US20200346969A1 - Crystallized glass of three-dimensional shape, chemically strengthened glass of three-dimensional shape, and method for producing crystallized glass of three-dimensional shape and chemically strengthened glass of three-dimensional shape - Google Patents

Crystallized glass of three-dimensional shape, chemically strengthened glass of three-dimensional shape, and method for producing crystallized glass of three-dimensional shape and chemically strengthened glass of three-dimensional shape Download PDF

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US20200346969A1
US20200346969A1 US16/936,533 US202016936533A US2020346969A1 US 20200346969 A1 US20200346969 A1 US 20200346969A1 US 202016936533 A US202016936533 A US 202016936533A US 2020346969 A1 US2020346969 A1 US 2020346969A1
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glass
less
crystal
dimensionally shaped
crystallized
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Qing Li
Kenji IMAKITA
Akio Koike
Eriko Maeda
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AGC Inc
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Asahi Glass Co Ltd
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Assigned to AGC Inc. reassignment AGC Inc. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: IMAKITA, KENJI, KOIKE, AKIO, MAEDA, ERIKO, LI, QING
Publication of US20200346969A1 publication Critical patent/US20200346969A1/en
Priority to US17/525,554 priority Critical patent/US20220064054A1/en
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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
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B23/00—Re-forming shaped glass
    • C03B23/02—Re-forming glass sheets
    • C03B23/023—Re-forming glass sheets by bending
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B23/00—Re-forming shaped glass
    • C03B23/02—Re-forming glass sheets
    • C03B23/023—Re-forming glass sheets by bending
    • C03B23/025—Re-forming glass sheets by bending by gravity
    • C03B23/0252—Re-forming glass sheets by bending by gravity by gravity only, e.g. sagging
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B23/00—Re-forming shaped glass
    • C03B23/02—Re-forming glass sheets
    • C03B23/023—Re-forming glass sheets by bending
    • C03B23/03—Re-forming glass sheets by bending by press-bending between shaping moulds
    • C03B23/0302—Re-forming glass sheets by bending by press-bending between shaping moulds between opposing full-face shaping moulds
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B23/00—Re-forming shaped glass
    • C03B23/02—Re-forming glass sheets
    • C03B23/023—Re-forming glass sheets by bending
    • C03B23/035—Re-forming glass sheets by bending using a gas cushion or by changing gas pressure, e.g. by applying vacuum or blowing for supporting the glass while bending
    • C03B23/0352—Re-forming glass sheets by bending using a gas cushion or by changing gas pressure, e.g. by applying vacuum or blowing for supporting the glass while bending by suction or blowing out for providing the deformation force to bend the glass sheet
    • C03B23/0357—Re-forming glass sheets by bending using a gas cushion or by changing gas pressure, e.g. by applying vacuum or blowing for supporting the glass while bending by suction or blowing out for providing the deformation force to bend the glass sheet by suction without blowing, e.g. with vacuum or by venturi effect
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B32/00—Thermal after-treatment of glass products not provided for in groups C03B19/00, C03B25/00 - C03B31/00 or C03B37/00, e.g. crystallisation, eliminating gas inclusions or other impurities; Hot-pressing vitrified, non-porous, shaped glass products
    • C03B32/02—Thermal crystallisation, e.g. for crystallising glass bodies into glass-ceramic articles
    • 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
    • C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
    • C03C1/004—Refining agents
    • 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
    • C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
    • C03C10/0018—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and monovalent metal oxide as main constituents
    • C03C10/0027—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and monovalent metal oxide as main constituents containing SiO2, Al2O3, Li2O as main constituents
    • 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
    • C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
    • C03C10/0054—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing PbO, SnO2, B2O3
    • 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
    • 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
    • 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
    • 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
    • C03C3/097—Glass compositions containing silica with 40% to 90% silica, by weight containing phosphorus, niobium or tantalum
    • 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
    • C03C4/00—Compositions for glass with special properties
    • C03C4/0028—Compositions for glass with special properties for crystal glass, e.g. lead-free crystal glass
    • 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
    • C03C2204/00—Glasses, glazes or enamels with special properties

Definitions

  • the present invention relates to a three-dimensionally shaped crystallized glass having high transparency and excellent chemical strengthening properties, and relates to a production method thereof.
  • the present invention also relates to a three-dimensionally shaped chemically strengthened glass and a production method thereof.
  • a thin chemically strengthened glass having high-strength is used as a cover glass of a display unit of a mobile device such as cell phone and smartphone or as a cover glass of an in-vehicle display member such as instrument panel and head-up display (HUD).
  • a cover glass having a three-dimensional shape is sometimes required so as to improve the operability and visibility.
  • the three-dimensionally shaped cover glass is produced by a method in which a flat glass sheet is heated and then subjected to bend-forming (sometimes referred to as three-dimensional forming) using forming molds (see, Patent Literature 1).
  • Patent Literature 2 discloses a lithium aluminosilicate glass capable of being three-dimensionally formed and chemically strengthened.
  • Patent Literature 3 discloses a chemically strengthened crystallized glass.
  • Patent Literature 1 International Publication WO2014/167894
  • Patent Literature 2 JP-T-2013-520385 (the term “JP-T” as used herein means a published Japanese translation of a PCT patent application)
  • Patent Literature 3 JP-T-2016-529201
  • the chemical strengthening properties of a crystallized glass are greatly affected by a glass composition and a precipitated crystal. Scratch resistance and transparency of the crystallized glass are also greatly affected by a glass composition and a precipitated crystal. In order to obtain a crystallized glass excellent in both chemical strengthening properties and transparency, the glass composition and precipitated crystal need to be subtly adjusted.
  • the method for obtaining a three-dimensionally shaped crystallized glass includes a method in which an amorphous glass is bend-formed and then crystallized, a method in which an amorphous glass is crystallized and then processed into a three-dimensional shape by grinding or other methods, and a method in which an amorphous glass is crystallized and then bend-formed.
  • an amorphous glass is bend-formed and then crystallized, since a heat treatment is performed after the forming, not only deformation is likely to occur but also a dimensional change is caused at the time of crystallization of the amorphous glass, thereby making it difficult to obtain a desired shape.
  • the method in which an amorphous glass is crystallized and then processed into a three-dimensional shape by grinding or other methods the grinding processing takes a long time and therefore the production efficiency is low.
  • a crystallized glass generally has a higher softening temperature, compared with an amorphous glass, and thus bend-forming thereof is difficult.
  • a transparent crystallized glass is heated at a high temperature so as to bend-form the glass, crystals in the crystallized glass are likely to grow excessively, thereby giving rise to a problem such as reduction in transparency.
  • an object of the present invention is to provide a three-dimensionally shaped crystallized glass for easily producing a three-dimensionally shaped chemically strengthened glass that is scratch-resistant and has excellent transparency.
  • an object of the present invention is to provide a three-dimensionally shaped chemically strengthened glass that is scratch-resistant and has excellent transparency, obtained by chemically strengthening the three-dimensionally shaped crystallized glass above.
  • an object of the present invention is to provide a production method of a chemically strengthened glass that is the three-dimensionally shaped crystallized glass above.
  • the present invention provides a three-dimensionally shaped crystallized glass including a crystal, the glass having a light transmittance of 80% or more in terms of a thickness of 0.8 mm and including, in mass % on an oxide basis, from 45 to 74% of SiO 2 , from 1 to 30% of Al 2 O 3 , from 1 to 25% of Li 2 O, from 0 to 10% of Na 2 O, from 0 to 5% of K 2 O, from 0 to 15% in total of either one or more of SnO 2 and ZrO 2 , and from 0 to 12% of P 2 O 5 .
  • the present invention provides a three-dimensionally shaped chemically strengthened glass having a compressive stress layer on a surface thereof, the glass being a crystallized glass including a crystal, having a light transmittance of 80% or more in terms of a thickness of 0.8 mm and including, in mass % on an oxide basis, from 45 to 74% of SiO 2 , from 1 to 30% of Al 2 O 3 , from 1 to 25% of Li 2 O, from 0 to 10% of Na 2 O, from 0 to 5% of K 2 O, from 0 to 15% in total of either one or more of SnO 2 and ZrO 2 , and from 0 to 12% of P 2 O 5 .
  • the present invention also provides a production method of a glass for chemical strengthening, the method including heating and crystallizing a glass including, in mass % on an oxide basis, from 45 to 74% of SiO 2 , from 1 to 30% of Al 2 O 3 , from 2 to 25% of Li 2 O, from 0 to 10% of Na 2 O, from 0 to 5% of K 2 O, from 0 to 15% in total of either one or more of SnO 2 and ZrO 2 , and from 0 to 12% of P 2 O 5 , and bend-forming a resulting crystallized glass under heating.
  • the present invention provides a production method of a chemically strengthened glass, including heating and crystallizing a glass including, in mass % on an oxide basis, from 45 to 74% of SiO 2 , from 1 to 30% of Al 2 O 3 , from 2 to 25% of Li 2 O, from 0 to 10% of Na 2 O, from 0 to 5% of K 2 O, from 0 to 15% in total of either one or more of SnO 2 and ZrO 2 , and from 0 to 12% of P 2 O 5 , bend-forming a resulting crystallized glass under heating, and thereafter, chemically strengthening the glass.
