the glass before the chemical strengthening has increased ion exchange capacity after the chemical strengthening higher, normalized Na 2 O surface concentration in the glass before the chemical strengthening And the amount of ion exchange are in an inversely proportional relationship.
- FIG. 6 shows the normalized bottom surface from the square of normalized Na 2 O surface concentration of the top surface on the horizontal axis.
- ⁇ (N—Na 2 O 2 ) is the square of the value measured by fluorescent X-ray analysis of the normalized Na 2 O surface concentration on the top and bottom surfaces of the glass subjected to chemical strengthening. It is the difference and is obtained by the following formula (1-2).
- ⁇ (N—Na 2 O 2 ) (Normalized Na 2 O surface concentration on top surface before chemical strengthening) 2
- ⁇ Normalized Na 2 O surface concentration on bottom surface before chemical strengthening
- Each Na 2 O concentration is a value calculated from the relative intensity ratio with respect to the standard sample by measuring the Na-K ⁇ ray intensity by the fluorescent X-ray method.
- concentration of Na 2 O depth 100 [mu] m position is the concentration of Na 2 O measured by X-ray fluorescence surface after scraping the glass from the surface to a depth of 100 [mu] m.
- the analysis depth of the value measured by fluorescent X-ray analysis using Na-K ⁇ rays is typically 3 ⁇ m.
- the difference in the square of the normalized Na 2 O surface concentration between the top surface and the bottom surface of the glass subjected to chemical strengthening is 0.040 or less, preferably 0.035 or less, 0.030 or less, or 0.025 or less. is there. Even if the polishing process before chemical strengthening is simplified or omitted by making the difference in square of the normalized Na 2 O surface concentration between the top surface and the bottom surface of the glass subjected to chemical strengthening 0.040 or less, The warp of the float glass after chemical strengthening can be reduced and excellent flatness can be obtained.
- ( ⁇ N-Na 2 O) 2 is the square of the difference between the values measured by fluorescent X-ray analysis of the normalized Na 2 O surface concentration on the top and bottom surfaces of the glass subjected to chemical strengthening. And is obtained by the following equation (7-2).
- ( ⁇ N-Na 2 O) 2 [( normalized Na 2 O surface concentration at the top surface before chemical strengthening) - (normalized Na 2 O surface concentration at the bottom surface of the front chemical strengthening) 2 Equation (7 2)
- the square difference of the normalized Na 2 O concentration difference between the top surface and the bottom surface of the glass used for chemical strengthening is 5.0 ⁇ 10 ⁇ 4 or less, preferably 4.5 ⁇ 10 ⁇ 4 or less. 0 ⁇ 10 ⁇ 4 or less or 3.5 ⁇ 10 ⁇ 4 or less.
- the normalized Na 2 O surface concentration on the top and bottom surfaces of the glass subjected to chemical strengthening is adjusted, ⁇ (N—Na 2 O 2 ) or ( ⁇ N—Na 2 O) 2 can be adjusted.
- ⁇ N—Na 2 O 2
- ⁇ N—Na 2 O 2 ⁇ N—Na 2 O 2
- Ion exchange amount 1 5.51 ⁇ (standardized Na 2 O surface concentration) ⁇ 0.038 ⁇ (Sn concentration)
- ion exchange amount may also be used to represent the ion exchange amount 1.
- normalized Na 2 O surface concentration is a value obtained by dividing the concentration of Na 2 O depth 100 ⁇ m position of the surface concentration of Na 2 O.
- each Na 2 O concentration is a value measured by fluorescent X-ray analysis using Na—K ⁇ rays.
- the Sn concentration is the Sn adhesion amount per unit area of the top surface and the bottom surface (unit: as SnO 2 ⁇ g / cm 2 ).
- the ⁇ ion exchange amount 1 is 0.32 or less, preferably 0.30 or less, 0.28 or less, 0.26 or less, or 0.24 or less.
- the difference in ion exchange amount 1 between the top surface and the bottom surface after chemical strengthening is obtained.
- a certain ⁇ ion exchange amount 1 can be adjusted. Specifically, for example, when the glass is slowly cooled, water vapor or SO 2 gas is sprayed on the top surface to lower the Na 2 O concentration on the top surface, and the flow rate of SO 2 gas sprayed on the bottom surface is reduced to prevent scratches. It is preferable to increase the Na 2 O concentration on the bottom surface, decrease the temperature upstream of the float bath, or increase the ambient hydrogen concentration to decrease the amount of Sn penetration into the bottom surface.
- ⁇ H / Si is a difference between values measured by SIMS analysis of a difference in hydrogen concentration between the top surface and the bottom surface before chemical strengthening (difference in normalized hydrogen concentration). 2).
- ⁇ H / Si (normalized hydrogen concentration on top surface before chemical strengthening)
- ⁇ normalized hydrogen concentration on bottom surface before chemical strengthening
- the Sn concentration difference is calculated from the Sn adhesion amount per unit area of the bottom surface (unit: as SnO 2 ⁇ g / cm 2 ) to the Sn adhesion amount per unit area of the top surface (unit: as SnO). 2 ⁇ g / cm 2 ), and when the glass does not contain SnO 2 , it is equal to the Sn adhesion amount per unit area of the bottom surface.
- the ⁇ ion exchange amount 1 is a value obtained by subtracting the ion exchange amount on the bottom surface from the ion exchange amount 1 on the top surface.
- the ion exchange amount is obtained by the above equation (2-1).
- FIG. 12 shows a graph in which W1 is plotted on the horizontal axis and ⁇ warpage is plotted on the vertical axis. From the graph shown in FIG. 12, it can be seen that there is a correlation between W1 and the ⁇ warpage amount.
- W1 is 56 or less, preferably 54 or less, 52 or less, or 50 or less.
- W1 can be adjusted by adjusting the hydrogen concentration and the Sn concentration on the bottom surface by the method described later in (A) of “7. Glass Manufacturing Method”. Specifically, for example, when the glass is slowly cooled, water vapor or SO 2 gas is sprayed on the top surface to lower the Na 2 O concentration on the top surface, and the flow rate of SO 2 gas sprayed on the bottom surface is reduced to prevent scratches. It is preferable to increase the Na 2 O concentration on the bottom surface, decrease the temperature upstream of the float bath, or increase the ambient hydrogen concentration to decrease the amount of Sn penetration into the bottom surface.
- the amount of ion exchange is a stress generation factor
- the hydrogen concentration in the glass surface layer is considered to be a stress relaxation factor. That is, it is considered that the glass density decreases as the hydrogen concentration in the glass surface layer increases. Since H in the glass exists in the SiOH state, and the SiOH is generated by cutting the continuous cross-linked structure Si—O—Si in the glass, the density of the glass decreases as the hydrogen concentration in the glass surface layer increases. It is thought that stress is relieved.
- the value obtained by dividing the ion exchange amount by the hydrogen concentration and the warpage amount are considered to have a correlation. .
- FIG. 8 shows a graph in which the horizontal axis shows the difference between values obtained by dividing the ion exchange amount on the top surface and the bottom surface by the normalized hydrogen concentration on the top surface and the bottom surface before chemical strengthening, and the vertical axis plots the ⁇ warpage amount. .
- ⁇ [(ion exchange amount) / (H / Si)] represents the ion exchange amount on the bottom surface from the value obtained by dividing the ion exchange amount on the top surface by the normalized hydrogen concentration H / Si. The value obtained by subtracting the value divided by the normalized hydrogen concentration H / Si.
- FIG. 13 shows a graph in which W2 is plotted on the horizontal axis and ⁇ warpage is plotted on the vertical axis. From the graph shown in FIG. 13, it can be seen that there is a correlation between W2 and the ⁇ warpage amount.
- W2 is 56 or less, preferably 54 or less, 52 or less, or 50 or less.
- W2 can be adjusted by adjusting the hydrogen concentration by the method described later in (7) “7. Manufacturing method of glass”. Specifically, for example, when the glass is slowly cooled, water vapor or SO 2 gas is sprayed on the top surface to lower the Na 2 O concentration on the top surface, and the flow rate of SO 2 gas sprayed on the bottom surface is reduced to prevent scratches. It is preferable to increase the Na 2 O concentration on the bottom surface, decrease the temperature upstream of the float bath, or increase the ambient hydrogen concentration to decrease the amount of Sn penetration into the bottom surface.
