WO2014084096A1 - Verre armé et procédé de fabrication associé - Google Patents

Verre armé et procédé de fabrication associé Download PDF

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Publication number
WO2014084096A1
WO2014084096A1 PCT/JP2013/081264 JP2013081264W WO2014084096A1 WO 2014084096 A1 WO2014084096 A1 WO 2014084096A1 JP 2013081264 W JP2013081264 W JP 2013081264W WO 2014084096 A1 WO2014084096 A1 WO 2014084096A1
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Prior art keywords
glass
compressive stress
hydrogen concentration
depth
strength
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PCT/JP2013/081264
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English (en)
Japanese (ja)
Inventor
文 山本
博之 大川
山中　一彦
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旭硝子株式会社
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Publication of WO2014084096A1 publication Critical patent/WO2014084096A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B24—GRINDING; POLISHING
    • B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
    • B24B7/00—Machines or devices designed for grinding plane surfaces on work, including polishing plane glass surfaces; Accessories therefor
    • B24B7/20—Machines or devices designed for grinding plane surfaces on work, including polishing plane glass surfaces; Accessories therefor characterised by a special design with respect to properties of the material of non-metallic articles to be ground
    • B24B7/22—Machines or devices designed for grinding plane surfaces on work, including polishing plane glass surfaces; Accessories therefor characterised by a special design with respect to properties of the material of non-metallic articles to be ground for grinding inorganic material, e.g. stone, ceramics, porcelain
    • B24B7/24—Machines or devices designed for grinding plane surfaces on work, including polishing plane glass surfaces; Accessories therefor characterised by a special design with respect to properties of the material of non-metallic articles to be ground for grinding inorganic material, e.g. stone, ceramics, porcelain for grinding or polishing glass
    • B24B7/242—Machines or devices designed for grinding plane surfaces on work, including polishing plane glass surfaces; Accessories therefor characterised by a special design with respect to properties of the material of non-metallic articles to be ground for grinding inorganic material, e.g. stone, ceramics, porcelain for grinding or polishing glass for plate glass
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B24—GRINDING; POLISHING
    • B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
    • B24B37/00—Lapping machines or devices; Accessories
    • B24B37/04—Lapping machines or devices; Accessories designed for working plane surfaces
    • 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
    • C03C15/00—Surface treatment of glass, not in the form of fibres or filaments, by etching
    • 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
    • C03C23/0085—Drying; Dehydroxylation
    • 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

Definitions

  • the present invention relates to tempered glass and a method for producing the same.
  • the conventional cover glass is strengthened by chemical strengthening or physical strengthening to form a compressive stress layer on the surface to enhance the scratch resistance.
  • Patent Document 1 discloses that the ion exchange layer having a potassium ion concentration exceeding 5000 ppm in the surface layer of the chemically strengthened glass substrate is removed thereafter.
  • a method is disclosed in which potassium ions are not ion-exchanged with hydronium ions at the time of cleaning, and thus the strength of the glass is increased by preventing the formation of a tensile stress layer that causes a decrease in strength.
  • the present inventors have found that the strength of the glass may decrease after chemical strengthening, the main cause of which is that chemical defects are generated when moisture in the atmosphere enters the glass. Moreover, it discovered that this phenomenon generate
  • an object of the present invention is to provide a tempered glass that effectively suppresses a reduction in the strength of the glass after tempering.
  • the present inventors have a correlation between the hydrogen profile in the surface layer of tempered glass and the strength of the glass, and by making the hydrogen concentration in the surface layer of the tempered glass into a specific range, the surface strength of the glass is dramatically improved. As a result, the present invention has been completed.
  • the present invention is as follows. 1.
  • the surface layer has a compressive stress layer, and the maximum hydrogen concentration in a region within 10 ⁇ m depth from the outermost surface of the compressive stress layer is not more than 5 times the minimum hydrogen concentration of 10 ⁇ m depth from the outermost surface. Tempered glass.
  • the maximum hydrogen concentration in the region within 10 ⁇ m depth from the outermost surface of the compressive stress layer and the lowest hydrogen concentration of 10 ⁇ m depth from the outermost surface 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 500 nA
  • Primary ion incident angle (angle from the direction perpendicular to the sample surface): 60 °
  • Raster size 300 ⁇ 300 ⁇ m 2
  • Detection area 12 ⁇ 12 ⁇ m 2
  • Secondary ion polarity Use of electron gun for negative neutralization 2.