  • a three-dimensionally shaped crystallized glass for easily producing a three-dimensionally shaped chemically strengthened glass that is scratch-resistant and has excellent transparency, is obtained.
  • the chemically strengthened glass of the present invention is scratch-resistant, has excellent transparency, and can be easily produced by chemically strengthening the three-dimensionally shaped crystallized glass of the present invention.
  • the three-dimensionally shaped crystallized glass of the present invention is obtained.
  • FIG. 1 is a perspective diagram illustrating one example of the shape of the three-dimensionally shaped glass of the present invention.
  • FIG. 2 is a perspective diagram illustrating one example of the shape of the three-dimensionally shaped glass of the present invention.
  • FIG. 3 is a perspective diagram illustrating one example of the shape of the three-dimensionally shaped glass of the present invention.
  • FIG. 4 is a diagram illustrating one example of the X-ray diffraction pattern of the crystallized glass.
  • FIG. 5 is a diagram illustrating one example of the X-ray diffraction pattern of the crystallized glass.
  • FIG. 6 is a schematic diagram illustrating a test method of bend formability for the crystallized glass; (a) of FIG. 6 illustrates the state before bending; and (b) of FIG. 6 illustrates the state of being heated and thus bent.
  • the “amorphous glass” and the “crystallized glass” are collectively referred to as “glass”.
  • the “amorphous glass” means a glass in which a diffraction peak indicating a crystal cannot be observed by a powder X-ray diffraction method.
  • the “crystallized glass” is a glass obtained by heating the “amorphous glass” to precipitate a crystal therein and means a glass containing a crystal.
  • the “chemically strengthened glass” means a glass having been subjected to a chemical strengthening treatment
  • the “glass for chemical strengthening” means a glass before being subjected to a chemical strengthening treatment
  • the “base composition of a chemically strengthened glass” means a glass composition of a glass for chemical strengthening. Unless an immoderate ion exchange treatment is performed, a glass composition of a part deeper than a depth of a compressive stress layer (DOL) in a chemically strengthened glass is the same as the base composition of the chemically strengthened glass.
  • DOL compressive stress layer
  • the glass composition is expressed in mass % on an oxide basis, and mass % is simply written as “%”.
  • the “substantially free of” means that the content is not higher than a level of impurities contained in raw materials or the like, i.e., the substance is not intentionally added.
  • the content of the component is specifically, for example, less than 0.1%.
  • the “stress profile” means a profile showing a compressive stress value by using a depth from a glass surface as the variable.
  • the tensile stress is expressed as a negative compressive stress.
  • the “compressive stress value (CS)” can be measured by thinning a cross section of a glass and analyzing the thinned sample with a birefringence imaging system.
  • the birefringence imaging system includes, for example, a birefringence imaging system Abrio-IM manufactured by Tokyo Instruments, Inc.
  • the value can also be measured by use of scattered-light photoelasticity.
  • the CS can be measured by making light incident from a surface of a glass and analyzing polarization of the scattered light.
  • the stress meter using scattered-light photoelasticity includes, for example, a scattered-light photoelastic stress meter SLP-1000 manufactured by Orihara Manufacturing Co., Ltd.
  • the “depth of compressive stress layer (DOL)” is a depth at which the compressive stress value (CS) is zero.
  • the surface compressive stress at a depth of DOL/4 is sometimes denoted by CS 1
  • the compressive stress at a depth of DOL/2 is sometimes denoted by CS 2 .
  • DOL 1 the depth at which the compressive stress value becomes CS/2
  • m 1 represented by the following expression is taken as an inclination of the stress profile from the glass surface to the depth DOL 1 .
  • m 2 represented by the following expression is taken as an inclination of the stress profile from the depth DOL/4 to the depth DOL/2.
  • m 3 represented by the following expression is taken as an inclination of the stress profile from the depth DOL/2 to the depth DOL.
  • CT internal tensile stress
  • the “light transmittance” means an average transmittance of light at a wavelength of 380 nm to 780 nm.
  • the “haze value” means a haze value measured with a C illuminant according to JIS K3761:2000.
  • Vickers hardness is a Vickers hardness (HV0.1) specified in JIS R1610:2003.
  • fracture toughness value means an indentation-fracture method (IF method) fracture toughness value specified in JIS R1607:2010.
  • the “three-dimensional shape” means a shape obtained by bending a flat sheet.
  • the three-dimensional shape is not limited to a shape having a uniform thickness as a whole but may be a shape having portions differing in the thickness.
  • FIG. 1 is a perspective diagram illustrating one example of the three-dimensionally shaped crystallized glass of the present embodiment (hereinafter, sometimes referred to as “the present three-dimensionally shaped glass”).
  • the present three-dimensionally shaped glass may have a convex shape.
  • a glass having a flat sheet shape in the central part is illustrated, but the present three-dimensionally shaped glass may be curved as a whole.
  • the present three-dimensionally shaped glass may have a three-dimensional shape composed of a plurality of R shapes as illustrated in FIG. 2 and FIG. 3 .
  • the present three-dimensionally shaped glass has high transparency and therefore, is suitable for a cover glass, etc. in the display part of a mobile terminal, etc.
  • the light transmittance in terms of a thickness of 0.8 mm of the present three-dimensionally shaped glass is preferably 80% or more, because the screen is viewed easily when used for a cover glass of a mobile display, and is more preferably 85% or more, still more preferably 86% or more, particularly preferably 88% or more.
  • the light transmittance of the present three-dimensionally shaped glass in terms of a thickness of 0.8 mm is preferably higher, but it is usually 91% or less, or 90% or less.
  • the light transmittance of 90% is comparable to that of a general amorphous glass.
  • the haze value of the present three-dimensionally shaped glass in terms of a thickness of 0.8 mm is preferably 1.5% or less, more preferably 1.2% or less, still more preferably 1% or less, yet still more preferably 0.8% or less, and most preferably 0.5% or less.
  • the haze value of the present three-dimensionally shaped glass in terms of a thickness of 0.8 mm is preferably 0.05% or more, more preferably 0.1% or more.
  • the present three-dimensionally shaped glass is a crystallized glass and therefore, the strength is high compared with an amorphous glass. In addition, the Vickers hardness is large, and the glass is scratch-resistant.
  • the Vickers hardness of the present three-dimensionally shaped glass is preferably 680 or more, more preferably 700 or more, and still more preferably 740 or more, yet still more preferably 780 or more, particularly preferably 800 or more.
  • the Vickers hardness of the present three-dimensionally shaped glass is preferably 1,100 or less, more preferably 1,050 or less, still more preferably 1,000 or less.
  • the crystallized glass (hereinafter, sometimes referred to as “the present crystallized glass”) constituting the present three-dimensionally shaped glass contains crystals, and it is preferable to contain a lithium aluminosilicate crystal or a lithium silicate crystal.
  • these crystals are also ion-exchanged during a chemical strengthening treatment and therefore, high strength is obtained.
  • the lithium aluminosilicate crystal include a ⁇ -spodumene crystal and a petalite crystal.
  • the lithium silicate crystal include a lithium metasilicate crystal and a lithium disilicate crystal.
  • the present crystallized glass In the case of increasing the strength after chemical strengthening, it is preferable for the present crystallized glass to contain a ⁇ -spodumene crystal. In the case of improving the transparency and formability while keeping the chemical strengthening properties, it is preferable for the present crystallized glass to contain a lithium metasilicate crystal.
  • the ⁇ -spodumene crystal is represented by LiAlSi 2 O 6 and is a crystal showing diffraction peaks at Bragg angles (2 ⁇ ) of 25.55° ⁇ 0.05°, 22.71° ⁇ 0.05°, and 28.20° ⁇ 0.05° in an X-ray diffraction spectrum.
  • FIG. 2 illustrates examples of X-ray diffraction patterns of a crystallized glass (a glass for chemical strengthening) containing a ⁇ -spodumene crystal and a crystallized glass (chemically strengthened glass) obtained by chemically strengthening the crystallized glass above.
  • the solid line is an X-ray diffraction pattern measured for the crystallized glass sheet before strengthening, and a diffraction line of the ⁇ -spodumene crystal indicated by black circles is observed in FIG. 2 .
  • the broken line shows an X-ray diffraction pattern measured for the crystallized glass (chemically strengthened glass) sheet after chemical strengthening. It is considered that the positions of diffraction peaks are shifted to the lower angle side by chemical strengthening because the lattice spacing is increased due to occurrence of ion exchange between small ions in the crystal and large ions in the molten salt.
  • the surface compressive stress (CS) tends to be increased by chemical strengthening, compared with a crystallized glass containing other crystals. This may be because the crystal structure of the ⁇ -spodumene crystal is dense and therefore, when ions in the precipitated crystal are substituted by larger ion through an ion exchange treatment for chemical strengthening, the compressive stress generated along with a change in the crystal structure increases.
  • the ⁇ -spodumene crystal is known to have a high crystal growth rate. Therefore, in the crystallized glass containing a ⁇ -spodumene crystal, the crystals contained therein easily growth and consequently, in many cases, such a glass has low transparency and large haze value. However, since the present three-dimensionally shaped glass contains a large number of microcrystals, the transparency is high and the haze value is small.
