WO2016152657A1 - 強化ガラス板の製造方法、ならびに強化用ガラス板の製造方法 - Google Patents
強化ガラス板の製造方法、ならびに強化用ガラス板の製造方法 Download PDFInfo
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- WO2016152657A1 WO2016152657A1 PCT/JP2016/058180 JP2016058180W WO2016152657A1 WO 2016152657 A1 WO2016152657 A1 WO 2016152657A1 JP 2016058180 W JP2016058180 W JP 2016058180W WO 2016152657 A1 WO2016152657 A1 WO 2016152657A1
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- tempered glass
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C21/00—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface
- C03C21/001—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions
- C03C21/002—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
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B27/00—Tempering or quenching glass products
- C03B27/02—Tempering or quenching glass products using liquid
- C03B27/03—Tempering or quenching glass products using liquid the liquid being a molten metal or a molten salt
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B33/00—Severing cooled glass
- C03B33/02—Cutting or splitting sheet glass or ribbons; Apparatus or machines therefor
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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
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
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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
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
- C03C17/23—Oxides
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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
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
- C03C17/23—Oxides
- C03C17/245—Oxides by deposition from the vapour phase
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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
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
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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
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
- C03C17/3417—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials all coatings being oxide coatings
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C21/00—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface
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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
- C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
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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
- 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
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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
- C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
- C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
- C03C3/087—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal containing calcium oxide, e.g. common sheet or container glass
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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
- C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
- C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
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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
- C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
- C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
- C03C3/093—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium containing zinc or zirconium
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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
- C03C2217/00—Coatings on glass
- C03C2217/20—Materials for coating a single layer on glass
- C03C2217/21—Oxides
- C03C2217/212—TiO2
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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
- C03C2217/00—Coatings on glass
- C03C2217/20—Materials for coating a single layer on glass
- C03C2217/21—Oxides
- C03C2217/214—Al2O3
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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
- C03C2217/00—Coatings on glass
- C03C2217/20—Materials for coating a single layer on glass
- C03C2217/21—Oxides
- C03C2217/215—In2O3
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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
- C03C2217/00—Coatings on glass
- C03C2217/20—Materials for coating a single layer on glass
- C03C2217/21—Oxides
- C03C2217/216—ZnO
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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
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/15—Deposition methods from the vapour phase
- C03C2218/154—Deposition methods from the vapour phase by sputtering
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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
- C03C2218/00—Methods for coating glass
- C03C2218/30—Aspects of methods for coating glass not covered above
- C03C2218/355—Temporary coating
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/50—Glass production, e.g. reusing waste heat during processing or shaping
- Y02P40/57—Improving the yield, e-g- reduction of reject rates
Definitions
- the present invention relates to a method for producing a tempered glass plate, and more specifically to a method for producing a tempered glass plate chemically strengthened by an ion exchange method.
- a tempered glass plate that has been chemically strengthened as a cover glass has been used for touch panel displays mounted on electronic devices such as smartphones and tablet PCs.
- Such a tempered glass plate is generally produced by chemically treating a glass plate containing an alkali metal as a composition with a tempering solution to form a compressive stress layer on the surface. Since such a tempered glass plate has a compressive stress layer on the main surface, the impact resistance to the main surface is improved. On the other hand, a tensile stress layer is formed inside such a tempered glass plate corresponding to the compressive stress layer on the main surface. And the damage (what is called self-destruction) by the crack of an end surface developing resulting from this tensile stress became a problem. Further, when the compressive stress layer is formed shallow on the entire glass plate so as to reduce such tensile stress, there is a problem that sufficient impact resistance cannot be obtained at the end face.
- Patent Document 1 the depth of the compressive stress layer on the main surface is reduced without reducing the compressive stress layer on the end surface by previously forming a film on the main surface and suppressing the progress of chemical strengthening from the end surface.
- a technique for controlling internal tension to reduce internal tensile stress is disclosed.
- Cited Document 1 discloses a tempered glass in which the balance between the compressive stresses of the main surface and the end face is appropriately set, a method for efficiently producing the tempered glass has not been sufficiently studied, and there is room for improvement. was there.
- the present invention has been made in view of such circumstances, and it is an object of the present invention to be able to efficiently manufacture a tempered glass sheet that hardly causes self-destruction and has high impact resistance at the end face.
- the method for producing a tempered glass plate of the present invention is a method for producing a tempered glass plate tempered using an ion exchange method, and the surface of the original glass plate is covered with an ion permeation suppression film that inhibits permeation of alkali metal ions.
- the film-forming glass plate is obtained, and after the film-forming step, the ion permeation suppressing film is coated by applying at least one of cutting, drilling, and end face processing to the film-coated glass plate.
- the balance between the tensile stress of the tempered glass sheet and the compressive stress of the end face can be easily adjusted suitably by performing a processing step such as cutting after the film forming step and before the strengthening step. Therefore, it is possible to efficiently produce a tempered glass plate having high impact resistance at the end face.