- ⁇ N—Na 2 O is a value obtained by dividing the Na 2 O concentration on the top and bottom surfaces of the glass subjected to chemical strengthening by the Na 2 O concentration at a depth of 100 ⁇ m.
- Na 2 O surface concentration difference which is determined by the following formula (5-2).
- each Na 2 O concentration is a value measured by fluorescent X-ray analysis using Na—K ⁇ rays.
- ⁇ N-Na 2 O (normalized Na 2 O surface concentration at the top surface) - (normalized Na 2 O surface concentration at the bottom surface)
- the Sn concentration difference is the Sn concentration difference between the top surface and the bottom surface before chemical strengthening, and the Sn adhesion amount per unit area of the bottom surface (unit: as SnO 2 ⁇ g / cm 2 ) is used per unit area of the top surface. This is a difference obtained by subtracting the Sn adhesion amount (unit: as SnO 2 ⁇ g / cm 2 ). When the glass does not contain SnO 2 , it is equal to the Sn adhesion amount per unit area of the bottom surface.
- FIG. 13 shows a graph in which W3 is plotted on the horizontal axis and ⁇ warpage is plotted on the vertical axis. From the graph shown in FIG. 12, it can be seen that there is a correlation between W3 and the ⁇ warpage amount.
- W3 is 58 or less, preferably 56 or less, 54 or less, or 52 or less.
- W3 can be adjusted by adjusting the Na 2 O concentration difference and the Sn concentration difference by the method described later in “A. Glass manufacturing method” (A). Specifically, for example, when the glass is slowly cooled, water vapor or SO 2 gas is sprayed on the top surface to lower the Na 2 O concentration on the top surface, and the flow rate of SO 2 gas sprayed on the bottom surface is reduced to prevent scratches. It is preferable to increase the Na 2 O concentration on the bottom surface, decrease the temperature upstream of the float bath, or increase the ambient hydrogen concentration to decrease the amount of Sn penetration into the bottom surface.
- FIG. 15 shows a graph in which the horizontal axis represents the difference between the ion exchange amounts 2 on the top surface and the bottom surface ( ⁇ ion exchange amount 2), and the vertical axis represents the ⁇ warpage amount. From the graph shown in FIG. 15, it can be seen that there is a correlation between the ⁇ ion exchange amount 2 and the ⁇ warpage amount.
- the ⁇ ion exchange amount 2 is 0.33 or less, preferably 0.31 or less, 0.29 or less, or 0.27 or less.
- Glass manufacturing method can do. Specifically, for example, when the glass is slowly cooled, water vapor or SO 2 gas is sprayed on the top surface to lower the Na 2 O concentration on the top surface, and the flow rate of SO 2 gas sprayed on the bottom surface is reduced to prevent scratches. It is preferable to increase the Na 2 O concentration on the bottom surface, decrease the temperature upstream of the float bath, or increase the ambient hydrogen concentration to decrease the amount of Sn penetration into the bottom surface.
- Glass manufacturing method Float glass has a small difference between the top surface and the bottom surface, and the difference in the amount of metal that enters the glass surface that comes into contact with the molten metal during float forming reduces the amount of warpage.
- the following methods (A) to (D) may be mentioned. These methods may be used alone or in combination.
- FIG. 10 is a longitudinal sectional view of a float glass manufacturing apparatus according to the present invention.
- 12 is a twill
- 22 is a fixed refractory under the twill
- 23 is a lip of a spout.
- the raw material is continuously supplied into the glass tank kiln, the raw material is melted in the high temperature area in the glass tank kiln, and the obtained molten glass is guided to the cooling area to adjust the temperature.
- the molten glass 1 whose temperature has been adjusted passes through the connection groove 11 and passes through the gap 2 formed by the twill 12 and the fixed refractory 22 located therebelow. Subsequently, it is supplied to the molten metal bath 5 through the lip 23 of the spout and formed into the glass ribbon 4.
- the float glass preferably has a thickness of 1.5 mm or less, more preferably 1.1 mm or less. Moreover, although it is typically 0.7 mm or more, a thinner one is used if necessary.
- examples of the composition of the float glass for chemical strengthening include the following glass compositions.
- (I) Composition expressed in mass%, SiO 2 60-60%, Al 2 O 3 0.01-8%, Na 2 O 8-22%, K 2 O 0-7%, RO (R Mg, Ca, Sr, Ba) 5 to 25% in total, ZrO 2 containing 0 to 5% glass
- a chemically strengthened float glass can be obtained by cutting the formed float glass into a predetermined size with a cutting machine (not shown) and then chemically strengthening.
- alkali metal ions typically Li ions or Na ions
- alkali ions typically, This is a process for forming a compressive stress layer on the glass surface by exchanging for K ions.
- the chemical strengthening treatment can be performed by a conventionally known method.
- FIG. 2 is a cross-sectional view of a display device in which a cover glass is arranged.
- front, rear, left and right are based on the direction of the arrow in the figure.
- the display device 10 generally includes a display panel 20 provided in the housing 15 and a cover glass 30 that covers the entire surface of the display panel 20 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 10 and preventing impact damage, and is formed of a single sheet of glass having a substantially flat shape as a whole. As shown in FIG. 11, the cover glass 30 may be installed so as to be separated from the display side (front side) of the display panel 20 (with an air layer), and has a translucent adhesive film (FIG. (Not shown) may be attached to the display side of the display panel 20.
- a translucent adhesive film FOG. (Not shown) may be attached to the display side of the display panel 20.
- a functional film 41 is provided on the front surface of the cover glass 30 that emits light from the display panel 20, and a functional film 42 is provided on the back surface on which light from the display panel 20 is incident, at a position corresponding to the display panel 20. ing.
- the functional films 41 and 42 are provided on both surfaces in FIG. 2, the functional films 41 and 42 are not limited thereto, 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.
- the display panel and the like cannot be seen from the outside, and the appearance is improved.
- symbol 44 may be not only a black layer but a white layer, for example.
- Example 1 Manufacture of float glass
- Glasses having the following compositions were produced by the float method so that the plate thickness was 0.7 mm, and cut into 10 cm ⁇ 10 cm to produce the float plate glasses of Examples 1 to 4.
- Composition B SiO 2 : 71.5%, Al 2 O 3 : 1.8%, Na 2 O: 13.5%, K 2 O: 0.26%, MgO: 4.64%, CaO: 7.
- the analysis conditions for secondary ion mass spectrometry were as follows.
- Measuring apparatus 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: 200 ⁇ 200 ⁇ m 2 Detection area: 40 ⁇ 40 ⁇ m 2 Sputter rate: 14 nm / sec Secondary ion polarity: minus Use of electron gun for neutralization
- H / Si represents a value obtained by dividing an average value of depth 0 to 10 ⁇ m by an average value of depth 105 to 110 ⁇ m.
- the "N-Na 2 O" a normalized Na 2 O surface concentration is a value obtained by dividing the concentration of Na 2 O in concentration of Na 2 O the depth 100 ⁇ m position.
- the Na 2 O concentration is a value calculated from the relative intensity ratio with the standard sample by measuring the Na-K ⁇ ray intensity by the fluorescent X-ray method.
- the ion exchange amount (K 2 O concentration) after chemical strengthening is shown in the column of K 2 O ion exchange amount in Table 1.
- the Sn concentration on the glass surface was determined by etching the glass surface with a hydrofluoric acid solution and quantifying the Sn concentration in the solution by ICP emission spectroscopy.
- ICP emission spectroscopic analyzer SPS3100 manufactured by SII Nano Technology Co., Ltd. was used.
- Normalized hydrogen concentration [0 to 10 ⁇ m average (H / Si) / 105 to 110 ⁇ m (average H / Si)] before chemical strengthening of the glasses of Examples 1 to 4, N—Na 2 O concentration (surface concentration / 100 ⁇ m depth) Position concentration, hereinafter also referred to as normalized Na 2 O surface concentration), K 2 O concentration and Sn concentration (attachment amount per unit area), ion exchange amount after chemical strengthening (K 2 O concentration), and ⁇ warpage amount were obtained. The results are shown in Table 1.