  • the lithium metasilicate crystal is represented by Li 2 SiO 3 and is a crystal showing diffraction peaks at Bragg angles (2 ⁇ ) of 26.98 ⁇ 0.2, 18.88 ⁇ 0.2, and 33.05 ⁇ 0.2 in an X-ray diffraction spectrum.
  • FIG. 3 illustrates an example of the X-ray diffraction pattern of a crystallized glass containing a lithium metasilicate crystal.
  • the crystallized glass containing a lithium metasilicate crystal has a high fracture toughness value compared with an amorphous glass, and intense fracture is difficult to occur even when a large compressive stress is formed by chemical strengthening.
  • An amorphous glass capable of precipitating a lithium metasilicate crystal may precipitate a lithium disilicate crystal depending on the heat treatment conditions, etc., and when a lithium metasilicate crystal and a lithium disilicate crystal are contained at the same time, the transparency is reduced. Then, in terms of enhancing the transparency, it is preferred that the crystallized glass containing lithium metasilicate does not contain lithium disilicate.
  • the phrase “does not contain lithium disilicate” as used herein means that in the above-described X-ray diffractometry, a diffraction peak of a lithium disilicate crystal is not observed.
  • the present crystallized glass preferably contains a petalite crystal or a lithium metasilicate crystal.
  • a crystallized glass containing such a crystal has a low crystallization treatment temperature and a low softening temperature and therefore, the forming temperature tends to be easily lowered.
  • the crystallinity of the present crystallized glass is preferably 10% or more, more preferably 15% or more, still more preferably 20% or more, particularly preferably 25% or more.
  • the crystallinity of the present crystallized glass is preferably 70% or less, more preferably 60% or less, particularly preferably 50% or less.
  • a low crystallinity is preferable also in terms of that bend-forming or the like is easily performed by heating.
  • the crystallinity can be calculated from X-ray diffraction intensity by a Rietveld method.
  • the Rietveld method is described in “Handbook of Crystal Analysis” edited by the “Handbook of Crystal Analysis” Editing Committee of the Crystallographic Society of Japan (published by Kyoritsu Shuppan Co., Ltd., 1999, pp. 492-499).
  • the average particle size of precipitated crystals in the present crystallized glass is preferably 300 nm or less, more preferably 200 nm or less, still more preferably 150 nm or less, and particularly preferably 100 nm or less.
  • the average particle size of precipitated crystals can be calculated from powder X-ray diffraction intensity by the Rietveld method.
  • the crystallized glass containing a ⁇ -spodumene crystal is also known to have a small thermal expansion coefficient.
  • the average thermal expansion coefficient thereof at 50° C. to 350° C. is preferably 30 ⁇ 10 ⁇ 7 /° C. or less, more preferably 25 ⁇ 10 ⁇ 7 /° C. or less, still more preferably 20 ⁇ 10 ⁇ 7 /° C. or less, and particularly preferably 15 ⁇ 10 ⁇ 7 /° C. or less.
  • the average thermal expansion coefficient at 50° C. to 350° C. is usually 10 ⁇ 10 ⁇ 7 /° C. or more.
  • the average thermal expansion coefficient thereof at 50° C. to 350° C. is preferably 10 ⁇ 10 ⁇ 7 /° C. or more, more preferably 11 ⁇ 10 ⁇ 7 /° C. or more, still more preferably 12 ⁇ 10 ⁇ 7 /° C. or more, and particularly preferably 13 ⁇ 10 ⁇ 7 /° C. or more. If the thermal expansion coefficient is too large, cracking is likely to occur during heat treatment. Accordingly, in the case where the present crystallized glass contains a lithium metasilicate crystal, the average thermal expansion coefficient thereof at 50° C. to 350° C. is preferably 160 ⁇ 10 ⁇ 7 /° C. or less, more preferably 150 ⁇ 10 ⁇ 7 /° C. or less, still preferably 140 ⁇ 10 ⁇ 7 /° C. or less.
  • the fracture toughness value of the present crystallized glass is preferably 0.8 MPa ⁇ m 1/2 or more, more preferably 1 MPa ⁇ m 1/2 or more. Within this range, fragments are less likely to scatter upon breakage of the strengthened glass.
  • the Young's modulus of the present crystallized glass is preferably 80 GPa or more, more preferably 86 GPa or more, still more preferably 90 GPa or more, and particularly preferably 100 GPa or more. When the Young's modulus is increased, fragments are less likely to scatter upon breakage of the strengthened glass.
  • the glass preferably includes, in mass % on an oxide basis, from 58 to 74% of SiO 2 , from 5 to 30% of Al 2 O 3 , from 1 to 14% of Li 2 O, from 0 to 5% of Na 2 O, from 0 to 2% of K 2 O, from 0.5 to 12% in total of either one or more of SnO 2 and ZrO 2 , and from 0 to 6% of P 2 O 5 .
  • composition above it is more preferable to include from 2 to 14% of Li 2 O, and it is also more preferred that the total (Na 2 O+K 2 O) of the contents of Na 2 O and K 2 O is from 1 to 5%.
  • the glass includes from 58 to 70% of SiO 2 , from 15 to 30% of Al 2 O 3 , from 2 to 10% of Li 2 O, from 0 to 5% of Na 2 O, from 0 to 2% of K 2 O, from 0.5 to 6% of SnO 2 , from 0.5 to 6% of ZrO 2 , and from 0 to 6% of P 2 O 5 and Na 2 O+K 2 O is from 1 to 5%.
  • the present three-dimensionally shaped glass is preferably a glass obtained by crystallizing an amorphous glass having the composition above.
  • the glass preferably includes, in mass % on an oxide basis, from 45 to 75% of SiO 2 , from 1 to 20% of Al 2 O 3 , from 10 to 25% of Li 2 O, from 0 to 12% of P 2 O 5 , from 0 to 15% of ZrO 2 , from 0 to 10% of Na 2 O, and from 0 to 5% of K 2 O.
  • the present three-dimensionally shaped glass is preferably chemically strengthened.
  • the three-dimensionally shaped chemically strengthened glass of this embodiment (hereinafter, sometimes referred to as “the present strengthened glass”) obtained by chemically strengthening the present three-dimensionally shaped glass is described.
  • the surface compressive stress (CS) of the present strengthened glass is preferably 600 MPa or more, because cracking is hardly caused by deformation such as deflection.
  • the surface compressive stress of the present strengthened glass is more preferably 800 MPa or more.
  • the depth of compressive stress layer (DOL) of the present strengthened glass is preferably 80 ⁇ m or more, because cracking hardly occurs even when the surface is flawed.
  • the DOL of the present strengthened glass is preferably 100 ⁇ m or more.
  • the maximum depth (hereinafter, sometimes referred to as “50 MPa depth”) at which the compressive stress value is 50 MPa or more is preferably 80 ⁇ m or more, because cracking hardly occurs even when the glass is dropped on a hard surface such as asphalt.
  • the 50 MPa depth is more preferably 90 ⁇ m or more, and particularly preferably 100 ⁇ m or more.
  • the inclination m 1 of the stress profile from the glass surface to the depth DOL 1 is preferably ⁇ 50 MPa/ ⁇ m or less, more preferably ⁇ 55 MPa/ ⁇ m or less, and still more preferably ⁇ 60 MPa/ ⁇ m or less.
  • the chemically strengthened glass is a glass having a compressive stress layer formed in the surface. Since a tensile stress is generated in a portion far from the surface, the stress profile thereof has a negative inclination from the surface at a depth of zero toward the inside. Accordingly, m 1 is a negative value, and when an absolute value thereof is large, a stress profile having a large surface compressive stress CS and a small internal tensile stress CT is obtained.
  • the inclination m 2 of the stress profile from a depth of DOL/4 to a depth of DOL/2 has a negative value.
  • the inclination m 2 is preferably ⁇ 5 MPa/ ⁇ m or more, more preferably ⁇ 3 MPa/ ⁇ m or more, and still more preferably ⁇ 2 MPa/ ⁇ m or more. If m 2 is too large, the 50 MPa depth is reduced, and there is a concern that the drop strength to asphalt may lack.
  • m 2 is preferably ⁇ 0.3 MPa/ ⁇ m or less, more preferably ⁇ 0.5 MPa/ ⁇ m or less, and still more preferably ⁇ 0.7 MPa/ ⁇ m or less.
  • the inclination m 3 of the stress profile from a depth of DOL/2 to DOL has a negative value.
  • m 3 is preferably ⁇ 5 MPa/mm or more, more preferably ⁇ 4 MPa/ ⁇ m or more, still more preferably ⁇ 3.5 MPa/ ⁇ m or more, and particularly preferably ⁇ 2 MPa/ ⁇ m or more. If the absolute value of m 3 is too small, the 50 MPa depth is reduced, and cracking is likely to occur when the glass is flawed.
  • m 3 is preferably ⁇ 0.3 MPa/ ⁇ m or less, more preferably ⁇ 0.5 MPa/ ⁇ m or less, and still more preferably ⁇ 0.7 MPa/ ⁇ m or less.
  • the ratio m 2 /m 3 of the inclination m 2 to the inclination m 3 is preferably 2 or less, because deep DOL and small CT are obtained.