- the ion permeation suppression film at least one of a metal oxide film, a metal nitride film, a metal carbide film, a metal oxynitride film, a metal oxycarbide film, and a metal carbonitride film may be formed. preferable.
- SiO 2 , Al 2 O 3 , SiN, SiC, Al 2 O 3 , AlN, ZrO 2 , TiO 2 , Ta 2 O 5 , Nb 2 O 5 , HfO 2 , SnO 2 are used as the ion permeation suppressing film. It is preferable to form a film layer containing at least one of the above.
- an inorganic film having a composition containing 60 to 96% SiO 2 and 4 to 40% Al 2 O 3 by mass% is formed as an ion permeation suppression film so as to have a thickness of 5 to 300 nm. It is preferable.
- the film forming step it is preferable to form an inorganic film having a composition containing 99% or more of SiO 2 by mass as the ion permeation suppression film.
- an ion permeation suppression film having a high ion permeation suppression effect and strength can be formed with a relatively inexpensive material.
- the film forming step it is preferable to form the ion permeation suppression film so as to have a thickness of 20 to 150 nm.
- the Young's modulus of the ion permeation suppression film is preferably 0.5 to 2.0 times that of the original glass plate.
- the function of the antireflection film can be obtained in the ion permeation suppression film.
- the strengthening step it is preferable to immerse the strengthening glass plate in a molten potassium nitrate at 350 to 500 ° C. for 2 to 24 hours.
- the original glass plate contains, as a glass composition, mass%, SiO 2 45 to 75%, Al 2 O 3 1 to 30%, Na 2 O 0 to 20%, K 2 O 0 to 20%, and thickness 0 It is preferably 0.01 to 1.5 mm.
- the easily peelable film is preferably an inorganic film containing at least one of In 2 O 3 and ZnO.
- the ion permeation suppression film can be easily peeled off without using a solvent that is highly toxic to the human body such as HF.
- the remaining ion permeation suppression film can be used as a functional film such as an antireflection film.
- the method for producing a strengthening glass plate according to the present invention is a method for producing a strengthening glass plate that is subjected to a strengthening treatment using an ion exchange method, and is an ion that suppresses permeation of alkali metal ions on the surface of the original glass plate.
- a processing step of forming an exposed portion that is not covered with the ion permeation suppression film in the film-coated glass plate is a method for producing a strengthening glass plate that is subjected to a strengthening treatment using an ion exchange method, and is an ion that suppresses permeation of alkali metal ions on the surface of the original glass plate.
- FIGS. 1A to 1E are diagrams showing an example of a method for producing a strengthened glass sheet and a strengthening glass sheet according to an embodiment of the present invention.
- the tempered glass sheets G4 and G5 of the present embodiment have an end face that reduces the internal tensile stress because the balance between the compressive stress value of the main surface and the compressive stress value of the end face is suitably controlled in the manufacturing process. High resistance to impact on The details will be described below.
- the preparation step is a step of preparing the original glass plate G1.
- the original glass plate G1 is a glass that can be tempered using an ion exchange method.
- the original glass plate G1 preferably contains SiO 2 45 to 75%, Al 2 O 3 1 to 30%, Na 2 O 0 to 20%, K 2 O 0 to 20% by mass% as a glass composition. . If the glass composition range is regulated as described above, it becomes easy to achieve both ion exchange performance and devitrification resistance at a high level.
- the original glass plate G1 has a thickness of, for example, 1.5 mm or less, preferably 1.3 mm or less, 1.1 mm or less, 1.0 mm or less, 0.8 mm or less, 0.7 mm or less, 0.6 mm or less, It is 0.5 mm or less, 0.4 mm or less, 0.3 mm or less, 0.2 mm or less, especially 0.1 mm or less.
- the thickness of the original glass plate G1 is preferably 0.01 mm or more.
- the dimensions of the original glass plate G1 are, for example, 480 ⁇ 320 mm to 3350 ⁇ 3950 mm.
- the original glass plate G1 is preferably formed using an overflow downdraw method, and its main surface S is not polished. If it is the original glass plate G1 shape
- the original glass plate G1 may be formed using a float process, and the main surface S may be polished.
- the film forming step is a step of obtaining the glass plate with film G2 by forming the ion permeation suppressing film M on the surface of the original glass plate G1.
- the ion permeation suppression film M is a film layer that suppresses permeation of alkali metal ions on the surface of the original glass plate G1 in the later-described strengthening step.
- the material of the ion permeation suppression film M any material may be used as long as the permeation of alkali metal ions can be suppressed. However, the mechanical strength and chemical durability which are not easily damaged in the processing process and the strengthening process described later. It is preferable to have.
- the Young's modulus of the ion permeation suppression film M is preferably 0.5 to 2.0 times the Young's modulus of the original glass plate G1. When the Young's modulus of the ion permeation suppression film M is 0.5 times or more of the Young's modulus of the original glass plate G1, the original glass plate G1 can be sufficiently protected in a processing step or the like, and defects such as scratches are hardly generated.