- N—Na 2 O concentration on the top surface is less than 1 is considered that SO 2 gas sprayed on the bottom surface wraps around the top surface. Further, the difference in the N—Na 2 O concentration on the top surface between, for example, Example 1 and Example 4 is considered to be due to the variation of the SO 2 gas spraying state.
- Example 2 And correlated to the concentration of Na 2 O difference and ⁇ warpage in the top surface and the bottom surface of the concentration of Na 2 O difference and ⁇ warpage chemical strengthening before soda-lime glass plate in the top surface and the bottom surface before chemical strengthening Therefore, the difference ⁇ (N ⁇ Na 2 O 2 ) between the squares of the normalized Na 2 O surface concentration between the top surface and the bottom surface is obtained from the data shown in Table 1, and the correlation with the ⁇ warpage amount is examined. did.
- FIG. 6 shows the difference ⁇ (N ⁇ Na 2 O 2 ) (Top-Bottom) of the normalized Na 2 O surface concentration between the top surface and the bottom surface of the glass subjected to chemical strengthening on the horizontal axis, and ⁇ on the vertical axis. It is the graph which plotted the amount of curvature.
- ⁇ N—Na 2 O 2
- ⁇ is the square of the value measured by fluorescent X-ray analysis of the normalized Na 2 O surface concentration on the top and bottom surfaces of the glass subjected to chemical strengthening. It is the difference and is obtained by the following formula (1-2).
- Na 2 O (normalized Na 2 O surface concentration at the top surface before chemical strengthening) 2 - (normalized Na 2 O surface concentration at the bottom surface of the front chemical strengthening) 2 Equation (1-2)
- Example 3 Difference in ion exchange amount and ⁇ warpage between top surface and bottom surface after chemical strengthening Since the difference in ion exchange amount between top surface and bottom surface and ⁇ warpage are considered to be correlated, the data shown in Table 1 The difference in ion exchange amount ( ⁇ ion exchange amount 1) was obtained from the above, and the correlation with the ⁇ warpage amount was examined.
- the ⁇ ion exchange amount 1 is a value obtained by subtracting the ion exchange amount 1 on the bottom surface from the ion exchange amount 1 on the top surface.
- FIG. 7 is a graph in which the horizontal axis represents the difference ⁇ ion exchange amount 1 between the ion exchange amounts 1 on the top surface and the bottom surface, and the vertical axis represents the ⁇ warp amount.
- the ⁇ warpage amount can be set to 58 ⁇ m or less.
- Example 4 Difference in hydrogen concentration, Sn concentration difference, ion exchange amount difference and ⁇ warpage before chemical strengthening Hydrogen concentration difference, Sn concentration difference, ion exchange amount difference between top surface and bottom surface before chemical strengthening Since it is considered that there is a correlation between the ⁇ warpage amounts, the following equation (3-1) was obtained as a result of multiple regression analysis based on the data shown in Table 1 using these as factors. Table 4 shows data used from the data shown in Table 1.
- ⁇ H / Si is a difference between values measured by SIMS analysis of a difference in hydrogen concentration between the top surface and the bottom surface before chemical strengthening (difference in normalized hydrogen concentration). 2).
- ⁇ H / Si (normalized hydrogen concentration on top surface before chemical strengthening)
- ⁇ normalized hydrogen concentration on bottom surface before chemical strengthening
- the ⁇ ion exchange amount 1 is a value obtained by subtracting the ion exchange amount on the bottom surface from the ion exchange amount on the top surface.
- the amount of ion exchange was determined by the above formula (2-1).
- FIG. 12 shows a graph in which W1 is plotted on the horizontal axis and ⁇ warpage is plotted on the vertical axis. From the graph shown in FIG. 12, it was found that there is a correlation between W1 and the ⁇ warpage amount. From the results shown in Table 4 and FIG. 12, it was found that by setting W1 to 56 or less, the ⁇ warpage amount can be set to 58 ⁇ m or less.
- Example 4 Difference in ion exchange amount between top and bottom surfaces and difference in hydrogen concentration and ⁇ warpage between top and bottom surfaces before chemical strengthening Difference in ion exchange amount between top and bottom surfaces and between top and bottom surfaces before chemical strengthening Since it is considered that there is a correlation between the difference in hydrogen concentration and the amount of ⁇ warp, from the data shown in Table 1, the difference in ion exchange amount between the top surface and the bottom surface and the difference in hydrogen concentration between the top surface and the bottom surface before chemical strengthening. And the correlation between the amount of ⁇ warp.
- FIG. 8 is a graph in which the horizontal axis represents the difference between the ion exchange amounts on the top surface and the bottom surface divided by the difference in hydrogen concentration between the top surface and the bottom surface before chemical strengthening, and the vertical axis represents the ⁇ warpage amount. .
- ⁇ [(ion exchange amount) / (H / Si)] represents the ion exchange amount on the bottom surface from the value obtained by dividing the ion exchange amount on the top surface by the normalized hydrogen concentration H / Si. The value obtained by subtracting the value divided by the normalized hydrogen concentration H / Si. The amount of ion exchange was determined by the above formula (2-1).
- FIG. 13 shows a graph in which W2 is plotted on the horizontal axis and ⁇ warpage is plotted on the vertical axis. From the graph shown in FIG. 13, it was found that there is a correlation between W2 and the ⁇ warpage amount. From the results shown in Table 5 and FIG. 13, it was found that by setting W2 to 56 or less, the ⁇ warpage amount can be set to 58 ⁇ m or less.
- Example 5 Na 2 O concentration difference and Sn concentration difference and ⁇ warpage amount between top surface and bottom surface before chemical strengthening Normalized Na 2 O surface concentration difference and Sn concentration and ⁇ warpage amount between top surface and bottom surface before chemical strengthening Since it is considered that there is a correlation, a multiple regression analysis was performed based on the data shown in Table 1 using these as factors. The results are shown in Table 6, FIG. 9 and FIG.
- ⁇ N-Na 2 O Na 2 O concentration of 100 ⁇ m position value obtained by subtracting the normalized Na 2 O surface concentration at the bottom surface from the normalized Na 2 O surface concentration at the top surface from the surface The difference between the two values is obtained by the following equation (5-2).
- ⁇ N-Na 2 O (normalized Na 2 O surface concentration at the top surface before chemical strengthening) - (normalized Na 2 O surface concentration at the bottom surface of the front chemical strengthening)
- FIG. 14 is a graph in which W3 is plotted on the horizontal axis and ⁇ warpage is plotted on the vertical axis. From the graph shown in FIG. 14, it was found that there is a correlation between W3 and the ⁇ warpage amount. From the results shown in Table 6 and FIG. 14, it was found that by setting W3 to 58 or less, the ⁇ warpage amount can be set to 58 ⁇ m or less.
- the ion exchange amount 2 and the warp of the glass after chemical strengthening include a difference in the ion exchange amount between the top surface and the bottom surface. Since this is considered to be an influence, the correlation between the difference ⁇ ion exchange amount 2 and the ⁇ warpage amount between the top surface and the bottom surface of the ion exchange amount 2 obtained by the equation (6-2) was examined.
- ⁇ ion exchange amount 2 ( ⁇ ion exchange amount 2 on the top surface) ⁇ ( ⁇ ion exchange amount 2 on the bottom surface) Equation (6-2)
- FIG. 15 shows a graph in which the horizontal axis represents the difference between the ion exchange amounts 2 on the top surface and the bottom surface ( ⁇ ion exchange amount 2), and the vertical axis represents the ⁇ warpage amount. From the graph shown in FIG. 15, it was found that there was a correlation between the ⁇ ion exchange amount 2 and the ⁇ warpage amount.
- the ⁇ warpage amount could be 58 ⁇ m or less by setting the ⁇ ion exchange amount 2 to 0.33 or less in the formula (6-1).