  • the ratio m 2 /m 3 is more preferably 1.5 or less, and still more preferably 1 or less.
  • the ratio m 2 /m 3 is preferably 0.3 or more, more preferably 0.5 or more, and still more preferably 0.7 or more.
  • the internal tensile stress (CT) of the present strengthened glass is preferably 110 MPa or less, because fragments are less likely to scatter upon breakage of the strengthened glass.
  • the CT is more preferably 100 MPa or less, still more preferably 90 MPa or less.
  • the CT is preferably 50 MPa or more, more preferably 55 MPa or more, and still more preferably 60 MPa or more.
  • the four point bending strength of the present strengthened glass is preferably 900 MPa or more.
  • the four point bending strength is measured using a test piece of 40 mm ⁇ 5 mm ⁇ 0.8 mm under the conditions of a lower span of 30 mm, an upper span of 10 mm and a cross head speed of 0.5 mm/min. An average value of 10 test pieces is taken as the four point bending strength.
  • the light transmittance and haze value of the present strengthened glass are substantially the same as those of the three-dimensionally shaped glass before chemical strengthening and therefore, descriptions thereof are omitted.
  • the present strengthened glass it is preferable for the present strengthened glass to contain a ⁇ -spodumene crystal.
  • the Vickers hardness of the present strengthened glass tends to be larger than that of the three-dimensionally shaped glass before strengthening.
  • the Vickers hardness of the present strengthened glass is preferably 720 or more, more preferably 740 or more, still more preferably 780 or more, and yet still more preferably 800 or more. On the other hand, the Vickers hardness of the present strengthened glass is usually 950 or less.
  • the glass composition of the present crystallized glass is described.
  • the composition of the present crystallized glass is as a whole the same as the composition of the amorphous glass before crystallization treatment.
  • the present strengthened glass is obtained by chemically strengthening the present three-dimensionally shaped glass composed of the present crystallized glass and unless an immoderate ion exchange treatment is performed, the composition of the present strengthened glass is as a whole the same as the composition of the present crystallized glass described below.
  • the present crystallized glass includes, in mass % on an oxide basis, from 45 to 74% of SiO 2 , from 1 to 30% of Al 2 O 3 , from 1 to 25% of Li 2 O, from 0 to 10% of Na 2 O, from 0 to 5% of K 2 O, from 0 to 15% in total of either one or more of SnO 2 and ZrO 2 , and from 0 to 12% of P 2 O 5 .
  • the glass preferably includes, in mass % on an oxide basis, from 58 to 74% of SiO 2 , from 5 to 30% of Al 2 O 3 , from 1 to 14% of Li 2 O, from 0 to 5% of Na 2 O, from 0 to 2% of K 2 O, from 0.5 to 12% in total of either one or more of SnO 2 and ZrO 2 , and from 0 to 6% of P 2 O 5 .
  • composition above it is more preferable to include from 2 to 14% of Li 2 O, and it is also more preferred that the total (Na 2 O+K 2 O) of the contents of Na 2 O and K 2 O is from 1 to 5%.
  • the glass includes, in mass % on an oxide basis, from 58 to 70% of SiO 2 , from 15 to 30% of Al 2 O 3 , from 2 to 10% of Li 2 O, from 0 to 5% of Na 2 O, from 0 to 2% of K 2 O, from 0.5 to 6% of SnO 2 , from 0.5 to 6% of ZrO 2 , and from 0 to 6% of P 2 O 5 and Na 2 O+K 2 O is from 1 to 5%.
  • the glass preferably includes, in mass % on an oxide basis, from 45 to 75% of SiO 2 , from 1 to 20% of Al 2 O 3 , from 10 to 25% of Li 2 O, from 0 to 12% of P 2 O 5 , from 0 to 15% of ZrO 2 , from 0 to 10% of Na 2 O, and from 0 to 5% of K 2 O.
  • SiO 2 is a component forming a network structure of the glass.
  • SiO 2 is a component enhancing the chemical durability, is a constituent component of a lithium aluminosilicate crystal, and is also a constituent component of a lithium silicate crystal.
  • the content of SiO 2 is 45% or more, preferably 50% or more, and more preferably 55% or more. In the case of increasing particularly the strength, the content of SiO 2 is preferably 58% or more, more preferably 60% or more, and still more preferably 64% or more. On the other hand, if the content of SiO 2 is too large, the meltability decreases significantly. Therefore, the content of SiO 2 is 74% or less, preferably 70% or less, more preferably 68% or less, and still more preferably 66% or less.
  • Al 2 O 3 is a component effective in increasing the surface compressive stress generated by chemical strengthening, and is essential.
  • Al 2 O 3 is a constituent component of a lithium aluminosilicate crystal.
  • the content of Al 2 O 3 is 1% or more, preferably 2% or more, more preferably 5% or more, and still more preferably 8% or more.
  • the content of Al 2 O 3 is more preferably 15% or more, and still more preferably 20% or more.
  • the content of Al 2 O 3 is 30% or less, and preferably 25% or less. In order to lower the forming temperature, the content of Al 2 O 3 is more preferably 20% or less, and still more preferably 15% or less.
  • Li 2 O is a component forming a surface compressive stress by the effect of ion exchange, is a constituent component of a lithium aluminosilicate crystal and a lithium silicate crystal, and is essential.
  • the content of Li 2 O is 1% or more, preferably 2% or more, more preferably 4% or more.
  • the content of Li 2 O is more preferably 10% or more, still more preferably 15% or more, and particularly preferably 20% or more.
  • the content of Li 2 O is preferably 25% or less, more preferably 22% or less, and still more preferably 20% or less.
  • the content of Li 2 O is preferably 14% or less, and in the case of precipitating a ⁇ -spodumene crystal, the content is preferably 10% or less, more preferably 8% or less, and still more preferably 6% or less.
  • the content ratio Li 2 O/Al 2 O 3 of Li 2 O and Al 2 O 3 is preferably 0.3 or less, because the transparency is improved.
  • Na 2 O is a component improving the meltability of the glass.
  • the content of Na 2 O in the present crystallized glass is preferably 0.5% or more, and more preferably 1% or more. If the content of Na 2 O is too large, a lithium aluminosilicate crystal or lithium silicate crystal becomes difficult to be precipitated, or the chemical strengthening properties are deteriorated. Therefore, the content of Na 2 O in the present crystallized glass is preferably 15% or less, more preferably 12% or less, and still more preferably 10% or less. For precipitating a ⁇ -spodumene crystal, the content of Na 2 O is preferably 5% or less, more preferably 4% or less, and still more preferably 3% or less.
  • K 2 O is a component lowering the melting temperature of the glass and may be contained.
  • the content thereof is preferably 0.5% or more, and more preferably 1% or more.
  • the content of K 2 O is more preferably 1.5% or more, and still more preferably 2% or more.
  • the total content Na 2 O+K 2 O of Na 2 O and K 2 O is preferably 1% or more, and more preferably 2% or more.
  • the content of K 2 O is preferably 8% or less, more preferably 7% or less, still more preferably 6% or less, and particularly preferably 5% or less.
  • the content of K 2 O is preferably 2% or less.
  • the total content Na 2 O+K 2 O of Na 2 O and K 2 O is excessively large, there is a concern that the transparency may be deteriorated.
  • the total content is preferably 5% or less, more preferably 4% or less, and still more preferably 3% or less.
  • the content of K 2 O is preferably 4% or less, more preferably 3% or less, and particularly preferably 2% or less.
  • Both ZrO 2 and SnO 2 are not essential but are a component constituting a crystal nucleus at the time of crystallization treatment, and it is preferable to contain either one or more of these.
  • the total content SnO 2 +ZrO 2 of SnO 2 and ZrO 2 is preferably 0.5% or more, and more preferably 1% or more.
  • the total content is preferably 3% or more, more preferably 4% or more, still more preferably 5% or more, particularly preferably 6% or more, and most preferably 7% or more.
  • the content of ZrO 2 is preferably 1% or more, more preferably 2% or more, still more preferably 4% or more, particularly preferably 6% or more, and most preferably 7% or more.
  • the SnO 2 +ZrO 2 is preferably 15% or less, and more preferably 14% or less.
  • the total content is preferably 12% or less, more preferably 10% or less, still more preferably 9% or less, and particularly preferably 8% or less.
  • the content of SnO 2 is preferably 0.5% or more, more preferably 1% or more, and still more preferably 1.5% or more.
  • the content of SnO 2 is preferably 6% or less, because a defect due to an unmelted material is difficult to occur in the glass, and the content is more preferably 5% or less, still more preferably 4% or less.
  • SnO 2 is also a component enhancing the solarization resistance.
  • the content of SnO 2 is preferably 1% or more, and more preferably 1.5% or more.
  • the content of ZrO 2 is preferably 0.5% or more, more preferably 1% or more. In this case, if the content of ZrO 2 exceeds 6%, devitrification readily occurs during melting, and the quality of the chemically strengthened glass may be deteriorated.
  • the content of ZrO 2 is preferably 6% or less, more preferably 5% or less, and still more preferably 4% or less.
  • the ZrO 2 content is preferably 1% or more, more preferably 2% or more, still more preferably 4% or more, particularly preferably 6% or more, and most preferably 7% or more.