- the ion permeation suppression film M is preferably a metal oxide, metal nitride, metal carbide, metal oxynitride, metal oxycarbide, metal carbonitride film, or the like.
- the material of the ion permeation suppression film M is SiO 2 , Al 2 O 3 , SiN, SiC, Al 2 O 3 , AlN, ZrO 2 , TiO 2 , Ta 2 O 5 , Nb 2 O 5 , HfO 2.
- a film containing one or more of SnO 2 can be obtained.
- the ion permeation suppression film M preferably satisfies the following formula (1) when the refractive index of the ion permeation suppression film M at a wavelength of 550 nm is n1 and the refractive index of the original glass plate G1 at a wavelength of 550 nm is n2. . n1-n2 ⁇ 0.4 (1)
- n1 and n2 more preferably satisfy the following formula (2), more preferably satisfy the following formula (3), and most preferably satisfy the following formula (4).
- the antireflection effect can be imparted to the ion permeation suppression film M by setting the refractive index n1 of the ion permeation suppression film M to a predetermined range or less with reference to the refractive index n2 of the original glass plate G1.
- the refractive index of the ion permeation suppression film M is about 1.52, whereas the refractive index of SiO 2 is about 1.46. Therefore, if SiO 2 is the main component of the ion permeation suppression film M, the refractive index of the ion permeation suppression film M can be easily made smaller than the refractive index of the original glass plate G1, and a function as an antireflection film can be easily imparted.
- the ion permeation suppression film M may be a film made of only SiO 2 .
- the ion permeation suppression film M may have a composition containing 99% or more of SiO 2 by mass. With such a composition, the ion permeation suppression film M can be formed easily and inexpensively. If in this manner the SiO 2 as a main component of the ion permeation suppressive film M, to enhance the ion permeability inhibiting effect, from the viewpoint of obtaining a high mechanical strength, in addition to SiO 2, the Young's modulus than SiO 2 is high any It is preferable to add these additives.
- additives include Al 2 O 3 , SiN, SiC, Al 2 O 3 , AlN, ZrO 2 , TiO 2 , Ta 2 O 5 , Nb 2 O 5 , HfO 2 , and SnO 2.
- Al 2 O 3 having a relatively low refractive index.
- the ion permeation suppression film M is an inorganic film containing SiO 2 as a main component and Al 2 O 3
- the ion permeation suppression film M contains 60% to 96% SiO 2 and 4 to 40% Al 2 O 3 in terms of mass% as a composition.
- the content of SiO 2 is preferably 60 to 96% by mass%, more preferably 65 to 90%, and still more preferably 70 to 85%.
- the content of SiO 2 is 60% or more, an antireflection effect is easily obtained.
- the strength of the original glass plate G1 hardly varies in the strengthening process, and the strength quality of the product is easily improved.
- the content of SiO 2 is 96% or less, the mechanical strength of the ion permeation suppression film M is increased and it is difficult to damage in the manufacturing process.
- the addition amount of Al 2 O 3 is preferably 4 to 40%.
- the content of Al 2 O 3 is 4% or more, it becomes easy to obtain an effect of suppressing ion permeation and an effect of improving mechanical strength and chemical resistance.
- the content of Al 2 O 3 is 40% or less, the permeation of alkali metal ions is not excessively inhibited, and the productivity in the strengthening process is improved.
- the ion permeation suppression film M having the above composition With the ion permeation suppression film M having the above composition, a desired ion permeation suppression effect, mechanical strength, and chemical resistance can be obtained with a relatively thin film thickness. Accordingly, it is possible to improve the production efficiency of the tempered glass sheet by shortening the film formation time of the ion permeation suppression film M or reducing the film material cost.
- the thickness of the ion permeation suppression film M is preferably 5 to 300 nm, more preferably 20 to 200 nm, still more preferably 20 to 150 nm, 40 to 120 nm, and most preferably 80 to 100 nm.
- the thickness of the ion permeation suppression film M is 5 nm or more, the permeation of alkali metal ions can be sufficiently suppressed.
- the thickness of the ion permeation suppression film M is 300 nm or less, the permeation of alkali metal ions is not excessively inhibited, and a sufficiently strong tempered glass plate can be easily obtained.
- the thickness of the ion permeation suppression film M is 20 to 150 nm, high resistance can be obtained for any of the following multiple modes (modes).
- modes A sharp protrusion exists at the tip of the drop, and the protrusion breaks through the surface compressive stress layer of the tempered glass and reaches the internal tensile stress layer. The first mode to break.
- a second mode in which the crack is developed and damaged by acting on the surface.
- a third mode in which an impact force acts on the end face of the tempered glass and breaks due to the development of minute cracks on the end face.