- Example 7 And correlated to the concentration of Na 2 O difference and ⁇ warpage in the top surface and the bottom surface of the concentration of Na 2 O difference and ⁇ warpage chemical strengthening before soda-lime glass plate in the top surface and the bottom surface before chemical strengthening it is considered, the square of the difference obtained by subtracting the normalized Na 2 O surface concentration of the bottom surface from the normalized Na 2 O surface concentration of the top surface from the data shown in Table 1 [ ⁇ N-Na 2 O ( Top-bottom) ] 2 was calculated
- Figure 16 is the square of the difference obtained by subtracting the normalized Na 2 O surface concentration of the bottom surface from the normalized Na 2 O surface concentration of the top surface subjected to chemical strengthening in the horizontal axis [ ⁇ N-Na 2 O (Top -Bottom) ] 2 is a graph in which the amount of ⁇ warp is plotted on the vertical axis.
- ( ⁇ N-Na 2 O) 2 is the square of the difference between the values measured by fluorescent X-ray analysis of the normalized Na 2 O surface concentration on the top and bottom surfaces of the glass subjected to chemical strengthening. It was obtained by the following formula (7-2).
- ( ⁇ N-Na 2 O) 2 [( normalized Na 2 O surface concentration at the top surface before chemical strengthening) - (normalized Na 2 O surface concentration at the bottom surface of the front chemical strengthening) 2 Equation (7 2)
- Table 9 shows the composition examples G1 to G16 of the mass percentage display of the float glass for chemical strengthening of the present invention, and the compressive stress CS (unit: MPa) and the compressive stress depth DOL (unit: ⁇ m) when they are chemically strengthened. 10 shows.
- Na 2 O / Al 2 O 3 is the content ratio of Na 2 O and Al 2 O 3
- RO is the total content of MgO
- CaO + SrO + BaO is the content of CaO
- strengthening temperature (unit: ° C.) and strengthening time (unit: h) are for the chemical strengthening
- KNO 3 is the concentration of KNO 3 in the molten salt used for chemical strengthening (unit: mass%)
- dol is the dol. Incidentally, the remaining components of that concentration of KNO 3 in the molten salt is not 100% is NaNO 3.
Abstract
Description
1.成形時に溶融金属と接するボトム面と、該ボトム面に対向するトップ面とを有する化学強化用フロートガラスであって、該トップ面におけるNa2O濃度をその深さ100μm位置のNa2O濃度で除した値であるトップ面の規格化Na2O表面濃度の2乗から該ボトム面におけるNa2O濃度をその深さ100μm位置のNa2O濃度で除した値であるボトム面の規格化Na2O表面濃度の2乗を減じた差Δ(N-Na2O2)が0.040以下である化学強化用フロートガラス。
ここで、それぞれのNa2O濃度はNa-Kα線を用いる蛍光X線分析により測定した値である。
2.成形時に溶融金属と接するボトム面と、該ボトム面に対向するトップ面とを有する化学強化用フロートガラスであって、該トップ面におけるイオン交換量1から該ボトム面におけるイオン交換量1を減じた値であるΔイオン交換量1が0.32以下である化学強化用フロートガラス。
ここで、イオン交換量1は下記式(2-1)により求められる値である。
イオン交換量1=5.51×(規格化Na2O表面濃度)-0.038×(Sn濃度)…式(2-1)
式(2-1)において、規格化Na2O表面濃度は表面のNa2O濃度をその深さ100μm位置のNa2O濃度で除した値である。ここで、Na2O濃度はNa-Kα線を用いる蛍光X線分析による測定値である。
また、Sn濃度はトップ面およびボトム面単位面積当たりのSn付着量(単位:as SnO2μg/cm2)である。本明細書で単位面積当たりのSn付着量の単位が「as SnO2μg/cm2」とされているのは、単位面積当たりのSn付着量が、SnがSnO2の形で存在するとしたときの1cm2あたりのSnO2換算付着質量で示されることを明示するためであり、本明細書においては単位面積当たりのSn付着量(単位:μg/cm2)は単位面積当たりのSn付着量(単位:as SnO2μg/cm2)と同義である。
3.成形時に溶融金属と接するボトム面と、該ボトム面に対向するトップ面とを有する化学強化用フロートガラスであって、下記式(3-1)により求められるW1が56以下である化学強化用フロートガラス。
W1=-16×(ΔH/Si)-6.47×(Sn濃度差)-43.8×(Δイオン交換量1)…式(3-1)
式(3-1)において、ΔH/Siは、トップ面における規格化水素濃度からボトム面における規格化水素濃度を減じた値である。規格化水素濃度とは、深さ0~10μmにおける平均水素濃度を深さ105~110μmにおける平均水素濃度で除した値であり、深さ0~10μmにおける平均水素濃度および深さ105~110μmにおける平均水素濃度は、以下の分析条件下で測定した値である。
(分析条件)
測定装置:四重極型質量分析器を有する二次イオン質量分析装置
一次イオン種:Cs+
一次加速電圧:5.0kV
一次イオンカレント:1μA
一次イオン入射角(試料面垂直方向からの角度):60°
ラスターサイズ:200×200μm2
検出領域:40×40μm2
二次イオン極性:マイナス中和用の電子銃使用有
式(3-1)において、Sn濃度差はボトム面単位面積当たりのSn付着量(単位:as SnO2μg/cm2)からトップ面単位面積当たりのSn付着量(単位:μg/cm2)を減じた差であり、ガラスがSnO2を含有しない場合はボトム面単位面積当たりのSn付着量に等しい。
式(3-1)において、Δイオン交換量1はトップ面におけるイオン交換量1から該ボトム面におけるイオン交換量1を減じた値である。
ここで、イオン交換量1は下記式により求められる。
イオン交換量1=5.51×(規格化Na2O表面濃度)-0.038×(Sn濃度)