  • the tempered glass according to item 1 wherein the compressive stress layer is formed by an ion exchange method.
  • 3. The tempered glass according to item 1 or 2, wherein the compressive stress layer has a compressive stress value of 400 MPa or more. 4).
  • a ball that places a glass plate on a ring made of stainless steel with a diameter of 30 mm, and that loads the sphere to the center of the ring under static load conditions with a sphere made of steel with a diameter of 10 mm in contact with the glass plate 5.
  • F ⁇ 1000 ⁇ t 2 wherein, F is the BOR strength (N) measured by the ball-on-ring test, and t is the thickness (mm) of the glass plate.
  • a molten salt containing KNO 3 is brought into contact with glass to form a compressive stress layer on the glass surface, and then the maximum hydrogen concentration in the region within 10 ⁇ m depth from the outermost surface of the compressive stress layer has a depth from the outermost surface.
  • a method for producing a tempered glass comprising removing a hydrogen-containing layer exceeding 5 times the minimum hydrogen concentration of 10 ⁇ m.
  • the hydrogen concentration in a region within 10 ⁇ m depth from the outermost surface of the compressive stress layer and the lowest hydrogen concentration at a depth of 10 ⁇ m from the outermost surface 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 500 nA
  • Primary ion incident angle (angle from the direction perpendicular to the sample surface): 60 °
  • Raster size 300 ⁇ 300 ⁇ m 2
  • Detection area 12 ⁇ 12 ⁇ m 2
  • Secondary ion polarity use of electron gun for negative neutralization 8.
  • the tempered glass of the present invention since the generation of defects due to moisture entering the glass is suppressed due to the hydrogen concentration of the surface layer being in a specific range, it is possible to suppress a decrease in strength after tempering, Shows high strength.
  • FIG. 1 is a schematic diagram for explaining a ball-on-ring test method.
  • FIG. 2 is a schematic diagram for explaining the method of the falling ball test.
  • FIG. 3 is a cross-sectional view of a flat panel display device using the tempered glass of the present invention as a cover glass for the flat panel display device.
  • FIG. 4A is a diagram showing the BOR intensity before and after polishing after strengthening.
  • FIG. 4B is a diagram showing the hydrogen concentration in the glass surface layer before and after polishing after strengthening.
  • FIG. 5A is a diagram showing the correlation between the post-strengthening polishing amount and the BOR intensity.
  • FIG. 5B is a diagram showing the correlation between the post-strengthening polishing amount and the falling ball strength (BD strength).
  • FIG. 6A is a diagram showing the correlation between the heat treatment temperature of the tempered glass and the BOR strength.
  • FIG.6 (b) is a figure which shows the hydrogen concentration in the glass surface layer before and behind heat processing of tempered glass.
  • FIG. 7 is a diagram showing the correlation between the hydrogen profile and the BOR intensity in the glass surface layer after the heat treatment.
  • FIG. 8 is a graph showing the correlation between the plate thickness and the BOR intensity.
  • FIG. 9 is a graph showing the correlation between the plate thickness and the falling ball strength.
  • the penetration depth of hydrogen into the glass depends on the diffusion coefficient, temperature and time, and the penetration amount of hydrogen is influenced by the moisture content in the atmosphere in addition to these.
  • the present inventors have found that the higher the hydrogen concentration of the glass, the lower the strength.
  • [ 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 500 nA
  • Primary ion incident angle 60 °
  • Raster size 300 ⁇ 300 ⁇ m 2
  • Detection area 12 ⁇ 12 ⁇ m 2
  • Secondary ion polarity Use of electron gun for negative neutralization
  • the sputtering rate is 150 nm / sec.
  • 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 hydrogen concentration C M divided by K. That is, [ 1 H ⁇ / 30 Si ⁇ ] is a direct indicator of the hydrogen concentration.
  • ADEPT 1010 manufactured by ULVAC-PHI can be mentioned.
  • the tempered glass of the present invention has a compressive stress layer on the surface layer, and the maximum hydrogen concentration in a region within 10 ⁇ m depth from the outermost surface of the compressive stress layer is 5 times or less than the minimum hydrogen concentration of 10 ⁇ m depth from the outermost surface. It is characterized by being.