  • the content of ZrO 2 is preferably 15% or less, more preferably 14% or less, still more preferably 12% or less, and particularly preferably 11% or less.
  • the ratio SnO 2 /(SnO 2 +ZrO 2 ) of the SnO 2 amount to the total amount of the both is preferably 0.3 or more, more preferably 0.35 or more, and still more preferably 0.45 or more.
  • the SnO 2 /(SnO 2 +ZrO 2 ) is preferably 0.7 or less, more preferably 0.65 or less, and still more preferably 0.60 or less.
  • TiO 2 serves as a component forming a crystal nucleus of the crystallized glass and therefore may be contained.
  • the content thereof is preferably 0.1% or more, more preferably 0.15% or more, and still more preferably 0.2% or more.
  • the content of TiO 2 exceeds 5%, devitrification readily occurs during melting, and the quality of the chemically strengthened glass may be deteriorated. Therefore, the content is preferably 5% or less, more preferably 3% or less, and still more preferably 1.5% or less.
  • the content thereof is preferably 0.5% or more, more preferably 0.1% or more, still more preferably 2% or more, particularly preferably 3% or more, and most preferably 4% or more.
  • the content of TiO 2 exceeds 10%, devitrification readily occurs during melting, and the quality of the chemically strengthened glass may be deteriorated. Therefore, the content is preferably 10% or less, more preferably 8% or less, and still more preferably 6% or less.
  • Fe 2 O 3 is contained in glass and the glass contains TiO 2 , a composite called an ilmenite composite is formed, and yellow or brown coloring is likely to occur.
  • Fe 2 O 3 is normally contained as impurity in glass and therefore, in order to prevent coloring, the content of TiO 2 is preferably 1% or less, more preferably 0.5% or less, still more preferably 0.25% or less, and it is particularly preferable that the glass is substantially free of TiO 2 .
  • P 2 O 5 is not essential but has an effect of encouraging phase separation of the glass and promoting the crystallization and therefore, may be contained.
  • its content is preferably 0.1% or more, more preferably 0.5% or more, still more preferably 1% or more, and particularly preferably 2% or more.
  • the content of P 2 O 5 is more preferably 4% or more, still more preferably 5% or more, and particularly preferably 6% or more.
  • the content of P 2 O 5 is large, acid resistance is deteriorated.
  • the content of P 2 O 5 is 15% or less, preferably 14% or less, more preferably 12% or less, still more preferably 11% or less, yet still more preferably 10% or less, particularly preferably 8% or less, and most preferably 7% or less.
  • the content of P 2 O 5 is preferably 6% or less, more preferably 5% or less, still more preferably 4% or less, particularly preferably 3% or less, and most preferably 2% or less.
  • B 2 O 3 is a component enhancing the chipping resistance and meltability of the glass for chemical strengthening or the chemically strengthened glass and may be contained.
  • B 2 O 3 is not essential, in the case of containing B 2 O 3 , the content thereof is preferably 0.5% or more, more preferably 1% or more, still more preferably 2% or more, for enhancing the meltability.
  • the content of B 2 O 3 exceeds 5%, striae are generated during melting and the quality of the glass for chemical strengthening is easily deteriorated. Therefore, the content of B 2 O 3 is preferably 5% or less, more preferably 4% or less, still more preferably 3% or less, and particularly preferably 1% or less.
  • MgO is a component increasing the surface compressive stress of the chemically strengthened glass, is a component suppressing scattering of fragments upon breakage of the chemically strengthened glass, and may be contained.
  • its content is preferably 0.5% or more, and more preferably 1% or more.
  • the content of MgO is preferably 5% or less, more preferably 4% or less, and still more preferably 3% or less.
  • CaO is a component enhancing the meltability of the glass and may be contained so as to prevent devitrification during melting and enhance the meltability while suppressing a rise in the thermal expansion coefficient.
  • the content thereof is preferably 0.5% or more, and more preferably 1% or more.
  • the content of CaO is preferably 4% or less, more preferably 3% or less, and particularly preferably 2% or less.
  • SrO is a component enhancing the meltability of the glass, is also a component enhancing the refractive index of the glass to make the refractive index of the residual glass phase after crystallization close to the refractive index of the precipitated crystal, thereby improving the light transmittance of the crystallized glass. Therefore, SrO may be contained.
  • the content thereof is preferably 0.1% or more, more preferably 0.5% or more, and still more preferably 1% or more.
  • the content of SrO is preferably 3% or less, more preferably 2.5% or less, still more preferably 2% or less, and particularly preferably 1% or less.
  • BaO is a component enhancing the meltability of the glass, is also a component enhancing the refractive index of the glass to make the refractive index of the residual glass phase after crystallization close to the refractive index of the lithium aluminosilicate crystal phase, thereby improving the light transmittance of the crystallized glass. Therefore, BaO may be contained. In the case of containing BaO, the content thereof is preferably 0.1% or more, more preferably 0.5% or more, and still more preferably 1% or more. On the other hand, if the BaO content is too large, the ion exchange rate decreases. Accordingly, the content of BaO is preferably 3% or less, more preferably 2.5% or less, still more preferably 2% or less, and particularly preferably 1% or less.
  • ZnO is a component decreasing the thermal expansion coefficient of the glass and increasing the chemical durability, is also a component enhancing the refractive index of the glass to make the refractive index of the residual glass phase after crystallization close to the refractive index of the lithium aluminosilicate crystal phase, thereby improving the light transmittance of the crystallized glass. Therefore, ZnO may be contained. In the case of containing ZnO, the content thereof is preferably 0.5% or more, more preferably 1% or more, still more preferably 1.5% or more, and particularly preferably 2% or more. On the other hand, for suppressing devitrification during melting, the content of ZnO is preferably 4% or less, more preferably 3% or less, and still more preferably 2% or less.
  • Y 2 O 3 , La 2 O 3 , Nb 2 O 5 and Ta 2 O 5 are effective in preventing fragments from scattering upon breakage of the glass and may be contained so as to increase the refractive index.
  • the total Y 2 O 3 +La 2 O 3 +Nb 2 O 5 of the contents of Y 2 O 3 , La 2 O 3 and Nb 2 O 5 is preferably 0.5% or more, more preferably 1% or more, still more preferably 1.5% or more, and particularly preferably 2% or more.
  • Y 2 O 3 +La 2 O 3 +Nb 2 O 5 is preferably 4% or less, more preferably 3% or less, still more preferably 2% or less, and particularly preferably 1% or less.
  • the total content Y 2 O 3 +La 2 O 3 +Nb 2 O 5 +Ta 2 O 5 of Y 2 O 3 , La 2 O 3 , Nb 2 O 5 and Ta 2 O 5 is preferably 0.5% or more, more preferably 1% or more, still more preferably 1.5% or more, and particularly preferably 2% or more. Furthermore, for the reason that the glass is less likely to devitrify during melting, Y 2 O 3 +La 2 O 3 ⁇ Nb 2 O 5 +Ta 2 O 5 is preferably 4% or less, more preferably 3% or less, still more preferably 2% or less, and particularly preferably 1% or less.
  • CeO 2 may be contained. CeO 2 is effective in oxidizing glass. In the case of containing a large amount of SnO 2 , CeO 2 may inhibit SnO 2 from being reduced to SnO that is a coloring component, thereby suppressing coloring. In the case of containing CeO 2 , the content thereof is preferably 0.03% or more, more preferably 0.05% or more, and still more preferably 0.07% or more. In the case of using CeO 2 as an oxidizer, if the content of CeO 2 is too large, the glass is readily colored. Therefore, for enhancing the transparency, the content of CeO 2 is preferably 1.5% or less, and more preferably 1.0% or less.
  • coloring component may be added.
  • coloring components include Co 3 O 4 , MnO 2 , Fe 2 O 3 , NiO, CuO, Cr 2 O 3 , V 2 O 5 , Bi 2 O 3 , SeO 2 , Er 2 O 3 , and Nd 2 O 3 .
  • the content of the coloring components is preferably 1% or less in total. In the case of increasing the light transmittance of the glass, it is preferable that the glass is substantially free of these components.
  • SO 3 a chloride, a fluoride, etc. may be appropriately contained as a refining agent at the time of glass melting. It is preferable not to contain As 2 O 3 . In the case of containing Sb 2 O 3 , the content thereof is preferably 0.3% or less, more preferably 0.1% or less, and most preferably nil.
  • the production method of a glass for chemical strengthening of this embodiment is a production method of a glass for chemical strengthening including heating and crystallizing an amorphous glass and bend-forming the resulting present crystallized glass under heating.
  • the present three-dimensionally shaped glass can be produced by the production method of a glass for chemical strengthening of the present invention.
  • the production method of a chemically strengthened glass of this embodiment is a production method of a chemically strengthened glass including heating and crystallizing an amorphous glass, bend-forming the resulting present crystallized glass under heating, and thereafter chemically strengthening the glass.
  • the three-dimensionally shaped chemically strengthened glass of this embodiment is obtained by the production method of a chemically strengthened glass of this embodiment.
  • the amorphous glass can be produced, for example, by the following method. Note that the following production method is an example of producing a sheet-like chemically strengthened glass.