前記式において、規格化Na2O表面濃度は、表面のNa2O濃度をその深さ100μm位置のNa2O濃度で除した値である。ここで、Na2O濃度はNa-Kα線を用いる蛍光X線分析による測定値である。
4.成形時に溶融金属と接するボトム面と、該ボトム面に対向するトップ面とを有する化学強化用フロートガラスであって、下記式(4-1)により求められるW2の絶対値が56以下である化学強化用フロートガラス。
W2=9.18×Δ[(イオン交換量)/(H/Si)]+49…式(4-1)
式(4-1)において、Δ[(イオン交換量)/(H/Si)]は、トップ面におけるイオン交換量1を同面における規格化水素濃度H/Siで除した値からボトム面におけるイオン交換量1を同面における規格化水素濃度H/Siで除した値を減じた値である。
ここで、イオン交換量1は下記式により求められる。
イオン交換量1=5.51×(規格化Na2O表面濃度)-0.038×(Sn濃度)
前記式において、規格化Na2O表面濃度は、表面のNa2O濃度をその深さ100μm位置のNa2O濃度で除した値である。ここで、Na2O濃度はNa-Kα線を用いる蛍光X線分析による測定値である。また、Sn濃度はトップ面およびボトム面単位面積当たりのSn付着量(単位:as SnO2μg/cm2)である。
規格化水素濃度とは、深さ1~10μmにおける平均水素濃度を深さ105~110μmにおける平均水素濃度で除した値であり、深さ1~10μmにおける平均水素濃度および深さ105~110μmにおける平均水素濃度は、以下の分析条件下で測定した値である。
(分析条件)
測定装置:四重極型質量分析器を有する二次イオン質量分析装置
一次イオン種:Cs+
一次加速電圧:5.0kV
一次イオンカレント:1μA
一次イオン入射角(試料面垂直方向からの角度):60°
ラスターサイズ:200×200μm2
検出領域:40×40μm2
二次イオン極性:マイナス中和用の電子銃使用有
5.成形時に溶融金属と接するボトム面と、該ボトム面に対向するトップ面とを有する化学強化用フロートガラスであって、下記式(5-1)により求められるW3が58以下である化学強化用フロートガラス。
W3=744×[(ΔN-Na2O)+0.01×(Sn濃度差)]…式(5-1)
式(5-1)において、ΔN-Na2Oは、トップ面における表面のNa2O濃度をその深さ100μm位置のNa2O濃度で除した値であるトップ面の規格化Na2O表面濃度からボトム面における表面のNa2O濃度をその深さ100μm位置のNa2O濃度で除した値であるボトム面の規格化Na2O表面濃度を減じた値である。ここで、それぞれのNa2O濃度はNa-Kα線を用いる蛍光X線分析による測定値である。
式(5-1)において、Sn濃度差は、ボトム面単位面積当たりのSn付着量(単位:as SnO2μg/cm2)からトップ面単位面積当たりのSn付着量(単位:as SnO2μg/cm2)を減じた差であり、ガラスがSnO2を含有しない場合はボトム面単位面積当たりのSn付着量に等しい。
6.成形時に溶融金属と接するボトム面と、該ボトム面に対向するトップ面とを有する化学強化用フロートガラスであって、該トップ面におけるイオン交換量2から該ボトム面におけるイオン交換量2を減じた値であるΔイオン交換量2が0.33以下である化学強化用フロートガラス。イオン交換量2は下記式(6-1)により求められる値である。
イオン交換量2=-0.02×(H/Si)+5.54×(N-Na2O濃度)-0.037×(Sn濃度)…式(6-1)
式(6-1)において、H/Siは規格化水素濃度であり、規格化水素濃度とは深さ0~10μmにおける平均水素濃度を深さ105~110μmにおける平均水素濃度で除した値であり、深さ0~10μmにおける平均水素濃度および深さ105~110μmにおける平均水素濃度は、以下の分析条件下で測定した値である。
(分析条件)
測定装置:四重極型質量分析器を有する二次イオン質量分析装置
一次イオン種:Cs+
一次加速電圧:5.0kV
一次イオンカレント:1μA
一次イオン入射角(試料面垂直方向からの角度):60°
ラスターサイズ:200×200μm2
検出領域:40×40μm2
二次イオン極性:マイナス中和用の電子銃使用有
式(6-1)においてN-Na2O濃度は表面Na2O濃度を深さ100μm位置のNa2O濃度で除した値である規格化Na2O表面濃度である。ここで、Na2O濃度はNa-Kα線を用いる蛍光X線分析による測定値である。
Sn濃度は、単位面積当たりのSn付着量(単位:as SnO2μg/cm2)である。
7.成形時に溶融金属と接するボトム面と、該ボトム面に対向するトップ面とを有する化学強化用フロートガラスであって、該トップ面におけるNa2O濃度をその深さ100μm位置のNa2O濃度で除した値であるトップ面の規格化Na2O表面濃度から該ボトム面におけるNa2O濃度をその深さ100μm位置のNa2O濃度で除した値であるボトム面の規格化Na2O表面濃度を減じた差ΔN-Na2Oの2乗(ΔN-Na2O)2が5.0×10-4以下である化学強化用フロートガラス。それぞれのNa2O濃度はNa-Kα線を用いる蛍光X線分析により測定した値である。
8.化学強化温度がT(単位:K)、化学強化時間がt(単位:時間)である化学強化に用いられ、且つSiO2を含有し、SiO2、Al2O3、MgO、CaO、SrO、BaO、ZrO2、Na2OおよびK2Oの各質量百分率表示含有量を用いて次式で求められるdolが20以下である前項1~7のいずれか1に記載の化学強化用フロートガラス。
dol=-0.13×Al2O3-1.88×MgO-2.41×CaO-1.85×SrO-1.35×BaO-1.59×ZrO2+1.50×Na2O+2.42×K2O-129359/T+9.28×t0.5+182.88
なお、Al2O3、MgO、CaO、SrO、BaO、ZrO2、Na2OおよびK2Oは必須成分ではない。化学強化に用いられる塩はKNO3濃度が95~100質量%であるものが典型的である。
9.質量百分率表示で、SiO2を60~80%、Al2O3を0~8%、Na2Oを8~22%、K2Oを0~7%、MgOを0~17%、CaOを0~22%、SrOを0~8%、BaOを0~8%、ZrO2を0~5%含有する前項1~8のいずれか1項に記載の化学強化用フロートガラス。ここでたとえば、「K2Oを0~7%」含有する、とはK2Oは必須ではないが7%まで含有してもよい、の意である。
好ましい組成範囲としては、SiO2を64~77%、Al2O3を0.01~7%、Na2Oを10~18%、K2Oを0~5%、MgOを1~10%、CaOを1~12%、SrOを0~5%、BaOを0~5%、ZrO2を0~3%である。
10.前項1~9のいずれか1に記載の化学強化用フロートガラスであって、質量百分率表示で、SiO2を60~80%、Al2O3を0.01~8%、Na2Oを8~22%、K2Oを0~7%、ZrO2を0~5%含有し、MgO、CaO、SrOまたはBaOを含有する場合MgO、CaO、SrOおよびBaOの含有量の合計が5~25%であり、Na2OおよびAl2O3の含有量の比Na2O/Al2O3が1.5以上である化学強化用フロートガラス。
11.前項10に記載の化学強化用フロートガラスであって、Na2O/Al2O3が6以下である化学強化用フロートガラス。
12.前項9、10または11に記載の化学強化用フロートガラスであって、CaO、SrOまたはBaOを含有しCaO、SrOおよびBaOの含有量の合計が1~7%である化学強化用フロートガラス。
13.圧縮応力深さが20μm以下である化学強化ガラスを製造する方法であって、前項1~12のいずれか1に記載の化学強化用ガラスを化学強化することを特徴とする化学強化ガラスの製造方法。
フロート法により製造したソーダライムガラスの表面のHプロファイル(1H-/30Si-)を二次イオン質量分析装置(SIMS)により分析したところ、ヤケ(水和および脱アルカリ)層の深さは約3μmであった。したがって、イオン交換深さを20μm以下に化学強化する際には、ボトム面とトップ面の化学強化の入り方に差が生じて反る原因として、トップ面とボトム面におけるヤケ程度の差が重要であると考えられる。
フロート法により製造したソーダライムガラスのボトム面におけるSn(錫)のプロファイル(120Sn-/30Si-)を二次イオン質量分析装置(SIMS)により分析したところ、イオン交換された層の深さとSnが侵入した深さは、約7μmであった。したがって、イオン交換深さしたがってDOLが典型的には20μm以下となるような低DOLの化学強化をする際には、ボトム面とトップ面の化学強化の入り方に差が生じて反る原因として、Sn濃度を考慮する必要がある場合があると考えられる。