- the optical film thickness (refractive index ⁇ physical film thickness) of the ion permeation suppression film M is set to 1/4 of the visible light wavelength. It is preferable to do.
- the optical film thickness of the ion permeation suppression film M is preferably 95 nm to 195 nm, and more preferably 130 nm to 160 nm.
- the film formation method of the ion permeation suppression film M is a PVD method (physical vapor deposition method) such as a sputtering method or a vacuum evaporation method, a CVD method (chemical vapor deposition method) such as a thermal CVD method or a plasma CVD method, dip coating, etc.
- a wet coating method such as a method or a slit coating method can be used.
- a sputtering method and a dip coating method are preferable.
- the sputtering method is used, the ion permeation suppression film M can be easily and uniformly formed.
- the dip coating method is used, the ion permeation suppression film M can be simultaneously formed on both the main surfaces of the glass plate with high productivity.
- the processing step shown in FIG. 1C is performed.
- the glass plate G2 with film is subjected to at least one of cutting processing, end surface processing, and drilling processing, and the reinforcing glass plate G3 having the exposed portion E that is not covered with the ion permeation suppression film M is obtained. It is a process to obtain. That is, the processing applied to the film-coated glass plate G2 may be one processing selected from cutting processing, end surface processing, or drilling processing, or two or more processing selected from these processing. It may be.
- the glass plate G3 for reinforcement is obtained by cutting the glass plate G2 with film as shown in FIG. 1C.
- a scribe line is formed on the planned cutting line of the film-coated glass plate G2 using a scribe chip, and the glass plate for strengthening G3 is obtained by cleaving along the scribe line.
- the main surface S of the strengthening glass plate G3 is still covered with the ion permeation suppression film M.
- the end surface of the reinforcing glass plate G3 is an exposed portion E that is not covered with the ion permeation suppression film M.
- a scribe line may be formed on the film-coated glass plate G2 using laser light, or fusing may be performed using laser light.
- the film-coated glass plate G2 may be mechanically cut using a tool such as a wire saw, or may be melted by partial etching using hydrofluoric acid.
- the exposed portion E may be formed by performing end face processing or the like. Specifically, the exposed portion E may be formed by pressing a processing tool such as a rotating grindstone or a polishing tape against the end face to perform grinding or polishing. Moreover, you may etch the end surface of the glass plate G2 with a film
- holes where the speakers, cameras, earphone jacks, switches, connectors, and the like are arranged may be drilled in the film-coated glass plate G2.
- the drilling process may be performed by, for example, machining using a drill or the like, or may be performed by partial dissolution by laser light, etching, or the like.
- the inner peripheral surface of the formed hole becomes the exposed portion E (not shown).
- the strengthening step is a step of obtaining a strengthened glass plate G4 with a film by chemically strengthening the strengthening glass plate G3 by an ion exchange method. Specifically, the strengthening glass plate G3 is immersed in a strengthening solution T of molten potassium nitrate at 350 to 500 ° C. for 2 to 24 hours.
- the tempering step sodium ions on the surface of the reinforcing glass plate G3 and potassium ions in the reinforcing liquid T are exchanged to obtain a tempered glass plate G4 having a compressive stress layer C on the surface.
- ion exchange is suppressed in the portion (main surface S) where the ion permeation suppression film M is provided compared to the exposed portion E where the surface of the original glass plate G1 is exposed. Therefore, the depth of the compressive stress layer is reduced.
- the ion exchange can proceed more easily than the portion where the ion permeation suppression film M is provided, and the depth of the compressive stress layer is increased.
- the depth of the compressive stress layer on the main surface of the tempered glass sheet G4 is smaller than that of the end surface, the internal tensile stress is smaller and higher at the end than the tempered glass reinforced entirely. Has impact resistance. Therefore, the damage resulting from the progress of the crack from the end can be suitably suppressed.
- the ion permeation suppression film M when the above-described inorganic composition material is adopted as the ion permeation suppression film M, even if it is immersed in the reinforcing liquid T with the film provided, it is reinforced compared to a conventional organic protective film or the like. It is difficult to deteriorate the liquid T.
- the processing conditions such as the processing temperature and immersion time in the tempering step may be appropriately determined according to the characteristics required for the tempered glass sheet G4.
- the processing conditions are preferably adjusted so that the depth of the compressive stress layer on the main surface S of the tempered glass sheet G4 is smaller than the depth of the compressive stress layer on the exposed portion E.
- the tempered glass plate G4 can be used as a product as it is, but the ion permeation suppression film M is peeled off depending on the application. You may do it. In the peeling process shown in FIG. 1E, the ion permeation suppression film M is peeled from the tempered glass plate G4 to obtain a tempered glass plate G5.
- the ion permeation suppression film M is removed by attaching an etching solution to the tempered glass plate G4.
- an etching solution to the tempered glass plate G4.