  • the maximum hydrogen concentration in the region within 10 ⁇ m depth from the outermost surface of the compressive stress layer is not more than 5 times, preferably not more than 3 times, and preferably not more than 2 times the minimum hydrogen concentration of 10 ⁇ m depth from the outermost surface. It is more preferable. If the maximum hydrogen concentration in the region within 10 ⁇ m depth from the outermost surface of the compressive stress layer is more than five times the minimum hydrogen concentration of 10 ⁇ m depth from the outermost surface, the surface strength of the tempered glass decreases.
  • the maximum hydrogen concentration and the minimum hydrogen concentration in a region within a depth of 10 ⁇ m from the outermost surface of the compressive stress layer are the values of [ 1 H ⁇ / 30 Si ⁇ ] measured under the analysis conditions.
  • the compressive stress value of the compressive stress layer is preferably 400 MPa or more, more preferably 500 MPa or more, and further preferably 600 MPa or more. .
  • the depth of the compressive stress layer is preferably 10 ⁇ m or more in order to make the effect of improving the strength by chemical strengthening effective.
  • the compressive stress layer is preferably deeper, more preferably 20 ⁇ m or more, further preferably 30 ⁇ m or more, typically 30 ⁇ m or more. It is.
  • the depth of the compressive stress layer is preferably 70 ⁇ m or less.
  • the compressive stress value of the compressive stress layer and the depth of the compressive stress layer of the chemically tempered glass of the present invention are determined by an electron probe microanalyzer (EPMA) or a surface stress meter (for example, FSM- manufactured by Orihara Seisakusho). 6000) or the like.
  • EPMA electron probe microanalyzer
  • a surface stress meter for example, FSM- manufactured by Orihara Seisakusho. 6000
  • the surface roughness Ra of the surface layer in the tempered glass of the present invention is preferably 0.1 to 10 nm, and more preferably 0.2 to 3 nm.
  • the surface roughness Ra of the compressive stress layer is 0.2 to 3 nm, when a film such as a functional film is attached to the glass surface after strengthening, the film and the glass are likely to be in close contact with each other. There is an advantage that it is difficult to peel off.
  • Ra is measured by an atomic force microscope (AFM) at a measurement size of 10 * 10 ⁇ m and a scan rate of 1 Hz.
  • the strength of the tempered glass of the present invention can be evaluated by a ball-on-ring test and a falling ball test.
  • the tempered glass of the present invention is a state in which a glass plate is disposed on a ring made of stainless steel having a diameter of 30 mm and a contact portion having a radius of curvature of 2.5 mm, and a sphere made of steel having a diameter of 10 mm is brought into contact with the glass plate.
  • the BOR strength F (N) measured by a ball-on-ring test in which the sphere is loaded at the center of the ring under a static load condition is F ⁇ 1000 ⁇ t 2 [where F is measured by a ball-on-ring test. BOR strength (N), and t is the plate thickness (mm) of the glass substrate. ] Is preferable, and it is more preferable that F ⁇ 1240 ⁇ t 2 .
  • the BOR strength F (N) is F ⁇ 1000 ⁇ t 2 , excellent strength is exhibited even when the plate is thinned.
  • FIG. 1 shows a schematic diagram for explaining the BOR test used in the present invention.
  • the glass plate 1 is pressed using a pressure jig 2 made of SUS304 with the glass plate 1 placed horizontally, and the strength of the glass plate 1 is measured. To do.
  • a glass plate 1 as a sample is horizontally installed on a receiving jig 3 made of SUS304. Above the glass plate 1, a pressurizing jig 2 for pressurizing the glass plate 1 is installed.
  • the central region of the glass plate 1 is pressurized from above the glass plate 1.
  • the test conditions are as follows. Sample thickness: 1.1 (mm) Lowering speed of the pressure jig 2: 1.0 (mm / min)
  • the tempered glass of the present invention has a falling ball strength E (J determined by the following formula in a falling ball test in which a glass plate is placed on a base made of stainless steel and a sphere made of stainless steel having a diameter of 32 mm is dropped onto the glass plate from above. )
  • E satisfies E ⁇ 1.0 ⁇ t 2, and more preferably E ⁇ 1.7 ⁇ t 2 .
  • E ⁇ 1.0 ⁇ t 2 excellent strength is exhibited even when thinned.
  • FIG. 2 shows a schematic diagram for explaining the falling ball test used in the present invention.