本発明の化学強化用フロートガラスは、フロート法により成形され、成形時に溶融金属と接するボトム面と、該ボトム面に対向するトップ面とを有する。以下に述べるように、トップ面とボトム面との水素濃度差はフロートガラスを化学強化することにより生じる反りの原因の一つである場合があると考えられる。
(分析条件)
測定装置:四重極型質量分析器を有する二次イオン質量分析装置
一次イオン種:Cs+
一次加速電圧:5.0kV
一次イオンカレント:1μA
一次イオン入射角(試料面垂直方向からの角度):60°
ラスターサイズ:200×200μm2
検出領域:40×40μm2
二次イオン極性:マイナス
中和用の電子銃使用有
IM1=A・IP・Y・CM・α1・βM・η (式1)
IM1/IRj=(CM・α1・βM)/(CR・αj・βR)=CM/K (式2)
ここでKは元素Mの元素Rに対する相対感度因子である。
K=(CR・αj・βR)/(α1・βM) (式3)
この場合、元素Mの濃度は(式4)より求められる。
CM=K・IM1/IRj (式4)
(分析条件)
測定装置:四重極型質量分析器を有する二次イオン質量分析装置
一次イオン種:Cs+
一次加速電圧:5.0kV
一次イオンカレント:1μA
一次イオン入射角(試料面垂直方向からの角度):60°
ラスターサイズ:200×200μm2
検出領域:40×40μm2
二次イオン極性:マイナス
中和用の電子銃使用有
(分析条件)
測定装置:四重極型質量分析器を有する二次イオン質量分析装置
一次イオン種:Cs+
一次加速電圧:5.0kV
一次イオンカレント:1μA
一次イオン入射角(試料面垂直方向からの角度):60°
ラスターサイズ:200×200μm2
検出領域:40×40μm2
スパッタレート:14nm/sec
二次イオン極性:マイナス
中和用の電子銃使用有
イオン交換量は応力発生因子であり、化学強化後のガラスにおけるK2O濃度と比例関係にある。したがって、トップ面とボトム面におけるイオン交換量の差はK2O濃度の差で分析することができる。K2O濃度は蛍光X線分析により分析することができる。
本発明の化学強化用フロートガラスは、化学強化後の反り量の小さいフロートガラスである。フロートガラスの反り量は、接触式表面形状測定器[例えば株式会社東京精密製サーフコム(商品名)]で測定することができる。
(式)Δ反り量=(化学強化後反り量)-(化学強化前反り量)
上記考察から、以下のパラメータが考えられる。
(1)化学強化前のトップ面とボトム面におけるNa2O濃度差とΔ反り量
ソーダライムガラスの化学強化後の反りを制御するためには、化学強化前のガラス表層におけるヤケ程度、水素濃度およびSn濃度のコントロールが重要であると考えられる。
図6に横軸にトップ面の規格化Na2O表面濃度の2乗からボトム面の規格化Na2O表面濃度の2乗を減じた差Δ(N-Na2O2)(Top-Bottom)、縦軸にΔ反り量をプロットしたグラフを示す。
Δ反り量=370×Δ(N-Na2O2)+45…式(1-1)
Δ(N-Na2O2)=(化学強化前のトップ面における規格化Na2O表面濃度)2-(化学強化前のボトム面における規格化Na2O表面濃度)2…式(1-2)
図16に横軸にトップ面におけるNa2O濃度をその深さ100μm位置のNa2O濃度で除した値であるトップ面の規格化Na2O表面濃度から該ボトム面におけるNa2O濃度をその深さ100μm位置のNa2O濃度で除した値であるボトム面の規格化Na2O表面濃度を減じた差の2乗[ΔN-Na2O(Top-Bottom)]2、縦軸にΔ反り量をプロットしたグラフを示す。
式(7-1)において(ΔN-Na2O)2は、化学強化に供するガラスのトップ面とボトム面における規格化Na2O表面濃度を蛍光X線分析により測定した値の差の2乗であり、下記式(7-2)により求められる。
(ΔN-Na2O)2=[(化学強化前のトップ面における規格化Na2O表面濃度)-(化学強化前のボトム面における規格化Na2O表面濃度)]2…式(7-2)
化学強化後のトップ面とボトム面におけるイオン交換量の差であるΔイオン交換量1とΔ反り量には相関関係があると考えられる。
イオン交換量1=5.51×(規格化Na2O表面濃度)-0.038×(Sn濃度)…式(2-1)
以下、イオン交換量という語はイオン交換量1を表すためにも用いることがある。
イオン交換量1の差=(トップ面におけるイオン交換量1)-(ボトム面におけるイオン交換量1)…式(2-2)
Δ反り量=103×(Δイオン交換量1)2+24…式(2-3)
化学強化前のトップ面とボトム面における水素濃度差、Sn濃度差、イオン交換量差およびにΔ反り量を因子として重回帰分析すると、下記式(3-1)が求められる。
ΔH/Si=(化学強化前のトップ面における規格化水素濃度)-(化学強化前のボトム面における規格化水素濃度)…式(3-2)
イオン交換量は応力発生因子であり、ガラス表層の水素濃度は応力緩和因子であると考えられる。すなわち、ガラス表層の水素濃度が高くなるほどガラスの密度は下がると考えられる。ガラス中のHはSiOHの状態で存在しており、SiOHはガラス中の連続的な架橋構造Si-O-Siが切断されて生成するため、ガラス表層の水素濃度が増える程ガラスの密度が下がり応力が緩和すると考えられる。
W2=9.18×Δ[(イオン交換量)/(H/Si)]+49…式(4-1)
ソーダライムガラスの化学強化後の反りを制御するためには、化学強化前のガラス表層のヤケの程度およびSn濃度のコントロールが重要であることから、化学強化前のトップ面とボトム面におけるNa2O濃度差およびSn濃度とΔ反り量には相関関係があると考えられる。
W3=744×[(ΔN-Na2O)+0.01×(Sn濃度差)]…式(5-1)
ΔN-Na2O=(トップ面における規格化Na2O表面濃度)-(ボトム面における規格化Na2O表面濃度)…式(5-2)
化学強化後のガラスの反りには、トップ面及びボトム面におけるイオン交換量の差が影響しており、イオン交換量には水素濃度、Na2O濃度およびSn濃度が関与していると考えられる。したがって、イオン交換量と規格化水素濃度、規格化Na2O表面濃度およびSn濃度は以下の式(6-1)で表される相関関係を示す。
イオン交換量2=-0.02×(H/Si)+5.54×(N-Na2O濃度)-0.037×(Sn濃度)…式(6-1)
Δイオン交換量2=(トップ面におけるΔイオン交換量2)-(ボトム面におけるΔイオン交換量2)…式(6-2)
フロートガラスにおけるトップ面とボトム面とのヤケ程度の差が小さく、且つフロート成形時において溶融金属と接触するガラス面に侵入する金属量の差が小さくしてΔ反り量を低減するための方法としては、例えば、以下の(A)~(D)に示す方法が挙げられる。これらの方法は単独で用いても、組み合わせてもよい。
(D)フロートバス上流域の温度を下げる。
(i)質量%で表示した組成で、SiO2を60~80%、Al2O3を0.01~8%、Na2Oを8~22%、K2Oを0~7%、RO(R=Mg、Ca、Sr、Ba)を合量で5~25%、ZrO2を0~5%を含むガラス
(ii)質量%で表示した組成で、SiO2を64~77%、Al2O3を0.01~7%、Na2Oを10~18%、K2Oを0~5%、MgOを1~10%、CaOを1~12%、SrOを0~5%、BaOを0~5%、ZrO2を0~3%であるガラス
(iii)質量%で表示した組成で、SiO2を60~80%、Al2O3を0.01~8%、Na2Oを8~22%、K2Oを0~7%、ZrO2を0~5%含有し、MgO、CaO、SrOまたはBaOを含有する場合MgO、CaO、SrOおよびBaOの含有量の合計が5~25%であり、Na2OおよびAl2O3の含有量の比Na2O/Al2O3が1.5以上であるガラス
(iv)質量%で表示した組成で、SiO2を60~80%、Al2O3を0.01~8%、Na2Oを8~22%、K2Oを0~7%、ZrO2を0~5%含有し、MgO、CaO、SrOまたはBaOを含有する場合MgO、CaO、SrOおよびBaOの含有量の合計が5~25%であり、Na2OおよびAl2O3の含有量の比Na2O/Al2O3が1.5以上6以下であるガラス
(v)質量%で表示した組成で、SiO2を60~80%、Al2O3を0.01~8%、Na2Oを8~22%、K2Oを0~7%、ZrO2を0~5%含有し、MgO、CaO、SrOまたはBaOを含有する場合MgO、CaO、SrOおよびBaOの含有量の合計が5~25%であり、CaO、SrOおよびBaOの含有量の合計が1~7%であり、Na2OおよびAl2O3の含有量の比Na2O/Al2O3が1.5以上であるガラス
〔フロートガラスの製造〕