  • Glass raw materials are prepared to obtain a glass having a desired composition, and heated and melted in a glass melting furnace. After that, the molten glass is homogenized by bubbling, stirring, addition of a refining agent, etc., then formed into a glass sheet with a predetermined thickness by a known forming method, and annealed. Alternatively, the molten glass may be formed into a sheet by a method in which the molten glass is formed into a block, annealed, and then cut.
  • Examples of the forming method of the sheet-like glass include a float process, a press process, a fusion process, and a down draw process. Particularly in the case of producing a large-size glass sheet, a float process is preferred. In addition, a continuously forming method other than a float process, for example, a fusion process or a down draw process, is also preferred.
  • a crystallized glass is obtained by heat-treating the amorphous glass obtained by the procedure above.
  • the heating treatment is preferably a two-step heating treatment in which the temperature is raised from room temperature to a first treatment temperature, followed by holding for a given time, and then raised to a second treatment temperature higher than the first treatment temperature, followed by holding for a given time.
  • the heating treatment is also preferably a three-step heating treatment in which the temperature is raised from room temperature to a first treatment temperature, followed by holding for a given time, then raised to a second treatment temperature higher than the first treatment temperature, followed by holding for a given time, and further raised to a third treatment temperature higher than the second treatment temperature, followed by holding for a given time.
  • the first treatment temperature is preferably within a temperature range at which the crystal nucleation rate increases in the glass composition
  • the second treatment temperature is preferably within a temperature range at which the crystal growth rate increases in the glass composition.
  • the holding time at the first treatment temperature is preferably long enough to produce a sufficient number of crystal nuclei. When a large number of crystal nuclei are produced, the size of each crystal is reduced and consequently a crystallized glass having high transparency is obtained.
  • the first treatment temperature is, for example, from 550 to 800° C.
  • the second treatment temperature is, for example, from 850 to 1,000° C.
  • the first treatment temperature is held for 2 to 10 hours, and the second treatment temperature is then held for 2 to 10 hours.
  • the crystallized glass obtained by the procedure above is ground and polished as necessary, to form a crystallized glass sheet.
  • cutting or chamfering is preferably performed before applying a chemical strengthening treatment, because a compressive stress layer is formed also on the end face by the later chemical strengthening treatment.
  • any method can be selected from existing bend-forming methods such as self-weight forming method, vacuum forming method and press forming method. Two or more kinds of bend-forming methods may be used in combination.
  • the self-weight forming method is a method in which a glass sheet is placed on a forming mold and the glass sheet is heated, then made to fit the forming mold by gravity to be bend-formed into a predetermined shape.
  • the vacuum forming method is a method in which a glass sheet is placed on a forming mold and after the periphery of the glass sheet is sealed, a space between the forming mold and the glass sheet is depressurized to apply a differential pressure between the front and back surfaces of the glass sheet so as to perform bend-forming. On this occasion, a pressure may be supplementarily applied to the upper surface side of the glass sheet.
  • the press forming is a method in which a glass sheet is placed between forming molds (upper mold and lower mold) and the glass sheet is heated and bend-formed into a predetermined shape by applying a press load between the upper and lower molds.
  • the glass is deformed by applying a force while the glass is heated.
  • the bend-forming (thermal bending) temperature is, for example, from 700 to 1,100° C., and preferably from 750 to 1,050° C.
  • the thermal bending temperature is preferably high relative to the maximum temperature of the crystallization treatment because thermal deformation readily occurs.
  • the difference between the maximum temperature of the crystallization treatment and the thermal bending temperature is preferably 10° C. or more, and more preferably 30° C. or more.
  • the difference between the maximum temperature of the crystallization treatment and the thermal bending temperature is preferably 120° C. or less, more preferably 100° C. or less, still more preferably 90° C. or less, and particularly preferably 60° C. or less.
  • the decrease of light transmittance by bend-forming is preferably 3% or less, more preferably 2% or less, still more preferably 1.5% or less, and particularly preferably 1% or less.
  • the light transmittance in terms of a thickness of 0.8 mm is preferably 85% or more, more preferably 87% or more, and particularly preferably 89% or more.
  • the chemical strengthening treatment is a treatment in which a glass is brought into contact with a metal salt by a method of, for example, immersing the glass in a metal salt (e.g., potassium nitrate) melt containing a metal ion having a large ionic radius (typically, Na ion or K ion), and a metal ion having a small ionic radius (typically Na ion or Li ion) in the glass is thereby replaced by a metal ion having a large ionic radius (typically Na ion or K ion for Li ion, and K ion for Na ion).
  • a metal salt e.g., potassium nitrate
  • Li—Na exchange of replacing Li ion in the glass by Na ion.
  • Na—K exchange of replacing Na ion in the glass by K ion.
  • Examples of the molten salt for performing the chemical strengthening treatment include a nitrate, a sulfate, a carbonate, and a chloride.
  • examples of the nitrate include lithium nitrate, sodium nitrate, potassium nitrate, cesium nitrate, and silver nitrate.
  • examples of the sulfates include lithium sulfate, sodium sulfate, potassium sulfate, cesium sulfate, and silver sulfate.
  • Examples of the carbonate include lithium carbonate, sodium carbonate, and potassium carbonate.
  • Examples of the chloride include lithium chloride, sodium chloride, potassium chloride, cesium chloride, and silver chloride.
  • One of these molten salts may be used alone, or a plurality of kinds thereof may be used in combination.
  • the treatment conditions such as time and temperature of the chemical strengthening treatment may be appropriately selected while taking into account the glass composition, the kind of molten salt, etc.
  • the present strengthened glass is preferably obtained, for example, by the following two-step chemical strengthening treatment.
  • the present three-dimensionally shaped glass is immersed in an Na ion-containing metal salt (e.g., sodium nitrate) at approximately from 350 to 500° C. for approximately from 0.1 to 10 hours.
  • an Na ion-containing metal salt e.g., sodium nitrate
  • This causes ion exchange between Li ion in the present three-dimensionally shaped glass and Na ion in the metal salt, and for example a compressive stress layer having a surface compressive stress of 200 MPa or more and a depth of compressive stress layer of 80 ⁇ m or more can thereby be formed.
  • the surface compressive stress introduced by this treatment exceeds 1,000 MPa, it is difficult to increase DOL while keeping CT low in the finally obtained present strengthened glass.
  • the surface compressive stress introduced by this treatment is preferably 900 MPa or less, more preferably 700 MPa or less, and still more preferably 600 MPa or less.
  • the glass after the treatment above is immersed in a K ion-containing metal salt (e.g., potassium nitrate) at approximately from 350 to 500° C. for approximately from 0.1 to 10 hours.
  • a K ion-containing metal salt e.g., potassium nitrate
  • a large compressive stress is consequently generated, for example, in a portion at a depth of about 10 ⁇ m or less of the compressive stress layer formed in the previous treatment.
  • the glass may be immersed in the K ion-containing metal salt after the glass is first immersed in the Na ion-containing metal salt and then held at 350 to 500° C. in the atmosphere for 1 to 5 hours.
  • the holding temperature is preferably from 425 to 475° C., and more preferably from 440 to 460° C.
  • Holding at a high temperature in the atmosphere allows Na ions introduced inside the glass from the metal salt by the first treatment to thermally diffuse in the glass, leading to formation of a more favorable stress profile.
  • the glass instead of holding in the atmosphere after immersion in an Na ion-containing metal salt, the glass may be immersed in a metal salt containing Na ion and Li ion (for example, a mixed salt of sodium nitrate and lithium nitrate) at 350 to 500° C. for 0.1 to 20 hours.
  • a metal salt containing Na ion and Li ion for example, a mixed salt of sodium nitrate and lithium nitrate
  • Immersion in the metal salt containing Na ion and Li ion causes ion exchange between Na ion in the glass and Li ion in the metal salt to form a more favorable stress profile, thereby improving the drop strength to asphalt.
  • the total treatment time is preferably 10 hours or less, more preferably 5 hours or less, and still more preferably 3 hours or less.
  • the total treatment time needs to be 0.5 hours or more, and more preferably 1 hour or more.
  • the three-dimensionally shaped chemically strengthened glass of the present embodiment obtained in the above-described manner is useful particularly as a cover glass used, for example, in a mobile device such as cell phone and smartphone.
  • the glass is also useful for a cover glass of a display device not intended to be portable, such as television, personal computer and touch panel.
  • the glass is also useful as a cover glass of, for example, an interior decoration of a car, an airplane, etc.
  • Glass raw materials of each of Glasses 1 to 8 were prepared to give a glass composition shown by mass % on an oxide basis in Table 1, and weighed so that 800 g of a glass can be obtained. Subsequently, the mixed glass raw materials were put in a platinum crucible, charged into an electric furnace at 1,500 to 1,700° C., melted for about 5 hours, degassed, and homogenized.
  • the obtained molten glass was cast into a mold, held for 1 hour at a temperature 30° C. higher than the glass transition point, and then cooled down to room temperature at a rate of 0.5° C./min to obtain a glass block.
  • the obtained glass block was processed into a sheet of approximately 60 mm ⁇ 60 mm ⁇ 1.5 mm and heat-treated under the conditions shown in Table 2 or 3 to obtain a crystallized glass (Ex. 1 to Ex. 14, and Ex. 16 to Ex. 19).