  • a glass plate 5 is placed on a base 4 made of stainless steel, and a sphere 6 made of stainless steel is dropped onto the glass plate 5 from above, and the strength of the glass plate 5 is evaluated.
  • the glass plate 5 is placed on a base 4 made of SUS304 (100 ⁇ 100 ⁇ 10 ⁇ 10 mm thick metal plate having a 40 ⁇ 40 mm hollow portion in the center).
  • a sphere 6 (made of SUS304) having a mass of 130 kg is dropped on the center of the glass plate 5, and the falling ball strength is calculated from the height (destruction height) when the sphere 6 is dropped when the glass plate 5 is broken by the above formula. Find (J).
  • Glass composition As the tempered glass of the present invention, glass having various compositions can be used as long as it has a composition that can be tempered by a tempering treatment and formed by a float method or a downdraw method.
  • a transparent glass plate made of aluminosilicate glass, soda lime glass, borate glass, lithium aluminosilicate glass, borosilicate glass, non-alkali glass, and other various glasses.
  • the composition expressed in mol% is SiO 2 55-75%, Al 2 O 3 5-15%, Li 2 O 0-15%, Na 2 O 10-20%, K 2 O Is represented by a glass (ii) mol% containing 0 to 10%, MgO 0 to 15%, CaO 0 to 5% and ZrO 2 0 to 5%, SiO 2 55 to 75%, Al 2 O 3 0-15%, Li 2 O 0-20%, Na 2 O 0-15%, MgO 0-5%, CaO 0-5% and ZrO 2 0-5% composition displaying a glass (iii) mol%, a SiO 2 68 ⁇ 80%, the Al 2 O 3 4 ⁇ 10% , a Na 2 O 5 ⁇ 15%, the K 2 O 0 ⁇ 1%, of MgO 4-15% and ZrO 2 is composition displaying a
  • the tempered glass of the present invention includes a tempered glass by chemical tempering and a tempered glass by physical tempering, and the tempering method is not particularly limited, but is a tempered glass by chemical tempering in which a compressive stress layer is formed by ion exchange method Is preferred.
  • the surface of the glass is ion-exchanged to form a surface layer in which compressive stress remains.
  • alkali metal ions typically Li ions, Na ions
  • alkali ions typically Is substituted for Na ions or K ions for Li ions and K ions for Na ions.
  • Conditions and methods for chemical strengthening are not particularly limited, and known methods can be used.
  • the chemical strengthening method is not particularly limited as long as Li 2 O or Na 2 O on the glass surface layer and Na 2 O or K 2 O in the molten salt can be ion-exchanged.
  • heated potassium nitrate (KNO) 3 The method of immersing glass in the molten salt containing is mentioned.
  • the conditions of the ion exchange treatment for forming a chemically strengthened layer (surface compressive stress layer) having a desired surface compressive stress on the glass vary depending on the thickness of the glass, but the temperature condition is preferably 520 ° C. or lower. 500 ° C. or lower, more preferably 350 ° C. or higher, and more preferably 400 ° C. or higher.
  • the ion exchange treatment time is preferably 1 to 72 hours, and more preferably 2 to 24 hours. In order to improve productivity, 12 hours or less is more preferable.
  • the molten salt include KNO 3 .
  • a method of immersing glass in KNO 3 molten salt at 400 to 500 ° C. for 1 to 72 hours is typical.
  • the tempered glass of the present invention can be produced by forming a compressive stress layer on the glass surface and then removing the hydrogen-containing layer on the surface layer of the compressive stress layer.
  • the hydrogen-containing layer is a layer in which the maximum hydrogen concentration in a region within 10 ⁇ m depth from the outermost surface of the compressive stress layer exceeds 5 times the minimum hydrogen concentration of 10 ⁇ m depth from the outermost surface.
  • the hydrogen concentration of the hydrogen-containing layer 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 500 nA
  • Primary ion incident angle (angle from the direction perpendicular to the sample surface): 60 °
  • Raster size 300 ⁇ 300 ⁇ m 2
  • Detection region 12 ⁇ 12 [mu] m 2 secondary ion polarity: an electron gun using perforated for minus neutralizing
  • Examples of the method for removing the hydrogen-containing layer include polishing or etching.
  • the polishing method is not limited.
  • rare earth oxides such as cerium oxide, zirconium oxide, aluminum oxide, magnesium oxide, silicon oxide (including colloidal silica), silicon carbide, manganese oxide, iron oxide, diamond, boron nitride, and zircon.