以下に示す組成のガラスを板厚が0.7mmとなるようにフロート法で製造し、10cm×10cmに切断して、例1~4のフロート板ガラスを作製した。
組成A:質量%表示の組成が、SiO2:71.5%、Al2O3:1.8%、Na2O:13.5%、K2O:0.26%、MgO:4.64%、CaO:7.83%、ZrO2:0.03%
組成B:SiO2:71.5%、Al2O3:1.8%、Na2O:13.5%、K2O:0.26%、MgO:4.64%、CaO:7.83%、ZrO2:0.03%
組成C:SiO2:71.5%、Al2O3:1.8%、Na2O:13.5%、K2O:0.26%、MgO:4.64%、CaO:7.83%、ZrO2:0.03%
(1)ガラス表層の水素濃度の測定
また、実施例1、2および比較例1~3の各フロートガラスの水素濃度を、二次イオン質量分析により深さ20μmまで分析した。フロートガラスの二次イオン質量分析による[1H-/30Si-]プロファイルを示すが、このプロファイルは水素濃度プロファイルと同視してよいものである。
測定装置:アルバック・ファイ社製 ADEPT1010
一次イオン種:Cs+
一次加速電圧:5.0kV
一次イオンカレント:1μA
一次イオン入射角(試料面垂直方向からの角度):60°
ラスターサイズ:200×200μm2
検出領域:40×40μm2
スパッタレート:14nm/sec
二次イオン極性:マイナス
中和用の電子銃使用有
化学強化前に株式会社東京精密製接触式表面形状測定器(サーフコム1400D(商品名))で反り量を測定した後、各フロートガラスを硝酸カリウム溶融塩により、425℃にて150分化学強化し、化学強化後の反り量も同様に測定し、(式)Δ反り量=化学強化後反り量-化学強化前反り量で表されるΔ反り量を算出した。なお、Δ反り量は、9cm角のフロートガラスにおけるΔ反り量を測定とした。
ガラス表層のNa2O濃度およびK2O濃度は、株式会社リガク社製ZSX PrimusIIを用いて蛍光X線分析によりそれぞれNa-Kα線、K-Kα線強度を測定し、標準試料との相対強度比から濃度を求めた。
ガラス表面のSn濃度は、ガラス表面をフッ化水素酸溶液でエッチングして溶液中のSn濃度をICP発光分光分析法により定量した。ICP発光分光分析装置はエスアイアイ・ナノテクノロジー株式会社製SPS3100を用いた。
化学強化前のトップ面とボトム面におけるNa2O濃度差とΔ反り量
化学強化前のソーダライムガラス板のトップ面とボトム面におけるNa2O濃度差とΔ反り量とは相関関係があると考えられることから、表1に示すデータからトップ面とボトム面における規格化Na2O表面濃度の2乗の差Δ(N-Na2O2)を求め、Δ反り量との相関関係について検討した。
Δ反り量=370×Δ(N-Na2O2)+45…式(1-1)
ΔNa2O=(化学強化前のトップ面における規格化Na2O表面濃度)2-(化学強化前のボトム面における規格化Na2O表面濃度)2…式(1-2)
化学強化後のトップ面とボトム面におけるイオン交換量差とΔ反り量
トップ面とボトム面におけるイオン交換量の差とΔ反り量には相関関係があると考えられることから、表1に示すデータからイオン交換量の差(Δイオン交換量1)を求め、Δ反り量との相関関係について検討した。
イオン交換量1=5.51×(規格化Na2O表面濃度)-0.038×(Sn濃度)…式(2-1)
Δ反り量=103×(Δイオン交換量1)+24…式(2-3)
化学強化前のトップ面とボトム面における水素濃度差、Sn濃度差およびイオン交換量差とΔ反り量
化学強化前のトップ面とボトム面における水素濃度差、Sn濃度差、イオン交換量差およびにΔ反り量に相関関係があると考えられることから、これらを因子として、表1に示すデータを元に重回帰分析した結果、下記式(3-1)が求められた。表4に、表1に示すデータから用いたデータを示す。
ΔH/Si=(化学強化前のトップ面における規格化水素濃度)-(化学強化前のボトム面における規格化水素濃度)…式(3-2)
トップ面とボトム面におけるイオン交換量差および化学強化前のトップ面とボトム面における水素濃度差とΔ反り量
トップ面とボトム面におけるイオン交換量の差および化学強化前のトップ面とボトム面における水素濃度差とΔ反り量には相関関係があると考えられることから、表1に示すデータから、トップ面とボトム面におけるイオン交換量差および化学強化前のトップ面とボトム面における水素濃度差とΔ反り量の相関関係について検討した。
W2=9.18×Δ[(イオン交換量)/(H/Si)]+49…式(4-1)
化学強化前のトップ面とボトム面におけるNa2O濃度差およびSn濃度差とΔ反り量
化学強化前のトップ面とボトム面における規格化Na2O表面濃度差およびSn濃度とΔ反り量には相関関係があると考えられることから、これらを因子として、表1に示すデータを元に重回帰分析した。その結果を表6、図9および図17に示す。
ΔN-Na2O=(化学強化前のトップ面における規格化Na2O表面濃度)-(化学強化前のボトム面における規格化Na2O表面濃度)…式(5-2)
イオン交換量(水素濃度、Na2O濃度およびSn濃度)の差とΔ反り量
イオン交換量には水素濃度、Na2O濃度およびSn濃度が関与していると考えられることから、表7に示すデータから相関式を求めた結果、下記式(6-1)が得られた。
イオン交換量2=-0.02×(H/Si)+5.54×(N-Na2O濃度)-0.037×(Sn濃度)…式(6-1)
Δイオン交換量2=(トップ面におけるΔイオン交換量2)-(ボトム面におけるΔイオン交換量2)…式(6-2)
化学強化前のトップ面とボトム面におけるNa2O濃度差とΔ反り量
化学強化前のソーダライムガラス板のトップ面とボトム面におけるNa2O濃度差とΔ反り量とは相関関係があると考えられることから、表1に示すデータからトップ面の規格化Na2O表面濃度からボトム面の規格化Na2O表面濃度を減じた差の2乗[ΔN-Na2O(Top-Bottom)]2を求め、Δ反り量との相関関係について検討した。
式(7-1)において(ΔN-Na2O)2は、化学強化に供するガラスのトップ面とボトム面における規格化Na2O表面濃度を蛍光X線分析により測定した値の差の2乗であり、下記式(7-2)により求めた。
(ΔN-Na2O)2=[(化学強化前のトップ面における規格化Na2O表面濃度)-(化学強化前のボトム面における規格化Na2O表面濃度)]2…式(7-2)
本発明の化学強化用フロートガラスの質量百分率表示の組成例G1~G16並びにそれらについて化学強化したときの圧縮応力CS(単位:MPa)および圧縮応力深さDOL(単位:μm)を表9、表10に示す。
5 溶融金属浴
10 ディスプレイ装置
15 筐体
20 表示パネル
30 カバーガラス
Claims (13)
- 成形時に溶融金属と接するボトム面と、該ボトム面に対向するトップ面とを有する化学強化用フロートガラスであって、該トップ面におけるNa2O濃度をその深さ100μm位置のNa2O濃度で除した値であるトップ面の規格化Na2O表面濃度の2乗から該ボトム面におけるNa2O濃度をその深さ100μm位置のNa2O濃度で除した値であるボトム面の規格化Na2O表面濃度の2乗を減じた差Δ(N-Na2O2)が0.040以下である化学強化用フロートガラス。
ここで、それぞれのNa2O濃度はNa-Kα線を用いる蛍光X線分析により測定した値である。 - 成形時に溶融金属と接するボトム面と、該ボトム面に対向するトップ面とを有する化学強化用フロートガラスであって、該トップ面におけるイオン交換量1から該ボトム面におけるイオン交換量1を減じた値であるΔイオン交換量1が0.32以下である化学強化用フロートガラス。
ここで、イオン交換量1は下記式(2-1)により求められる値である。
イオン交換量1=5.51×(規格化Na2O表面濃度)-0.038×(Sn濃度)…式(2-1)
式(2-1)において、規格化Na2O表面濃度は表面のNa2O濃度をその深さ100μm位置のNa2O濃度で除した値である。ここで、Na2O濃度はNa-Kα線を用いる蛍光X線分析による測定値である。
また、Sn濃度はトップ面およびボトム面単位面積当たりのSn付着量(単位:μg/cm2)であり、単位面積当たりのSn付着量はSnがSnO2の形で存在するとしたときの1cm2あたりのSnO2換算付着質量である。 - 成形時に溶融金属と接するボトム面と、該ボトム面に対向するトップ面とを有する化学強化用フロートガラスであって、下記式(3-1)により求められるW1が56以下である化学強化用フロートガラス。
W1=-16×(ΔH/Si)-6.47×(Sn濃度差)-43.8×(Δイオン交換量1)…式(3-1)