  • a crystallized glass (Ex. 1 to Ex. 14, and Ex. 16 to Ex. 19).
  • 750° C. 4 h is written in the upper stage
  • 920° C. 4 h is written in the lower stage
  • the obtained crystallized glass was evaluated for the density, Young's modulus, thermal expansion coefficient, precipitated crystal, Vickers hardness, fracture toughness value, light transmittance, and bend formability as follows.
  • chemical strengthening treatment was performed and the strengthening properties were evaluated. The results are shown in Table 2 or 3. The blank in the Table indicates unmeasured.
  • the density [unit: g/cm 3 ] was measured by the Archimedes method after processing by minor polishing into a thickness of 0.8 mm.
  • the Young's modulus [unit: GPa] was measured by an ultrasonic method after processing by mirror polishing into a thickness of 0.8 mm.
  • a thermal expansion curve was obtained using a thermal dilatometer (TD5000SA manufactured by Bruker AXS GmbH.) by setting the temperature rise rate at 10° C./min.
  • an average linear thermal expansion coefficient [unit: ⁇ 10 ⁇ 7 /° C.] at 50° C. to 350° C. was measured from the obtained thermal expansion curve.
  • Powder X-ray diffraction was measured under the following conditions to identify the precipitated crystal (main crystal).
  • crystallinity degree of crystallinity
  • crystal grain size crystal size [unit: nm] were calculated using a Rietveld method.
  • ⁇ SP stands for a ⁇ -spodumene crystal
  • P stands for a petalite crystal
  • LD stands for lithium disilicate
  • LS stands for lithium metasilicate
  • ⁇ Q stands for ⁇ -quartz.
  • Measurement apparatus SmartLab manufactured by Rigaku Corporation
  • an average transmittance (transmittance before forming, transmittance after forming) [unit: %] for light at a wavelength of 380 to 780 nm was measured before the later-described bend formability test and after the test with a configuration using, as a detector, an integrating sphere unit for a spectrophotometer (LAMBDA950 manufactured by PerkinElmer, Inc.), and the difference therebetween was also calculated.
  • the Vickers hardness was measured by pressing an indenter under a load of 100 gf for 15 seconds by use of a Shimadzu micro-Vickers hardness tester (HMV-2 manufactured by Shimadzu Corporation). Incidentally, the Vickers hardness was measured in the same manner also after the later-described chemical strengthening treatment (Vickers hardness before strengthening, Vickers hardness after strengthening).
  • a fracture toughness value after a chemical strengthening treatment was determined by an indentation fracture method (IF method) using a Vickers hardness tester (FLC-50V manufactured by Future-Tech Corp.). Indentation was performed under a load of 3 kgf in an atmosphere at a temperature of 22° C. and a relative humidity of 40%. The indentation length was measured in the same atmosphere 20 minutes after the indentation. Measurement was performed at 10 points for each sample, and an average value was calculated and taken as the fracture toughness value [unit: MPa ⁇ m 1/2 ].
  • a high alumina insulating firebrick (BAL-99 manufactured by Isolite Insulating Products Co., Ltd.) was processed to prepare two supporting bricks 1 and one loading brick 3 , each having a rod shape of 20 mm ⁇ 20 mm ⁇ 120 mm. Supporting bricks 1 were placed in parallel at an interval of 40 mm in an electric furnace, and the loading brick 3 was also placed in the same electric furnace, followed by preheating.
  • the obtained crystallized glass was processed into 60 mm ⁇ 10 mm ⁇ 0.8 mm, and both surfaces of 60 mm ⁇ 10 mm were mirror-polished.
  • the crystallized glass sheet 2 was put on two supporting bricks 1 , the loading brick 3 (weight: 85 g) was put on the crystallized glass sheet 2 , and these were held for 10 minutes. After the elapse of 10 minutes, the loading brick 3 was removed from the surface of the crystallized glass sheet 2 , and the crystallized glass sheet 2 was taken out from the electric furnace and cooled.
  • the deformation amount h (bend-deformation amount) of the crystallized glass, as illustrated in (b) of FIG. 6 , was measured.
  • “-” means that the glass was scarcely deformed and the deformation amount could not be measured.
  • preheating was performed at a temperature at which the crystallized glass has an equilibrium viscosity of about 10 18 Pa ⁇ s.
  • the deformation was performed by moving the convex mold downward at a temperature at which the crystallized glass has an equilibrium viscosity of about 10 11.5 Pa ⁇ s, followed by pressing the glass with 2,000 N at a maximum.
  • the crystallized glasses of all of Ex. 16 to Ex. 19 were formed into a three-dimensional shape having a curvature radius of 2,000 mm.
  • the obtained crystallized glass was subjected to a chemical strengthening treatment under the following conditions.
  • the glass was immersed in a molten salt of sodium nitrate at 450° C. for 30 minutes, then immersed in a molten salt of potassium nitrate at 450° C. for 30 minutes, thereby performing chemical strengthening.
  • the glass was immersed in a lithium sulfate-potassium sulfate mixed salt (in which the mass ratio between the lithium sulfate and potassium sulfate was 90:10) at 740° C. for 240 minutes, thereby performing chemical strengthening.
  • a lithium sulfate-potassium sulfate mixed salt in which the mass ratio between the lithium sulfate and potassium sulfate was 90:10
  • a stress value was measured using a surface stress meter FSM-6000 manufactured by Orihara Manufacturing Co., Ltd. and a measuring device SLP1000 utilizing scattered-light photoelasticity manufactured by Orihara Manufacturing Co., Ltd., and a compressive stress value CS [unit: MPa] on the glass surface, a depth DOL [unit: ⁇ m] at which the compressive stress value becomes zero, an internal tensile stress (CT) [unit: MPa], and a maximum depth (50 MPa depth) [unit: ⁇ m] at which the compressive stress value is 50 MPa or more, were read out.
  • CT internal tensile stress
  • m 1 represented by the following expression was determined from the depth DOL 1 at which the compressive stress value is CS/2.
  • m 2 represented by the following expression was determined from the compressive stress CS 1 at the depth DOL/4 and the compressive stress CS 2 at the depth DOL/2.
  • m 3 represented by the following expression was determined from the compressive stress CS 2 at the depth DOL/2.
  • a glass sheet composed of Glass 1 was bent at 1,000° C. in the same manner as in Ex. 1 and then crystallized under the same crystallization conditions as in Ex. 1. As a result, deformation was again caused, and the glass sheet retuned to the same flat sheet shape as the tray used for the crystallization treatment. This result indicates that the method of performing bend-forming after crystallization makes it easy to retain a desired shape.
  • Ex. 1 to Ex. 3 were crystallized glasses obtained by crystallizing glass sheets composed of Glass 1 under the same crystallization conditions, in which a ⁇ -spodumene crystal was the main crystal.
  • the bend-forming temperature must be appropriately adjusted.
  • Ex. 4 and Ex. 5 were the same as Ex. 1 except that the second treatment temperature in the two-step heating treatment (crystallization treatment) is low, and the change in transparency due to bending treatment was increased, compared with Ex. 1. It is thought that since crystallization before bending treatment was insufficient, the change in transmittance at the time of bending treatment was increased.
  • Ex. 6 to Ex. 8 were crystallized glasses obtained by crystallizing glass sheets composed of Glass 2 under the same crystallization conditions, in which a ⁇ -spodumene crystal was the main crystal.
  • Ex. 9 to Ex. 11 were crystallized glasses obtained by crystallizing glass sheets composed of Glass 3 under the same crystallization conditions, in which ⁇ -quartz was the main crystal.
  • Ex. 12 to Ex. 14 were crystallized glasses obtained by crystallizing glass sheets composed of Glass 4 under the same crystallization conditions, and were crystallized glasses containing a petalite crystal.
  • Ex. 12 When Ex. 12 is compared with Ex. 1 and Ex. 6, the amount of change by bend forming was large in Ex. 12 which was a crystallized glass containing a petalite crystal, and bending thereof was easy.
  • Ex. 16 to Ex. 19 were crystallized glasses obtained by crystallizing glass sheets composed of Glass 5 to Glass 8, respectively, and all were crystallized glasses containing a lithium metasilicate crystal.
  • a crystallized glass containing a lithium metasilicate crystal is characterized in that not only sufficiently high CS and DOL are obtained after chemical strengthening but also the transmittance before thermal bending is high. It is seen that when forming is performed at an appropriate bending temperature as in Ex. 16, a sufficiently large deformation amount is obtained and at the same time, the change in transparency can be suppressed.