- the ion permeation suppression film M is a film containing SiO 2
- a solution containing fluorine, TMAH, EDP, KOH, or the like can be used as an etchant, and a hydrofluoric acid solution is particularly preferably used as an etchant.
- the peeling step only the ion permeation suppression film M on one main surface side may be removed, or the ion permeation suppression films M on both main surfaces may be removed. Further, the ion permeation suppression film M may be partially removed from each main surface, or the ion permeation suppression film M may be entirely removed.
- the etching solution is partially attached using a spray, roll, brush, etc., or the tempered glass plate G4 is partially masked to make the etching solution.
- the film can be removed by immersion.
- the entire tempered glass plate G4 When removing all of the ion permeation suppression film M, the entire tempered glass plate G4 may be immersed in an etching solution. Thus, if the tempered glass board G4 whole is immersed in etching liquid, the tempered glass board G5 which further reduced the intensity
- the end face can be easily set as the exposed portion E in the processing step, and the tempered glass sheet G4 is less damaged from the end face.
- G5 can be manufactured efficiently.
- the original glass plate G1 can be protected with high mechanical strength and chemical durability while suitably suppressing the permeation of alkali metal ions with a very thin film thickness. Therefore, the tempered glass plates G4 and G5 can be efficiently manufactured with high productivity.
- the surface of the strengthening glass plate G3 obtained in the manufacturing process of the above-described strengthening glass plates G4 and G5 is protected by the ion permeation suppression film M, for example, the film forming process and the strengthening process exist far apart. This can prevent damage during transportation.
- the strengthening process of the strengthening process can be performed as it is without stripping the ion permeation suppression film M, there is an advantage that it is not necessary to strip the protective film before the strengthening process.
- the material of the ion permeation suppression film M described above is an example, and any material may be used as long as it is a film capable of suppressing permeation of alkali metal ions.
- the glass plate Before and after each of the above-described preparation process, film formation process, processing process, strengthening process, and peeling process, the glass plate may be appropriately washed and dried.
- any one of cutting, end face processing, and drilling processing may be performed on the reinforcing glass plate.
- the film forming step and the strengthening step may be performed in a state where the processed surface (end surface) of the reinforcing glass plate is masked with, for example, a resin.
- the case where the single-layer ion permeation suppression film M is provided in the film formation process has been described as an example.
- a plurality of film layers having different characteristics including the ion permeation suppression film M are provided on the main surface S. May be.
- a step of providing an easily peelable film between the ion permeation suppression film and the main surface S may be further provided (not shown).
- the easily peelable film is an inorganic film containing, for example, at least one of In 2 O 3 and ZnO.
- An easily peelable film containing In 2 O 3 or ZnO can be easily peeled with an acidic etching solution such as hydrochloric acid.
- the easily peelable film containing ZnO can be easily peeled off with an alkaline etching solution such as potassium hydroxide.
- an alkaline etching solution such as potassium hydroxide.
- the easily peelable film can be formed by any method such as sputtering, CVD, dip coating, spin coating, or spray coating.
- Nos. 1 to 3 represent examples of the present invention, and No. 4 represents a comparative example.
- the glass composition contains glass so as to contain 61.6% SiO 2 , 19.6% Al 2 O 3 , 0.8% B 2 O 3 , 16% Na 2 O, and 2% K 2 O by mass%.
- the raw materials were mixed and melted, and molded using an overflow downdraw method to obtain a plurality of original glass plates having a thickness of 0.4 mm.
- an ion permeation suppression film having the composition and thickness shown in Table 1 was formed on the original glass plate obtained above using a sputtering method, and then cut into a rectangular shape having a size of 65 ⁇ 130 mm by scribing. A reinforcing glass plate having an exposed portion was obtained.
- the surface compressive stress value CS1 and the surface stress depth DOL1 were calculated by observing the number of interference fringes and their intervals with a stress meter (FSM-6000 manufactured by Orihara Seisakusho).
- the internal tensile stress CT was calculated based on the following equation (5) using the surface compressive stress value CS1 and the surface stress depth DOL1.
- CT (CS1 ⁇ DOL1) / (t ⁇ 2DOL1) (5) t: thickness of glass sample (mm)
- the end face stress depth DOL2 was separately measured by the following method. Specifically, each of the above samples was sliced in a direction perpendicular to the main surface to prepare a cross-sectional sample having a thickness of 200 ⁇ m. Thereafter, the depth of the compressive stress layer on the end face of each cross-sectional sample was observed and measured using a polarizing microscope (WPA-micro manufactured by Photonic Lattice Co., Ltd.). For comparison, the surface stress depth was measured as DOL3 by the same method.
- WPA-micro manufactured by Photonic Lattice Co., Ltd.
- the membrane Young's modulus E1 is the Young's modulus of the ion permeation suppression membrane.
- the mass ratio of each component in the membrane composition, the known density of each component, and the known Young's modulus of each component are used to express the following formulas (6) to (8): ).
- 1 / E1 ⁇ SiO2 / E SiO2 + ⁇ Al2O3 / E Al2O3 ...