式(3-1)において、ΔH/Siは、トップ面における規格化水素濃度からボトム面における規格化水素濃度を減じた値である。規格化水素濃度とは、深さ0~10μmにおける平均水素濃度を深さ105~110μmにおける平均水素濃度で除した値であり、深さ0~10μmにおける平均水素濃度および深さ105~110μmにおける平均水素濃度は、以下の分析条件下で測定した値である。
(分析条件)
測定装置:四重極型質量分析器を有する二次イオン質量分析装置
一次イオン種:Cs+
一次加速電圧:5.0kV
一次イオンカレント:1μA
一次イオン入射角(試料面垂直方向からの角度):60°
ラスターサイズ:200×200μm2
検出領域:40×40μm2
二次イオン極性:マイナス
中和用の電子銃使用有
式(3-1)において、Sn濃度差はボトム面単位面積当たりのSn付着量(単位:μg/cm2)からトップ面単位面積当たりのSn付着量(単位:μg/cm2)を減じた差であり、単位面積当たりのSn付着量はSnがSnO2の形で存在するとしたときの1cm2あたりのSnO2換算付着質量である。
式(3-1)において、Δイオン交換量1はトップ面におけるイオン交換量1から該ボトム面におけるイオン交換量1を減じた値である。イオン交換量1は下記式により求められる。
イオン交換量1=5.51×(規格化Na2O表面濃度)-0.038×(Sn濃度)
前記式において、規格化Na2O表面濃度は、表面のNa2O濃度をその深さ100μm位置のNa2O濃度で除した値である。ここで、Na2O濃度はNa-Kα線を用いる蛍光X線分析による測定値である。 - 成形時に溶融金属と接するボトム面と、該ボトム面に対向するトップ面とを有する化学強化用フロートガラスであって、下記式(4-1)により求められるW2の絶対値が56以下である化学強化用フロートガラス。
W2=9.18×Δ[(イオン交換量1)/(H/Si)]+49…式(4-1)
式(4-1)において、Δ[(イオン交換量1)/(H/Si)]は、トップ面におけるイオン交換量1を同面における規格化水素濃度H/Siで除した値からボトム面におけるイオン交換量1を同面における規格化水素濃度H/Siで除した値を減じた値である。
ここで、イオン交換量1は下記式により求められる。
イオン交換量1=5.51×(規格化Na2O表面濃度)-0.038×(Sn濃度)
前記式において、規格化Na2O表面濃度は、表面のNa2O濃度をその深さ100μm位置のNa2O濃度で除した値である。ここで、Na2O濃度はNa-Kα線を用いる蛍光X線分析による測定値である。また、Sn濃度はトップ面およびボトム面単位面積当たりのSn付着量(単位:μg/cm2)であり、単位面積当たりのSn付着量はSnがSnO2の形で存在するとしたときの1cm2あたりのSnO2換算付着質量である。
規格化水素濃度とは、深さ1~10μmにおける平均水素濃度を深さ105~110μmにおける平均水素濃度で除した値であり、深さ1~10μmにおける平均水素濃度および深さ105~110μmにおける平均水素濃度は、以下の分析条件下で測定した値である。
(分析条件)
測定装置:四重極型質量分析器を有する二次イオン質量分析装置
一次イオン種:Cs+
一次加速電圧:5.0kV
一次イオンカレント:1μA
一次イオン入射角(試料面垂直方向からの角度):60°
ラスターサイズ:200×200μm2
検出領域:40×40μm2
二次イオン極性:マイナス
中和用の電子銃使用有 - 成形時に溶融金属と接するボトム面と、該ボトム面に対向するトップ面とを有する化学強化用フロートガラスであって、下記式(5-1)により求められるW3が58以下である化学強化用フロートガラス。
W3=744×[(ΔN-Na2O)+0.01×(Sn濃度差)]…式(5-1)
式(5-1)において、ΔN-Na2Oは、トップ面における表面のNa2O濃度をその深さ100μm位置のNa2O濃度で除した値であるトップ面の規格化Na2O表面濃度からボトム面における表面のNa2O濃度をその深さ100μm位置のNa2O濃度で除した値であるボトム面の規格化Na2O表面濃度を減じた値である。ここで、それぞれのNa2O濃度はNa-Kα線を用いる蛍光X線分析による測定値である。
式(5-1)において、Sn濃度差は、ボトム面単位面積当たりのSn付着量(単位:μg/cm2)からトップ面単位面積当たりのSn付着量(単位:μg/cm2)を減じた差であり、単位面積当たりのSn付着量はSnがSnO2の形で存在するとしたときの1cm2あたりのSnO2換算付着質量である。 - 成形時に溶融金属と接するボトム面と、該ボトム面に対向するトップ面とを有する化学強化用フロートガラスであって、該トップ面におけるイオン交換量2から該ボトム面におけるイオン交換量2を減じた値であるΔイオン交換量2が0.33以下である化学強化用フロートガラス。
ここで、イオン交換量2は下記式(6-1)により求められる値である。
イオン交換量2=-0.02×(H/Si)+5.54×(N-Na2O濃度)-0.037×(Sn濃度)…式(6-1)
式(6-1)において、H/Siは規格化水素濃度であり、規格化水素濃度とは深さ0~10μmにおける平均水素濃度を深さ105~110μmにおける平均水素濃度で除した値であり、深さ0~10μmにおける平均水素濃度および深さ105~110μmにおける平均水素濃度は、以下の分析条件下で測定した値である。
(分析条件)
測定装置:四重極型質量分析器を有する二次イオン質量分析装置
一次イオン種:Cs+
一次加速電圧:5.0kV
一次イオンカレント:1μA
一次イオン入射角(試料面垂直方向からの角度):60°
ラスターサイズ:200×200μm2
検出領域:40×40μm2
二次イオン極性:マイナス
中和用の電子銃使用有
式(6-1)においてN-Na2O濃度は表面Na2O濃度を深さ100μm位置のNa2O濃度で除した値である規格化Na2O表面濃度である。ここで、Na2O濃度はNa-Kα線を用いる蛍光X線分析による測定値である。
Sn濃度は、単位面積当たりのSn付着量(単位:μg/cm2)であり、Sn付着量はSnがSnO2の形で存在するとしたときのSnO2換算付着質量である。 - 成形時に溶融金属と接するボトム面と、該ボトム面に対向するトップ面とを有する化学強化用フロートガラスであって、該トップ面におけるNa2O濃度をその深さ100μm位置のNa2O濃度で除した値であるトップ面の規格化Na2O表面濃度から該ボトム面におけるNa2O濃度をその深さ100μm位置のNa2O濃度で除した値であるボトム面の規格化Na2O表面濃度を減じた差ΔN-Na2Oの2乗(ΔN-Na2O)2が5.0×10-4以下である化学強化用フロートガラス。それぞれのNa2O濃度はNa-Kα線を用いる蛍光X線分析により測定した値である。
- 化学強化温度がT(単位:K)、化学強化時間がt(単位:時間)である化学強化に用いられ、且つSiO2を含有し、SiO2、Al2O3、MgO、CaO、SrO、BaO、ZrO2、Na2OおよびK2Oの各質量百分率表示含有量を用いて次式で求められるdolが20以下である請求項1~7のいずれか1項に記載の化学強化用フロートガラス。
dol=-0.13×Al2O3-1.88×MgO-2.41×CaO-1.85×SrO-1.35×BaO-1.59×ZrO2+1.50×Na2O+2.42×K2O-129359/T+9.28×t0.5+182.88 - 質量百分率表示で、SiO2を60~80%、Al2O3を0~8%、Na2Oを8~22%、K2Oを0~7%、MgOを0~17%、CaOを0~22%、SrOを0~8%、BaOを0~8%、ZrO2を0~5%含有する請求項1~8のいずれか1項に記載の化学強化用フロートガラス。
- 請求項1~9のいずれか1項に記載の化学強化用フロートガラスであって、質量百分率表示で、SiO2を60~80%、Al2O3を0.01~8%、Na2Oを8~22%、K2Oを0~7%、ZrO2を0~5%含有し、MgO、CaO、SrOまたはBaOを含有する場合MgO、CaO、SrOおよびBaOの含有量の合計が5~25%であり、Na2OおよびAl2O3の含有量の比Na2O/Al2O3が1.5以上である化学強化用フロートガラス。
- 請求項10に記載の化学強化用フロートガラスであって、Na2O/Al2O3が6以下である化学強化用フロートガラス。
- 請求項9、10または11に記載の化学強化用フロートガラスであって、CaO、SrOまたはBaOを含有しCaO、SrOおよびBaOの含有量の合計が1~7%である化学強化用フロートガラス。
- 圧縮応力深さが20μm以下である化学強化ガラスを製造する方法であって、請求項1~12のいずれか1項に記載の化学強化用ガラスを化学強化することを特徴とする化学強化ガラスの製造方法。
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