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Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20200385301A1 (en) * 2017-11-30 2020-12-10 Corning Incorporated Systems and methods for vacuum-forming aspheric mirrors
CN112321162A (zh) * 2020-11-13 2021-02-05 重庆鑫景特种玻璃有限公司 蓝紫光低透过率玻璃陶瓷及其制备方法、玻璃制品
US20210155524A1 (en) * 2019-11-26 2021-05-27 Corning Incorporated 3d glass-ceramic articles and methods for making the same
US20220204389A1 (en) * 2020-12-31 2022-06-30 Cdgm Glass Co., Ltd. Microcrystalline glass, microcrystalline glass product and manufacturing method thereof
CN114790081A (zh) * 2021-01-25 2022-07-26 程珵 一种晶化玻璃原材及其制备方法和应用
US11505491B2 (en) 2020-09-04 2022-11-22 AGC Inc. Glass ceramic and chemically strengthened glass
US11643361B2 (en) * 2018-12-27 2023-05-09 Uti Inc. Method of increasing strength of glass substrate for optical filter and tempered-glass optical filter made thereby
WO2023082935A1 (fr) * 2021-11-11 2023-05-19 深圳旭安光学有限公司 Verre cristallin et verre cristallin renforcé et leurs procédés de préparation
EP4194416A1 (fr) 2021-12-10 2023-06-14 Schott Ag Plaque de recouvrement vitrocéramique, son procédé de fabrication ainsi que son utilisation et appareil d'affichage numérique comprenant une telle plaque de recouvrement
DE102021132738A1 (de) 2021-12-10 2023-06-15 Schott Ag Glaskeramische Deckscheibe, Verfahren zu deren Herstellung sowie deren Verwendung und digitales Anzeigegerät umfassend eine solche Deckscheibe
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WO2024109495A1 (fr) * 2022-11-22 2024-05-30 湖南旗滨新材料有限公司 Verre microcristallin 3d, son procédé de préparation et verre microcristallin pré-cristallisé
US12065376B2 (en) * 2021-02-26 2024-08-20 AGC Inc. Chemically strengthened glass and manufacturing method thereof
RU2826245C1 (ru) * 2020-12-31 2024-09-06 СиДиДжиЭм ГЛАСС КО., ЛТД Микрокристаллическое стекло, изделие из микрокристаллического стекла и способ их изготовления
EP4265573A4 (fr) * 2021-01-25 2024-09-11 Chongqing Aureavia Hi Tech Glass Co Ltd Vitrocéramique 3d, son procédé de préparation et son application
US12103397B2 (en) 2017-10-10 2024-10-01 Corning Incorporated Vehicle interior systems having a curved cover glass with improved reliability and methods for forming the same
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050143246A1 (en) * 2003-12-17 2005-06-30 Comte Marie J.M. Glass and glass-ceramic materials, articles and method of preparing the same
JP2010116315A (ja) * 2008-10-15 2010-05-27 Central Glass Co Ltd 結晶化ガラス
US20140134397A1 (en) * 2012-11-08 2014-05-15 Corning Incorporated Durable glass ceramic cover glass for electronic devices
WO2017179401A1 (fr) * 2016-04-14 2017-10-19 株式会社 オハラ Procédé de fabrication d'un élément en verre cristallisé ayant une forme incurvée

Family Cites Families (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61101434A (ja) * 1984-10-23 1986-05-20 Nippon Sheet Glass Co Ltd 透明結晶化ガラス
JPH0696460B2 (ja) * 1989-06-19 1994-11-30 日本板硝子株式会社 低膨張透明結晶化ガラス
US7000430B1 (en) * 1999-03-23 2006-02-21 Schott Ag Method of forming glass-ceramic parts and/or glass parts
JP3767260B2 (ja) 1999-08-02 2006-04-19 日本電気硝子株式会社 Ｌｉ２Ｏ−Ａｌ２Ｏ３−ＳｉＯ２系結晶化ガラス及び結晶性ガラス
JP2005053711A (ja) 2003-08-04 2005-03-03 Nippon Electric Glass Co Ltd Ｌｉ２Ｏ−Ａｌ２Ｏ３−ＳｉＯ２系結晶化ガラス及びその製造方法
US7727917B2 (en) 2003-10-24 2010-06-01 Schott Ag Lithia-alumina-silica containing glass compositions and glasses suitable for chemical tempering and articles made using the chemically tempered glass
US9586860B2 (en) * 2012-11-20 2017-03-07 Corning Incorporated Method of making three dimensional glass ceramic article
US9701573B2 (en) 2013-09-06 2017-07-11 Corning Incorporated High strength glass-ceramics having lithium disilicate and beta-spodumene structures
FR3020359B1 (fr) 2014-04-29 2016-05-06 Eurokera Plaque en verre partiellement cristallise
US9359243B2 (en) 2014-05-13 2016-06-07 Corning Incorporated Transparent glass-ceramic articles, glass-ceramic precursor glasses and methods for forming the same
EP3572384B1 (fr) 2014-10-08 2020-11-18 Corning Incorporated Vitrocéramiques haute résistance présentant des structures de pétalite et de silicate de lithium
US11267747B2 (en) 2015-03-24 2022-03-08 Corning Incorporated High strength, scratch resistant and transparent glass-based materials
TWI808058B (zh) 2016-06-24 2023-07-11 美商康寧公司 玻璃陶瓷、包含其之製品、及製造其之方法
CN110958992A (zh) * 2017-07-26 2020-04-03 Ａｇｃ株式会社 化学强化玻璃及其制造方法
WO2019105250A1 (fr) 2017-12-01 2019-06-06 成都光明光电股份有限公司 Vitrocéramique et substrat correspondant
WO2020018309A2 (fr) * 2018-07-16 2020-01-23 Corning Incorporated Articles en vitrocéramique à résistance accrue à la fracture et leurs procédés de production
WO2020097046A1 (fr) * 2018-11-05 2020-05-14 Corning Incorporated Procédés de fabrication d'articles tridimensionnels en vitrocéramique

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050143246A1 (en) * 2003-12-17 2005-06-30 Comte Marie J.M. Glass and glass-ceramic materials, articles and method of preparing the same
JP2010116315A (ja) * 2008-10-15 2010-05-27 Central Glass Co Ltd 結晶化ガラス
US20140134397A1 (en) * 2012-11-08 2014-05-15 Corning Incorporated Durable glass ceramic cover glass for electronic devices
WO2017179401A1 (fr) * 2016-04-14 2017-10-19 株式会社 オハラ Procédé de fabrication d'un élément en verre cristallisé ayant une forme incurvée

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CN112321162B (zh) * 2020-11-13 2023-05-30 重庆鑫景特种玻璃有限公司 蓝紫光低透过率玻璃陶瓷及其制备方法、玻璃制品
EP4197979A4 (fr) * 2020-12-31 2024-01-24 CDGM Glass Co., Ltd Verre microcristallin, produit de verre microcristallin et procédé de fabrication associé
US11548808B2 (en) * 2020-12-31 2023-01-10 Cdgm Glass Co., Ltd. Microcrystalline glass, microcrystalline glass product and manufacturing method thereof
WO2022142526A1 (fr) * 2020-12-31 2022-07-07 成都光明光电股份有限公司 Verre microcristallin, produit de verre microcristallin et procédé de fabrication associé
US20220204389A1 (en) * 2020-12-31 2022-06-30 Cdgm Glass Co., Ltd. Microcrystalline glass, microcrystalline glass product and manufacturing method thereof
RU2826245C1 (ru) * 2020-12-31 2024-09-06 СиДиДжиЭм ГЛАСС КО., ЛТД Микрокристаллическое стекло, изделие из микрокристаллического стекла и способ их изготовления
CN114790081A (zh) * 2021-01-25 2022-07-26 程珵 一种晶化玻璃原材及其制备方法和应用
EP4276077A4 (fr) * 2021-01-25 2024-09-25 Chongqing Aureavia Hi Tech Glass Co Ltd Matière première de verre cristallisée, procédé de préparation s'y rapportant et son utilisation
EP4265573A4 (fr) * 2021-01-25 2024-09-11 Chongqing Aureavia Hi Tech Glass Co Ltd Vitrocéramique 3d, son procédé de préparation et son application
EP4105187A4 (fr) * 2021-01-28 2024-01-24 CDGM Glass Co. Ltd. Verre microcristallin, et produit de verre microcristallin et procédé de fabrication associé
US12065376B2 (en) * 2021-02-26 2024-08-20 AGC Inc. Chemically strengthened glass and manufacturing method thereof
WO2023082935A1 (fr) * 2021-11-11 2023-05-19 深圳旭安光学有限公司 Verre cristallin et verre cristallin renforcé et leurs procédés de préparation
DE102021132738A1 (de) 2021-12-10 2023-06-15 Schott Ag Glaskeramische Deckscheibe, Verfahren zu deren Herstellung sowie deren Verwendung und digitales Anzeigegerät umfassend eine solche Deckscheibe
EP4194416A1 (fr) 2021-12-10 2023-06-14 Schott Ag Plaque de recouvrement vitrocéramique, son procédé de fabrication ainsi que son utilisation et appareil d'affichage numérique comprenant une telle plaque de recouvrement
WO2024109495A1 (fr) * 2022-11-22 2024-05-30 湖南旗滨新材料有限公司 Verre microcristallin 3d, son procédé de préparation et verre microcristallin pré-cristallisé
US12122236B2 (en) 2023-09-05 2024-10-22 Corning Incorporated Cold forming of complexly curved glass articles

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JP7537546B2 (ja) 2024-08-21
WO2019167850A1 (fr) 2019-09-06
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JP2023076759A (ja) 2023-06-01
US20220064054A1 (en) 2022-03-03
JPWO2019167850A1 (ja) 2021-02-04

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