  • polishing glass using the slurry containing abrasive grains, such as these is mentioned. These abrasive grains may be used alone or in combination of two or more.
  • polishing with a slurry containing colloidal silica having an average particle diameter of 80 nm or less as abrasive grains can be performed on the surface of the glass plate. It is preferable because it can be uniformly polished and a sufficient strength can be achieved.
  • a slurry containing known abrasive grains such as rare earth oxides such as cerium oxide, zirconium oxide, aluminum oxide, magnesium oxide, silicon oxide, silicon carbide, manganese oxide, iron oxide, diamond, boron nitride and zircon. It is more preferable to perform polishing using a slurry containing colloidal silica having an average particle size of 80 nm or less as abrasive grains after polishing.
  • Polishing both surfaces of the glass is preferable because warpage can be reduced by making the hydrogen concentration of the surface layer uniform on both surfaces of the glass.
  • an aqueous solution containing a glass-soluble chemical is used as an etching solution.
  • An aqueous solution containing fluoride may be used for the glass-soluble chemical.
  • the fluoride include hydrogen fluoride, ammonium fluoride, potassium fluoride, and sodium fluoride.
  • These aqueous solutions may contain an inorganic acid and / or an organic acid.
  • the inorganic acid one or more kinds may be selected from hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid and the like, and as the organic acid, one kind or two kinds or more may be selected from acetic acid, succinic acid and the like.
  • the etching rate is preferably 0.1 ⁇ m / cm 2 / min or more, and more preferably 1 ⁇ m / cm 2 / min or more.
  • the etching rate can be adjusted by appropriately adjusting the composition of the glass used for chemical strengthening, the temperature or concentration of the etching solution, and the like.
  • the etching temperature is usually preferably 10 ° C. to 60 ° C., more preferably 20 ° C. to 40 ° C. Furthermore, the etching time is usually preferably from 30 seconds to 30 minutes, more preferably from 1 minute to 10 minutes. These etching conditions can be appropriately selected by those skilled in the art so that the reaction product does not precipitate depending on the material of the glass substrate used.
  • Etching on both surfaces of the glass is preferable because warpage can be reduced by making the hydrogen concentration of the surface layer uniform on both surfaces of the glass.
  • the washing method is not particularly limited, and a known method can be used. For example, washing can be performed with an aqueous solution of sulfuric acid, hydrochloric acid, nitric acid, or the like while applying ultrasonic waves.
  • the method for producing tempered glass varies depending on the application, and is not particularly limited as other steps other than the hydrogen-containing layer removing step after the tempering step.
  • An example is shown below, but the present invention is not limited to this example.
  • the prepared glass base plate is formed into a desired size and shape to be finally finished through processes such as cutting, drilling, notching, polishing, and thread chamfering. At this time, in order to improve the handling of the subsequent process and reduce the process cost, it is cut into a size larger than the desired size to be finally finished, and after all the processing steps are completed, the desired size is obtained. It may be formed into a shape.
  • the formed glass is tempered by chemical strengthening or physical strengthening, and then the hydrogen-containing layer is removed to form tempered glass.
  • the tempered glass is subjected to, for example, printing, antireflection coating, functional film bonding, etc., and a cover glass is manufactured.
  • the tempered glass of the present invention can be used for a cover glass for a display such as a mobile phone, a digital camera or a touch panel display.
  • 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 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. 3, the cover glass 30 may be installed so as to be separated from the display side (front side) of the display panel 20 (having 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 is provided on the back surface of the cover glass 30 on which light from the display panel 20 enters at a position corresponding to the display panel 20. 42 is provided.
  • the functional films 41 and 42 are provided on both surfaces in FIG. 3, the functional films 41 and 42 are not limited to this and may be provided on the front surface or the back surface, or may be omitted.
  • the functional films 41 and 42 have functions such as anti-reflection of ambient light, prevention of impact breakage, electromagnetic wave shielding, near-infrared shielding, color tone correction, and / or scratch resistance improvement, and thickness and shape are used for applications. It is selected as appropriate.
  • the functional films 41 and 42 are formed, for example, by attaching a resin film to the cover glass 30. Or you may form by thin film formation methods, such as a vapor deposition method, a sputtering method, or CVD method.