- SiO2 SiO 2 ratio by volume ⁇ Al2O3: Al 2 O 3 volume ratio
- SiO2 ( WSiO2 / dSiO2 ) / ( WSiO2 / dSiO2 + WAl2O3 / dAl2O3 )
- 2 Al2O3 ( WAl2O3 / dAl2O3 ) / ( WSiO2 / dSiO2 + WAl2O3 / dAl2O3 )
- W SiO2 SiO 2 mass ratio in the film composition
- W Al2O3 mass ratio of Al 2 O 3 in the film composition
- d Al2 O3 density of Al 2 O 3 (
- the glass plate Young's modulus E2 is the Young's modulus of the original glass plate and is a value measured using a resonance method.
- the reflectance is a value obtained by measuring the single-sided reflectance of each tempered glass plate sample at a wavelength of 550 nm using a microspectrophotometer (Olympus USPM-RUIII).
- Film refractive index n1 a value obtained by measuring the refractive index of the ion permeation suppression film of each sample at a wavelength of 550 nm using a microspectrophotometer (Olympus USPM-RUIII).
- the glass plate refractive index n2 is a value obtained by measuring the refractive index of the original glass plate at a wavelength of 550 nm using a microspectrophotometer (USPM-RUIII manufactured by Olympus).
- sample No. Nos. 1 to 3 are formed by strengthening the ion permeation suppression film on the main surface and having an exposed portion on the end surface, so that the end surface has the same level of compressive stress as that of the sample of the comparative example.
- Compressive stress is comparative sample No. It is smaller than 4. That is, sample no. In Nos. 1 to 3, the balance of compressive stress is easily and suitably set. As a result, the internal tensile stress is reduced, self-destruction is unlikely to occur, and high impact resistance is obtained at the end face. It is done.
- FIGS. 2 to 4 are views showing resistance to breakage in different modes of the tempered glass according to the embodiment of the present invention.
- Example No. A plurality of tempered glass samples having different ion permeation suppression film thicknesses were prepared in the same manner as in Example 1. Specifically, a plurality of samples having film thicknesses of 0 nm, 80 nm, 100 nm, 150 nm, 200 nm, and 300 nm were prepared, and a breakage test corresponding to the first to third modes described above was performed. Specifically, a falling ball test using 100th sandpaper, a falling ball test using 320th sandpaper, and an end impact test were performed.
- the falling ball test using 100th sandpaper is a test that assumes damage in the first mode described above. Specifically, on a base made of granite, a tempered glass having a size of 50 mm in length and 50 mm in width, a sandpaper with a 15 mm square size and 100th sandpaper (the sandpaper is arranged so that the rubbing surface contacts the tempered glass) Arranged in order, a 4 g steel ball was dropped onto a sandpaper from a height of 5 cm, and an evaluation was made based on whether or not a breaking fracture occurred. Thirty samples were tested for each film thickness described above, and the probability of non-breakage was determined from the number of samples that did not break apart. The sandpaper was replaced with a new one for each sample.
- FIG. 2 is a diagram showing the results of a falling ball test using 100th sandpaper.
- the horizontal axis indicates the thickness of the ion permeation suppression film
- the vertical axis indicates the non-breakage probability. According to FIG. 2, it is shown that the greater the thickness of the ion permeation suppression film, the higher the non-breakage probability and the less the damage is caused in the first mode.
- the falling ball test using 320th sandpaper is a test assuming damage in the second mode described above. Specifically, on a base made of SUS surface plate, an acrylic plate with a thickness of 30 mm, a sandpaper of number 320 with a 15 mm square size (sandpaper is placed so that the rubbing surface is in contact with the tempered glass), 50 mm long ⁇ Laminated glass in the order of 50mm width tempered glass and acrylic plate with 4mm thickness, dropped 130g steel ball on the acrylic plate placed on the top, and measured the height at which the tempered glass breaks It is a thing.
- breakage height The height obtained (hereinafter referred to as breakage height) was determined as an average value. In addition, when it did not divide even if it cracked, it was judged that it broke when the crack which entered into the perpendicular direction reached the depth more than half of board thickness.
- FIG. 3 is a diagram showing the results of a falling ball test using 320th sandpaper.
- the horizontal axis indicates the thickness of the ion permeation suppression film
- the vertical axis indicates the height of breakage. According to FIG. 3, it is shown that the smaller the thickness of the ion permeation suppression film, the lower the falling height of the hard ball at the time of breakage, and it is difficult to break in the second mode.
- the end face impact test is a test that assumes damage in the third mode described above. Specifically, as described in Chinese Utility Model No. 2051414736, the head of the hammer member fixed so as to be swingable in the height direction at the handle side end is swung up and collided with the end face of the sample clamped in a horizontal posture. The height at which the sample breaks was measured. The length from the fulcrum of the hammer to the head was 500 mm, the arm weight was 225 g, and the head weight was 11.3 g.
- the hammer member was made to collide while raising the swing height in 1 cm increments, the swing height at which the sample was damaged was recorded, the damaged height was Weibull plotted, and the failure probability was 63%
- the height (hereinafter referred to as the swing-up height) was obtained as an average value.
- FIG. 4 is a diagram showing the results of the end face impact test.
- the horizontal axis indicates the thickness of the ion permeation suppression film
- the vertical axis indicates the swing-up height.
- high strength is shown in the range where the thickness of the ion permeation suppression film is greater than 0 nm and less than 300 nm, and those outside the range have lower end face strength than those within the range. ing.
- tempered glass for display covers of portable devices is not easily damaged in any of the first to third modes.
- the thickness of the ion permeation suppression film is in the range of 50 to 150 nm, more preferably 80 to 100 nm, it is preferable that any mode does not easily break.
- the tempered glass plate and the method for producing the same of the present invention are useful as a glass substrate used for a touch panel display and the like, and a method for producing the same.
Abstract
Description
n1-n2≦0.4 …(1)
n1-n2≦0.4 …(1)
ここで、n1とn2は、下記(2)式を満たすことがより好ましく、下記(3)式を満たすことがさらに好ましく、下記(4)式を満たすことが最も好ましい。
n1-n2≦0.2 …(2)
n1-n2≦0.1 …(3)
n1<n2 …(4)
このように、元ガラス板G1の屈折率n2を基準としてイオン透過抑制膜Mの屈折率n1を所定範囲以下とすることによって、イオン透過抑制膜Mに反射防止効果を付与できる。
(1)落下先に鋭利な突起物が存在し、その突起物が強化ガラスの表面圧縮応力層を突き破り内部引張応力層まで達することによりクラックが発生し、該クラックが内部引張応力によって進展して破損する第一のモード。
(2)落下先に鈍角な突起物が存在し、その突起物が、強化ガラスの表面圧縮応力層を貫通しない深さでクラックを形成するとともに、圧縮応力を超える大きさの引張応力を強化ガラス表面に作用させたことによって該クラックを進展させて破損する第二のモード。
(3)強化ガラスの端面へ衝撃力が作用し、端面の微小クラック等が進展することにより破損する第三のモード。
上記実施形態では、成膜工程において、単層のイオン透過抑制膜Mを設けた場合を一例として説明したが、主表面S上にはイオン透過抑制膜Mを含む特性の異なる膜層を複数設けても良い。例えば、イオン透過抑制膜と主表面Sとの間に易剥離性膜を設ける工程をさらに備えても良い(図示せず)。易剥離性膜は、例えば、In2O3およびZnOの少なくとも何れかを含有する無機膜である。In2O3やZnOを含む易剥離性膜は塩酸等の酸性エッチング液で容易に剥離可能である。また、ZnOを含む易剥離性膜は水酸化カリウム等のアルカリ性エッチング液で容易に剥離できる。このような易剥離性膜を設けることによって、上述剥離工程において容易にイオン透過抑制膜Mを剥離できる。なお、易剥離性膜は、スパッタ法、CVD法、ディップコート法、スピンコート法、スプレーコート法等の任意の方法で形成可能である。
CT=(CS1×DOL1)/(t-2DOL1) …(5)
t:ガラス試料の厚み(mm)
1/E1=∨SiO2/ESiO2+∨Al2O3/EAl2O3 …(6)
∨SiO2:SiO2の体積比率
∨Al2O3:Al2O3の体積比率
ESiO2:SiO2のヤング率(=72 GPa)
EAl2O3:Al2O3のヤング率 (=380 GPa)
∨SiO2=(WSiO2/dSiO2)/(WSiO2/dSiO2+WAl2O3/dAl2O3) …(7)
∨Al2O3=(WAl2O3/dAl2O3)/(WSiO2/dSiO2+WAl2O3/dAl2O3)
…(8)
WSiO2:膜組成におけるSiO2の質量比
WAl2O3:膜組成におけるAl2O3の質量比
dSiO2:SiO2の密度(=2.65 g/cm3)
dAl2O3:Al2O3の密度(=3.95 g/cm3)