  • Reference numeral 44 denotes a black layer, which is, for example, a coating formed by applying ink containing pigment particles to the cover glass 30, irradiating it with ultraviolet rays, or baking it, followed by cooling.
  • 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 baking it, followed by cooling.
  • the glass plate is immersed in KNO 3 molten salt, subjected to ion exchange treatment, and then chemically strengthened by cooling to near room temperature. At this time, the temperature of the KNO 3 molten salt was 435 ° C., and the immersion time was 4 hours. The obtained chemically strengthened glass was washed with water and subjected to the next step.
  • colloidal silica polishing As a polishing slurry, colloidal silica having an average particle diameter (d50) of 80 nm (Compoule 80; manufactured by Fujimi Incorporated) is dispersed in water to prepare a slurry, and a glass plate is polished at a polishing rate (single side). ): Polished with a polishing pad (Suede type H2093NX; manufactured by Fujibo Atago Co., Ltd.) at 0.03 ⁇ m / min.
  • a polishing pad Sudede type H2093NX; manufactured by Fujibo Atago Co., Ltd.
  • the analysis conditions for secondary ion mass spectrometry were as follows. Measuring device: Secondary ion mass spectrometer having a quadrupole mass analyzer Primary ion species: Cs + Primary acceleration voltage: 5.0 kV Primary ion current: 500 nA Primary ion incident angle (angle from the direction perpendicular to the sample surface): 60 ° Raster size: 300 ⁇ 300 ⁇ m 2 Detection area: 12 ⁇ 12 ⁇ m 2 Secondary ion polarity: Use of electron gun for negative neutralization
  • FIG. 1 is a schematic diagram for explaining the ball-on-ring test used in the present invention.
  • a glass plate 1 serving as a sample is horizontally installed on a receiving jig 3 made of SUS304 (diameter 30 mm, contact portion curvature R2.5 mm, contact portion is hardened steel, mirror finish). Above the glass plate 1, a pressurizing jig 2 for pressurizing the glass plate 1 is installed.
  • region of the glass plate 1 was pressurized from the upper direction of the glass plate 1 obtained after the Example and the comparative example.
  • the test conditions are as follows. Sample thickness: 1.1 (mm) Lowering speed of the pressure jig 2: 1.0 (mm / min) At this time, the breaking load (unit N) when the glass was broken was defined as BOR strength, and the average value of 20 measurements was defined as BOR average strength.
  • FIG. 2 is a schematic diagram for explaining the falling ball test used in the present invention.
  • the sphere 6 was dropped on the glass plate 5 and the strength of the glass plate 5 was evaluated.
  • the glass plate 5 was placed on a base 4 made of SUS304 (a vertical 100 ⁇ 100 ⁇ 10 mm thick metal plate having a 40 ⁇ 40 mm hollow portion in the center).
  • Example 1 A glass plate that has not been polished after chemical strengthening (hereinafter also referred to as an unpolished glass plate after strengthening), and a glass plate in which a region of 2 ⁇ m from the surface layer has been polished by colloidal silica polishing after chemical strengthening (hereinafter, after strengthening) The BOR strength in a polished glass plate) was measured. The result is shown in FIG.
  • the glass plate that has been polished after tempering has a significantly increased BOR strength compared with the glass plate that has not been polished after tempering, although CS is relatively decreased.
  • FIG. 5A shows the correlation between the BOR strength measured by the ball-on-ring test and the amount of the glass plate polished after strengthening.
  • FIG. 5B shows the correlation between the BD strength measured by the falling ball test and the amount of polishing the glass plate after strengthening.
  • the maximum hydrogen concentration in a region within 10 ⁇ m depth from the outermost surface of the compressive stress layer was 0.13, and the lowest hydrogen concentration at a depth of 10 ⁇ m from the outermost surface was 0.11. That is, the maximum hydrogen concentration in the region within 10 ⁇ m depth from the outermost surface of the compressive stress layer was 1.2 times the lowest hydrogen concentration of 10 ⁇ m depth from the outermost surface.
  • the hydrogen concentration is a value of [ 1 H ⁇ / 30 Si ⁇ ] measured under the above analysis conditions.
  • the maximum hydrogen concentration in the region within 10 ⁇ m depth from the outermost surface of the compressive stress layer in the tempered glass is not more than 5 times the minimum hydrogen concentration of 10 ⁇ m depth from the outermost surface. It turns out that it can improve.