ガラス板屈折率n2は、顕微分光測定器(オリンパス社製USPM-RUIII)を用いて波長550nmにおける元ガラス板の屈折率を測定した値である。
G2 膜付ガラス板
G3 強化用ガラス板
G4、G5 強化ガラス板
M イオン透過抑制膜
E 露出部
Claims (14)
- イオン交換法を用いて強化された強化ガラス板の製造方法であって、
元ガラス板の表面をアルカリ金属イオンの透過を抑制するイオン透過抑制膜で被覆して膜付ガラス板を得る成膜工程と、
前記成膜工程の後に、切断加工、孔あけ加工、および端面加工の少なくとも何れかの加工を前記膜付ガラス板に施すことによって前記イオン透過抑制膜に被覆されない露出部を設けた強化用ガラス板を得る加工工程と、
前記加工工程の後に、強化用ガラス板をイオン交換法により化学強化して強化ガラス板を得る強化工程と、を備えることを特徴とする、強化ガラス板の製造方法。 - 前記成膜工程において、前記イオン透過抑制膜として、金属酸化物膜、金属窒化物膜、金属炭化物膜、金属酸窒化物膜、金属酸炭化物膜、金属炭窒化物膜の少なくとも何れかを形成することを特徴とする、請求項1に記載の強化ガラス板の製造方法。
- 前記成膜工程において、前記イオン透過抑制膜としてSiO2、Al2O3、SiN、SiC、Al2O3、AlN、ZrO2、TiO2、Ta2O5、Nb2O5、HfO2、SnO2の少なくとも何れかを含有する膜層を形成することを特徴とする、請求項2に記載の強化ガラス板の製造方法。
- 前記成膜工程において、前記イオン透過抑制膜として、質量%でSiO2を60~96%、Al2O3を4~40%含有する組成を有する無機膜を形成することを特徴とする、請求項3に記載の強化ガラス板の製造方法。
- 前記成膜工程において、前記イオン透過抑制膜として、質量%でSiO2を99%以上含有する組成を有する無機膜を形成することを特徴とする、請求項3に記載の強化ガラス板の製造方法。
- 前記成膜工程において、厚さが20~150nmとなるよう前記イオン透過抑制膜を形成する、請求項1~4の何れか1項に記載の強化ガラス板の製造方法。
- 前記イオン透過抑制膜のヤング率が、前記元ガラス板のヤング率の0.5~2.0倍であることを特徴とする、請求項1~6の何れか1項に記載の強化ガラス板の製造方法。
- 前記イオン透過抑制膜の屈折率をn1、前記元ガラス板の屈折率をn2とした場合に、下記(1)式を満たすことを特徴とする、請求項1~7の何れか1項に記載の強化ガラス板の製造方法。
n1-n2≦0.4 …(1) - 前記強化工程において、前記強化用ガラス板を350~500℃の硝酸カリウム溶融塩中に2~24間浸漬することを特徴とする、請求項1~8の何れか1項に記載の強化ガラス板の製造方法。
- 前記元ガラス板が、ガラス組成として質量%で、SiO2 45~75%、Al2O3 1~30%、Na2O 0~20%、K2O 0~20%を含有し、厚さ0.01~1.5mmであることを特徴とする、請求項1~9の何れか1項に記載の強化ガラス板の製造方法。
- 前記イオン透過抑制膜と元ガラス板との間に易剥離性膜を設ける工程をさらに備えることを特徴とする、請求項1~10の何れか1項に記載の強化ガラス板の製造方法。
- 前記易剥離性膜は、In2O3およびZnOの少なくとも何れかを含有する無機膜であることを特徴とする、請求項11に記載の強化ガラス板の製造方法。
- 前記強化工程の後に前記強化ガラス板の少なくとも一方主面から前記イオン透過抑制膜を剥離する剥離工程をさらに備えることを特徴とする、請求項1~12の何れか1項に記載の強化ガラス板の製造方法。
- イオン交換法を用いた強化処理に供される強化用ガラス板の製造方法であって、
元ガラス板の表面をアルカリ金属イオンの透過を抑制するイオン透過抑制膜で被覆して膜付ガラス板を得る成膜工程と、
前記成膜工程の後に、前記膜付ガラス板に対し、切断加工、孔あけ加工、および端面加工の少なくとも何れかの加工を施すことによって前記膜付ガラス板において前記イオン透過抑制膜に被覆されない露出部を形成する加工工程と、を備える強化用ガラス板の製造方法。
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WO2018066314A1 (ja) * | 2016-10-07 | 2018-04-12 | 日本電気硝子株式会社 | 強化ガラス板の製造方法、膜付ガラス板及び強化ガラス板 |
WO2018097096A1 (ja) * | 2016-11-22 | 2018-05-31 | 日本電気硝子株式会社 | 強化ガラス板、強化ガラス板の製造方法 |
WO2020262293A1 (ja) * | 2019-06-27 | 2020-12-30 | Agc株式会社 | 強化ガラス板およびその製造方法 |
WO2020262292A1 (ja) * | 2019-06-27 | 2020-12-30 | Agc株式会社 | 強化ガラス板およびその製造方法 |
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KR102493138B1 (ko) | 2023-01-30 |
KR20170129678A (ko) | 2017-11-27 |
TWI639569B (zh) | 2018-11-01 |
TW201704180A (zh) | 2017-02-01 |
US20180057400A1 (en) | 2018-03-01 |
JPWO2016152657A1 (ja) | 2018-01-11 |
US10723651B2 (en) | 2020-07-28 |
CN107108347A (zh) | 2017-08-29 |
CN107108347B (zh) | 2020-02-11 |
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