  • Example 3 The correlation between the annealing temperature in the atmosphere and the BOR strength of the tempered polished glass was examined.
  • FIG. 6A shows the result of measuring the BOR strength after polishing a chemically strengthened glass plate by 2 ⁇ m and annealing in air at each temperature for 4 hours.
  • FIG. 6B shows the result of analyzing the hydrogen concentration of the glass surface layer by secondary ion mass spectrometry when there is no annealing treatment and when annealing is performed at 350 ° C. for 4 hours. From the results shown in FIGS. 6 (a) and 6 (b), it was found that the strength of the glass was lowered by increasing the hydrogen concentration in the glass surface layer by heat treatment.
  • Example 4 In order to investigate the correlation between the hydrogen profile in the glass after the heat treatment and the strength of the glass, a glass in which the hydrogen concentration in the surface layer of the glass was changed by changing the heat treatment conditions was prepared, and the BOR strength of each glass was measured. . The result is shown in FIG.
  • FIG. 8 a graph showing the correlation between the plate thickness and the BOR strength is shown in FIG.
  • the ⁇ plot shows a sample (Example) in which the maximum hydrogen concentration in the region within 10 ⁇ m depth from the outermost surface of the compressive stress layer is 5 times or less than the lowest hydrogen concentration of 10 ⁇ m depth from the outermost surface.
  • BOR intensity is shown.
  • the ⁇ plot shows the BOR intensity of a sample (comparative example) in which the maximum hydrogen concentration in the region within 10 ⁇ m depth from the outermost surface of the compressive stress layer exceeds 5 times the minimum hydrogen concentration of 10 ⁇ m depth from the outermost surface. is there.
  • the conventional product has a BOR strength of ⁇ plot.
  • the solid line plot F 1000 ⁇ t 2 is the threshold value. Therefore, it was found that by setting F ⁇ 1000 ⁇ t 2 , the glass exhibits excellent BOR strength even when it is thinned.
  • FIG. 9 A graph showing the correlation between the plate thickness and the falling ball strength is shown in FIG.
  • the ⁇ plot shows a sample (Example) in which the maximum hydrogen concentration in the region within 10 ⁇ m depth from the outermost surface of the compressive stress layer is 5 times or less than the minimum hydrogen concentration of 10 ⁇ m depth from the outermost surface. Indicates falling ball strength.
  • a plot shows the falling ball strength of a sample (comparative example) in which the maximum hydrogen concentration in the region within 10 ⁇ m depth from the outermost surface of the compressive stress layer exceeds 5 times the lowest hydrogen concentration of 10 ⁇ m depth from the outermost surface.
  • the conventional product has a falling ball strength of ⁇ plot.
  • ⁇ t 2 is at its threshold. Therefore, it was found that by setting E ⁇ 1.0 ⁇ t 2 , the glass exhibits excellent falling ball strength even when it is thinned.
  • Table 1 summarizes the above results.
  • the surface roughness Ra is a value measured with an atomic force microscope at a measurement size of 10 * 10 ⁇ m.
  • ⁇ CS is the compressive stress value of the compressive stress layer
  • DOL is the compressive depth of the compressive stress layer, and is a value measured with a surface stress meter (FSM-6000 manufactured by Orihara Seisakusho).
  • the H content ratio is a ratio of the maximum hydrogen concentration in a region within 10 ⁇ m depth from the outermost surface of the compressive stress layer and the minimum hydrogen concentration of 10 ⁇ m depth from the outermost surface.

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  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
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  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
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  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
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  • Inorganic Chemistry (AREA)
  • Surface Treatment Of Glass (AREA)

Abstract

La présente invention concerne un verre armé dans lequel on empêche efficacement la résistance du verre de diminuer après armature. La présente invention concerne un verre armé caractérisé en ce qu'une couche de contrainte de compression est présente sur la couche superficielle et en ce que la concentration en hydrogène maximum à une profondeur de 10 μm par rapport à la surface la plus externe de la couche de contrainte de compression n'est pas supérieure à cinq fois la concentration en hydrogène minimum à une profondeur de 10 μm par rapport à la surface la plus externe.
PCT/JP2013/081264 2012-11-30 2013-11-20 Verre armé et procédé de fabrication associé WO2014084096A1 (fr)

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JP2023040122A (ja) * 2017-06-23 2023-03-22 Ａｇｃ株式会社 化学強化ガラス

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